Eni S.p.A.

Exploration & Production Division

00342.HTP.PRC.PRG Rev.1 January 2005 Page 1 of 175

DESIGN CRITERIA

GAS SWEETENING PROCESSES

SELECTION CHARACTERISTICS AND CRITERIA

00342.HTP.PRC.PRG
Rev.1 January 2005

Eni S.p.A.
Exploration & Production Division

00342.HTP.PRC.PRG Rev.1 January 2005 Page 2 of 175

TABLE OF CONTENTS
1-SCOPE OF WORK: AIM OF SWEETENING

2- PROCESS CHOICE CRITERIA 2.1- Required depuration level and other possibile impurity 2.2- Delivery specifies and ecological discharge 2.3- Toxic problems 2.4- Corrosion allowance 2.5- Decision schemes and plant costs 3- CHEMICAL AND/OR PHYSICAL ABSORBING PROCESS FOR SOUR GAS SWEETENING 3.1- CHEMICAL ABSORBING WITH DEA AND MDEA SOLUTIONS 3.1.1- Physical and chemicals properties of amines 3.1.2- Absorbing mechanisms and regeneration 3.1.3- Column design 3.1.4- Other main items design 3.1.5- Construction materials 3.1.6- Foaming problems and amine loss 3.1.7- Classic absorbing scheme 3.1.8- Split-Flow scheme 3.1.9- Double stage Scheme 3.1.10- Plant simulations 3.2- SELEXOL PROCESS 3.2.1- Process description 3.2.2- Used schemes 3.2.3- Design and measuring criteria 3.2.4- Construction materials 3.3- SULFINOL PROCESS 3.2.1- Process description 3.2.2- Used schemes 3.2.3- Design and measuring criteria 3.2.4- Construction materials 4- OXIDATIVES PROCESS FOR SULPHIDRIC ACID OXIDATION 4.1- LO-CAT process 4.1.1- Plant schemes 4.2- Monterotondo process with biological oxidation 4.3- CLAUS process and variations 4.3.1- Process description, involved reactions and used catalysts 4.3.2- Items 4.3.3- Use and treatment of produced sulphur 4.3.4- Base scheme plant 4.3.5- Process variations 4.3.6- Construction materials 4.3.7- Further process development 5- CRYOGENIC PROCESS FOR CARBON DIOXIDE REDUCTION 5.1- RYAN-HOLMES process 5.2- CRYOFRAC process 5.2.1- Process description

Eni S.p.A.
Exploration & Production Division 5.2.2- Used schemes 5.2.3- Construction materials 5.3- RANDALL process 6- APPENDIX- UNEMPLOYED PROCESS 6.1- Not regenerative process 6.2- Chemical absorbing with alcaline carbonates 6.3- MEA and MEA-DEG solutions absorbing 6.4- Other process 7- GLOSSARY 8- BIBLIOGRAFY

00342.HTP.PRC.PRG Rev.1 January 2005 Page 3 of 175

Eni S.p.A.
Exploration & Production Division

00342.HTP.PRC.PRG Rev.1 January 2005 Page 4 of 175

1.

SCOPE OF THE WORK: AIMS OF SWEETENING

This document aims to improve the know-how of gas sweetening plant operators, to help them understand application limits and choose the most appropriate process for each specific application. The study is also part of the ongoing process to standardize the types of plants most frequently used by ENI E&P and its Subsidiaries. Sweetening natural gas and associated gas consists in removing sour gases such as H2S and CO2 from the gas stream. Sweetening is performed to obtain a product that does not cause safety or environment pollution problems when used. H2S is a highly toxic gas: exposure for a few minutes to just several hundred ppm of this gas can be fatal. During combustion the H2S contained in the natural gas transforms into SO2, a product which is just as toxic and which can be discharged into the atmosphere only in limited quantities. In cases where natural gas has a high sour gas content, sweetening is necessary also to avoid corrosion problems in the transport and distribution network. Sometimes the content has to be reduced to control the heat value and/or to make the gas produced interchangeable. A regeneration type sweetening plant releases all the absorbed H2S and CO2 during the regeneration stage; as , unlike , cannot be discharged into the atmosphere, it has to be conveyed to a recovery plant for transformation into elementary sulphur. Only in the case of very limited H2S rates is it possible to send the gas to an incinerator for transformation in SO2 before being discharged into the atmosphere. Sulphur recovery is of primary importance in gas sweetening processes both for environmental protection purposes and because it has an economic value: the sulphur recovered from the sour gases is one of the main supply sources for the chemical industry. Processes based on the Claus reaction are mainly used to recover sulphur from H2S. Finally, Tail Gas Clean Up plants which treat the gas discharged from sulphur recovery plants are worthy of mention: in short, these units greatly improve the sulphur recovery efficiency of Claus units, reducing the quantity of SO2 discharged into the atmosphere and further limiting the environmental impact of natural gas treatment systems.

Eni S.p.A.
Exploration & Production Division 2. 2.1. PROCESS SELECTION CRITERIA Purification Level

00342.HTP.PRC.PRG Rev.1 January 2005 Page 5 of 175

As mentioned above, natural gas can contain both H2S and CO2 or just one of these sour gases. In certain cases, even although H2S and CO2 are both present, the concentration of either of them may be considered acceptable for the sweet gas specification. The acceptable quantities of H2S and CO2 vary from country to country and can fall within the following ranges: - H2S 1.3 - 4 ppm Vol. - CO2 1-3 % Vol. In the case of Italian gas pipelines, the gas specifications are defined on a case by case basis and depending on local situations; for example, the tolerance is greater for a gas to be reinjected than for a gas to be transferred through a gas pipeline, while a non-sour gas transported through a pipeline can be accepted also with a higher CO2 content. Approximate limit values for impurities are: H2S CO2 Dew point of hydrocarbons Dew point of H2O 3 1.5 ppm Vol. % Vol.

-5°C at all pressures between 1 and 70 eff. bar -10°C at 70 eff. bar

The total accepted organic sulphur content is 150 mgr/m3 expressed as sulphur, of which a maximum of 15 mgr/m3 of mercaptans, expressed as sulphur. Other limits are the net heat value which must be 9100 Kcal/m3 +/- 5% and the Wobbe Index which must be between 11,500 and 12,500. While no exceptions to the maximum acceptable content of H2S are envisaged, the CO2 content is sometimes tolerated up to 3.0% Vol.; more conservative limits may be set for the H2S and organic sulphur content on a case by case basis. In the sweetening of synthesis gas the CO2 content must be reduced to 500 ppm Vol.; in the production of liquid gas the CO2 content must be reduced to 50-100 ppm to prevent liquefaction of the CO2. However, in the case of gas used for steam reforming or methanation, the maximum tolerated sulphur compound content is just 0.2 ppm Vol. Gas pipeline specifications do not indicate the maximum tolerable limits of HCN which are lower than 0.1 ppm for gas used in methanation or other processes such as steam reforming.

Eni S.p.A.
Exploration & Production Division

00342.HTP.PRC.PRG Rev.1 January 2005 Page 6 of 175

In the case of liquid gas production, the dew point of the water must drop to between -150°C and -160°C, while the dew point of hydrocarbons must be between -40°C and -50°C in all the pressure ranges between the maximum operating pressure and the atmospheric pressure. 2.1.1. Gas containing only CO2. Absorption processes in liquid phase generally allow the purification values specified to be achieved. The primary amines are able to reduce the CO2 content in the gas produced to partial pressures of around 10 mm H2O abs. The activated potassium carbonates can reduce CO2 partial pressure values in the treated gas to 200 mm H2O abs. If the absorption pressure is sufficiently high, physical solvents can also be used to achieve partial pressure values of around 1000 mm H2O abs. 2.1.2. Gas containing only H2O Amine solutions in water or organic solvents are able to reach the purity level required even at fairly low absorption pressures; see figure 4.2.1 for MEA solutions (20% weight) and figure 6.1.5 for other amines. A physical solution can be used if the gas to be treated is at a sufficiently high pressure. 2.1.3 Gas containing both H2S and CO2 If the gas contains both H2S and CO2, it is often useful to use a selective process for the H2S as this process will leave the amount of CO2 permitted by the specification in the treated gas. This will result in savings because a smaller rate of solution will be needed for absorption purposes. Selective processes that can be used are: oxidation in liquid phase, tertiary amines and physical or chemical-physical processes. At low pressure, oxidation processes in liquid phase such as STRETFORD, LOCAT and SULFINT can be used. However, STRETFORD will only tolerate a low CO2 content in the gas supplied. Selective amines such as methyldiethanolamine (MDEA) and diisopropanolamine (DIPA) can be used at medium pressures; EXXON has developed a selective wet process that uses stereo hindered amines which, as such, have the same selectivity characteristics as tertiary amines. Physical solvents such as SELEXOL, which are suitable at high pressures, can be used in plants designed ad hoc also to selectively absorb H2S. The selectivity of the physical solvents is based on the fact that the relative volatility of CO2 is very high compared to that of H2S. Primary and secondary amines can be used to obtain the specified purification value if the process does not need to be selective.

Eni S.p.A.
Exploration & Production Division

00342.HTP.PRC.PRG Rev.1 January 2005 Page 7 of 175

In figure 4.2.1 the operating pressure, the H2S/CO2 ratio in the crude gas to be treated and the H2S purification value that can be reached in gas scrubbed using an MDEA solution (20% weight) as absorbing medium are correlated. The curves are based on a consumption of steam for regeneration purposes of 120 Kg/m3 of solution; with a consumption of steam of 150 Kg/m3 of solution, the results of the purification can be up to 70% higher than the values shown. The use of MEA – DEG solutions in standard concentration (MEA 20% - DEG 75% - H2O 5%) can lead to an improvement in the purification result of 50% compared to the values indicated. The purification results that can be obtained with other amines are shown in figure 6.1.5. Note that, when high quantities of sour gas have to be absorbed, it is possible to use a process which offers a good result in terms of absorption (high pick-up), followed by a process able to achieve the required purification level, even with low pick-up. This procedure is used in the HI-PURE process: a solution of active potassium carbonate is used to absorb most of the sour gas (bulk removal); final absorption of the sour gas to just a few ppm, which is not economically viable with an active carbonate solution, is performed using an amine solution in a completely separate unit installed downstream of the active carbonate absorption unit. In this way the final result is a gas which fully respects the specifications using a lower total rate of absorbing solutions than what would have been needed if just one of the two procedures had been used. 2.2. Delivery specifications and environmental constraints of discharges It is important to remember that almost none of the solutions used in gas sweetening processes can be discharged directly into drains but must be treated at the very least in a biological system. Therefore, precautions must be taken when replacing or discharging absorbing solutions and specialized companies used for the disposal of non-biodegradable or harmful waste. The environmental problems of the various plants will now be discussed. 2.2.1. Absorption processes The effluent from these processes is a gas current containing all the sour gases that have been removed from the crude gas. If the sour gas contains H2S then a Claus sour gas treatment unit must be installed downstream of the sweetening plant to recover the elementary sulphur; in this case H2S rich currents (25% vol. min.) will have to be treated with a minimum potential of not less than 500 Kg/day. Oxidation processes should be applied in cases of sour gas potential of less than 500 Kg/day or in the case of very limited concentrations of H2S. If the H2S is present in the sour gas in extremely limited quantities, under current laws on atmospheric protection, it would be possible to convey the sour gas to an

Eni S.p.A.
Exploration & Production Division

00342.HTP.PRC.PRG Rev.1 January 2005 Page 8 of 175

incinerator which oxidizes the H2S to SO2 before being released into the atmosphere at a suitable height above ground level. However, a Claus unit with final incinerator will always be envisaged for the oxidation to SO2 of the residual sulphur compounds in the tail gas; an emergency flare is also needed to burn the sour gas should the Claus unit not be operational. 2.2.2. Oxidation processes Oxidation processes in liquid phase are able to offer high sulphur recovery factors with very low emissions. However, these processes are based on rather delicate oxidation-reduction reactions and secondary reactions which slowly degrade the solution. The production of the degradation must be constantly purged, creating ecological problems due to the toxicity of most of the solutions used in these processes. The new generation liquid phase oxidation processes (LO-CAT, SULFINT and to a certain extent also STRETFORD) use absorbing solutions which are not poisonous and which are in any case biodegradable so many of the barriers to the intensive development of these processes have been broken down. The sulphur produced in oxidation processes is generally of a much lower quality than that produced in the Claus units. Indeed, it is difficult to find a market outlet for it unless it is further purified. 2.2.3. Cryogenic processes Cryogenic processes, often used for the decarbonation of gas, do not pose environment related problems.

2.3.

Toxicity issues Due to the heightened awareness in recent times of safety and ecology related questions, some processes, while being very efficient, are rarely used or have been almost completely abandoned. Solution toxicity problems are encountered in the following processes: - processes which use active potassium carbonate with arsenite/arseniate. - processes which use potassium carbonate with organic activator and concentrated MEA (and sometimes DEA) processes: indeed the latter use vanadic anhydride or antimonium salts as a corrosion inhibitor. - oxidation processes that use Vanadium or Arsenic salts as oxygen carrier. Blowdowns of the solutions used in these processes are not biodegradable and can only be used in very small quantities in biological treatment systems and only for some processes.

Eni S.p.A.
Exploration & Production Division

00342.HTP.PRC.PRG Rev.1 January 2005 Page 9 of 175

The amines and solutions used in almost all the physical and chemical-physical processes are not easily biodegradable and cannot therefore be discharged into drains or treated biologically, except in very small quantities. The relatively high cost of the solutions and the related ecological problems mean that closed systems have to be installed in almost all sweetening processes which envisage absorption with water solutions to collect the continuous and discontinuous blowdown and recycle it in the operative units. 2.4. Corrosion and protection Corrosion problems are mainly encountered in wet absorption plants. Corrosion may be due in some parts of the plant to the action of wet CO2 and H2S, while stress-corrosion cracking phenomena may occur in other parts. The possibility of corrosion due to the acid attack of CO2 and H2S is common to all processes of this type. The processes which have created most corrosion problems are those which use active potassium carbonate or amine solutions in concentrations of more than 20%. Different corrosion phenomena have been observed in plants which use amine or potassium solutions depending on which amine was used, its concentration, the presence of degradation products or other impurities, the sour gas rate, as well as the temperature and velocity at which the solution flows through the equipment and pipes. The main cause of corrosion is the presence of sour gas such as CO2 and H2S in a water environment. Figure 2.4.1 shows the corrosion effect on MEA-DEG and MDEA solutions. It has generally been noted that corrosion takes place more rapidly in the presence of CO2 alone as this can form soluble iron salts at high temperature. Instead, the acid attack of generates insoluble salts which form a film which is not sufficiently thick to protect against further corrosion. Therefore, in the presence of small concentrations of H2S, the joint action of H2S and CO2 sometimes acts as a corrosion retardant. Besides sour gases, another important cause of corrosion are the products of the degradation of the amines which form due to irreversible reaction of the amine and certain impurities present in the gas to be treated. It has been noted that the products of the degradation of monoethonolamine are more corrosive than those of diethanolamine while corrosion phenomena are more limited in plants that use diisopropanolamine or methyldietanolamine. Corrosion is also favoured by erosion caused by suspended solids in the solution such as iron sulphide formed through the action of the H2S. Stress-corrosion typical of alkaline attack has sometimes been noted; these phenomena generally occur after the plants have been in operation for some years.

Eni S.p.A.
Exploration & Production Division

00342.HTP.PRC.PRG Rev.1 January 2005 Page 10 of 175

However, the situation which most often favours corrosion is the high concentration of acid gas along with high temperature. This situation generally occurs in the solution/solution exchanger in the high temperature zone, rich solution side and in the regenerator head. The regeneration column is also subject to corrosion above all in the head zone where the concentration of acid gas and the temperatures are higher. The boiler and head condenser, pipe side, where the process fluid normally flows, are also subject to a high risk of corrosion. Measures can be taken to reduce corrosion to acceptable limits for efficient management of the plant. The main criterion to follow is to use corrosion resistant materials instead of carbon steel in the areas most at risk of corrosion. 304 or 316 type stainless steel is the most commonly used material. The following equipment is usually made of corrosion resistant alloys: solution/solution exchanger, boiler, regenerator head condenser, some parts of the regeneration column and a portion of the piping. One measure which it is always advisable is to avoid zones in the exchangers with a very high wall temperature. This implies that very hot heating fluids should not be used in the boiler and that very high pressures should not be used in the regeneration process. It is also important to prevent oxygen, which provokes the degradation of the solution, from coming into contact with said solution. Therefore, blowdown collection tanks and solution storage tanks must be kept in an inert atmosphere. Special care must be taken to ensure that there are no suspended solids in the solution; filters must therefore be used. Another criterion for limiting corrosion is to use heavy metal based corrosion inhibitors such as Vanadium and Antimony. These corrosion inhibitors are used above all in plants where potassium carbonates and high concentration MEA and DEA solutions are used. Along with corrosion inhibitors there should be continuous control of the oxyreducing potential of the solution. There has been a growing tendency recently to subject all the carbon steel equipment and pipes that come into contact with amine solutions operating a high and low temperature to an annealing treatment. Recent studies have shown that, although this has not completely eliminated the stress-corrosion cracking phenomena, annealing has greatly reduced its statistical incidence.

Eni S.p.A.
Exploration & Production Division

00342.HTP.PRC.PRG Rev.1 January 2005 Page 11 of 175

Programmed inspections of equipment and pipes is recommended during annual plant shut-downs; however, common investigation techniques such as ultrasound and penetrating fluids are not always effective in highlighting corrosion; it is better to used magnetic particle type investigation systems with fluorescent fluids. In all cases where repairs have to be made, the welding must be annealed.

Eni S.p.A.
Exploration & Production Division

00342.HTP.PRC.PRG Rev.1 January 2005 Page 12 of 175

ACCIAIO AL CARBONIO

(A)

MEA 15% peso DEG 80% peso H2O 5% peso MDEA 50% peso

(B)

CORROSION PENETRATION- mm

CONTACT TIME - hours FIGURE 2.4.1 - CORROSION OF MEA/DEG AND MDEA SOLUTIONS

Eni S.p.A.
Exploration & Production Division 2.5. Decision-taking scheme and engineering costs

00342.HTP.PRC.PRG Rev.1 January 2005 Page 13 of 175

The sweetening processes considered have been applied in many plants and so the related problems are well-known. Plants which use dry adsorption processes generally cause fewer operating problems. Indeed, adsorption and regeneration cycles have been automated and so many installations now operate unmanned. Plants that use wet absorption processes are without doubt more common. These plants are easy to run although the condition of the circulating solution has to be kept under control. One operating problem is caused by the use of absorbing solution reclaiming systems. Another operative problem can be caused by the installation of a Claus unit downstream of the sweetening system even although nowadays reliable continuous analyzers are available which greatly simplify operations. The machines can incur normal maintenance problems; in chemical absorption plants the machines comprise pumps for the circulation of solution and condensate while in physical absorption plants besides pumps there are often compressors with the purpose of recycling part of the hydrocarbons released during regeneration of the solution or of extracting and recompressing the gases generated during the various flash stages. Wet oxidation plants are those which most often cause operating problems. Indeed, they are based on a very delicate chemism which therefore requires precise analytical control. They generally also entail the complex problem of the disposal of solution blowdowns and the extraction and purification of the sulphur produced. Plants which use non-regenerative processes are technologically simple plants which therefore cause no problems in normal operating conditions. However, it is not easy to remove and handle the rich adsorbent mass which must then be disposed. Case histories of cryogenic separation plants are too few to have statistics available about the operating problems. A typical operative problem of amine or activated carbonate absorption plants is the formation of foam, often due to the presence of liquid hydrocarbons in the circulating solution; the widespread presence of foams causes the choking-up of the absorption and regeneration columns which can result in uncontrollable entrainment of liquids by the gas. The risk of the solutions foaming can be reduced greatly by taking measures when designing the plants such as using scrubbing solutions at temperatures above dew point in hydrocarbons of the crude gas to be treated, suitably insulating the bottom

Eni S.p.A.
Exploration & Production Division

00342.HTP.PRC.PRG Rev.1 January 2005 Page 14 of 175

of the absorber, supercooling the crude gas to be treated and complete separation of liquids upstream of the acid gas absorption column. The use of activated carbon filters to retain liquid hydrocarbons or other surfactant substances completes the list of precautions to take. Economic evaluation of the investment and operating cost of a plant is the decisive criterion for the choice; this evaluation requires a specific study which takes into consideration the industrial context the plant will be built in. To choose the best solution a study should be made of the process as a whole in order to assess the engineering and operating costs of the alternatives chosen. The fundamental factor of the cost of an absorption plant is the rate of circulating fluid, while secondary cost factors include the operating pressure and the acid gas pick-up. The operating cost is sometimes affected by local situations which can change the economic viability of one process compared to others with investment costs varying by 10% to 30%. The results of a feasibility study carried out for different sweetening cases are given below for the sake of information. 2.6 2.6.1 Sweetening of gas containing only CO2. Case 1 – Average pressure Operating pressure incoming CO2 outgoing CO2 Cost factors of the utilities considered: Electrical energy Fuel gas (Kwh ) (1000 Kcal ) 2.1 1.0 40 eff. bar 43 % vol. 2 % vol.

Eni S.p.A.
Exploration & Production Division

00342.HTP.PRC.PRG Rev.1 January 2005 Page 15 of 175

Process

MEA Classical

MEA With additives 35 0.35 0.51 0.72 0.48

DGA

BENFIELD

Concentration sol. (% weight) Net pick-up (mol GA/mol sol.) Solution rate Investment Total cost of purification 2.6.2 Case 2 – High pressure Operating pressure incoming CO2 outgoing CO2

20 0.3 1 1 1

60 0.30 0.57 0.90 0.75

30 0.67 0.71 0.39

72 eff. bar 13 % vol. 1.4 % vol.

Cost factors of the utilities considered: Electrical energy Fuel gas Process Concentration of sol. (% weight) Circulating sol. (m3/h) Hourly cost of utilities Investment 2.6.3 Case 3 – High pressure Gas rate Operating pressure incoming CO2 outgoing CO2 Cost factors of the utilities considered: Steam Electrical energy Fuel gas Process (kg) (Kwh) (1000 Kcal) MEA 0.25 1.00 0.275 SULFINOL-D 93,000 Nm3/h 53 bar abs. 1.0 % vol. 0.005 % vol. (Kwh) (1000 Kcal) MEA 20 1 1 1 1.0 0.08 DEA 35 0.6 0.63 0.72 40 0.33/0.95 0.68 0.78 MDEA Two-stage

MOLECULAR SIEVE 1.87

Investment

1.0

0.925

Eni S.p.A.
Exploration & Production Division Total cost of purification 2.6.4 Case 4 – High pressure Gas rate Operating pressure incoming CO2 outgoing CO2 Cost factors of the utilities considered: Steam Electrical energy (Kg) (Kwh) 0.25 1.00 PHYSICAL 1.9 1.3 140,000 53 1.0 0.005 1.0 0.84

00342.HTP.PRC.PRG Rev.1 January 2005 Page 16 of 175

0.45

Nm3/h bar abs. % vol. % vol.

Process SULFINOL Investment 1.0 Total cost of purification 1.0 2.6.5 Case 5 – High pressure Gas rate Operating pressure incoming CO2 outgoing CO2 Process Circulation of sol. Consumption of electrical energy 2.6.6 Case 6 – High pressure Gas rate Operating pressure incoming CO2 outgoing CO2 Process Investment Circulation of sol. Steam consumption Total operating cost 2.6.7 Case 7 – High pressure DEA-SNEA 1 1 1 1 MDEA 1.10 0.75

292,000 100 12 1 SULFINOL-M 1 1

Nm3/h bar abs. % vol. % vol. SELEXOL 1.60 2.10

422,600 54 2.17 100

Nm3/h bar abs. % vol. ppm vol. activated MDEA 1.40 1.14 0.97 0.91

SULFINOL-D 1.08 1.24 0.90 1.07

Eni S.p.A.
Exploration & Production Division Gas rate Operating pressure incoming CO2 outgoing CO2 Process Investment 2.6.8 DEA-SNEA 1 417,700 54 1.0 100

00342.HTP.PRC.PRG Rev.1 January 2005 Page 17 of 175

Nm3/h bar abs. % vol. ppm vol.

SULFINOL-D 1.14

Sweetening of gas containing only H2S.

2.6.8.1 Case 1 – High pressure Operating pressure incoming H2S outgoing H2S Process Amine concentration (% weight) Circulation of solution Regeneration steam 2.6.8.2 Case 2 – Low pressure Operating pressure incoming H2S outgoing H2S Process Amine concentration (% weight) Circulation of solution Regeneration steam DEA 21 1 1 7 17 30 bar abs. % vol. ppm vol. DIPA 26.5 0.71 0.75 DIPA 53 0.48 0.61 DEA 21 1 1 81 1.5 10 bar abs. % vol. ppm vol. DIPA 26.5 0.71 0.76 DIPA 53 0.44 0.58

2.6.9

Sweetening of gas containing both CO2 and H2S

2.6.9.1 Case 1 – High pressure Operating pressure incoming CO2 outgoing CO2 incoming H2S outgoing H2S Cost factors considered 82 5.0 1.5 0.1 1.5 bar abs. % vol. % vol. % vol. ppm vol.

Eni S.p.A.
Exploration & Production Division Electrical energy Fuel gas Process Solution rate Investment Total cost of purification 2.6.9.2 Case 2 – Average pressure Operating pressure incoming CO2 outgoing CO2 incoming H2S outgoing H2S Process Concentration weight) Net pick-up (mol/mol amine) Solution rate Consumption of regeneration steam Investment 2.6.10 (% DEA 25 40 10 0.5 5 400 bar abs. % vol. % vol. % vol. ppm vol. (Kwh) (1000 Kcal) 2.1 1

00342.HTP.PRC.PRG Rev.1 January 2005 Page 18 of 175

SELEXOL 1 1 1

SULFINOL 0.89 0.87 0.35

DGA 60

SULFINOL-D 45

0.67 1 1 1

0.26 1.06 2.03 1

0.44 1.06 0.62 1

Sweetening of gas containing CO2 with re-injection of CO2 Refer to figures 2.6.1, 2.6.2 and 2.6.3 taken from Hydrocarbon Processing, May 1982, “Pick treatment for high CO2 removal” by C.S. Goddin, which show energy consumption and operating costs for the decarbonation of streams with a variable CO2 content, taking into consideration the cost of different utilities. The diagrams have been prepared assuming the following operating parameters: Pressure of crude gas Pressure of sweetened gas Pressure of produced CO2 CO2 incoming supply CO2 in outgoing sweet gas H2S incoming supply H2S in outgoing sweet gas H2S in the CO2 produced 19 eff. bar 43 eff. bar 30 eff. bar variable 1.5 % vol. variable from 0.1 to 0.2 % vol. 1.5 ppm vol. 100 ppm vol.

It has been envisaged that the gas arriving from cryogenic treatment and from the membranes is brought into line with the specification by means of sweetening with DEA. Investment costs of the various processes:

Eni S.p.A.
Exploration & Production Division

00342.HTP.PRC.PRG Rev.1 January 2005 Page 19 of 175

%CO2 in the crude gas 20 40 60 80 90

DEA 1 1 1 1 1

CRYOGENIC 1.67 1.27 1.10 0.78 0.71

MEMBRANES 1.01 0.91 0.70 0.58

In figures 2.6.2 and 2.6.3 the operating cost of the final CO2 sweetening using a DEA solution must be added to the operating cost of the alternatives with cryogenic plant and membranes; the cost of the alternative with DEA, as indicated, includes the final sweetening of the CO2.

Eni S.p.A.
Exploration & Production Division

00342.HTP.PRC.PRG Rev.1 January 2005 Page 20 of 175

ENERGY REQUIRED – kcal/ Nm3 of CO2

CRIOGENICO MEMBRANE

CO2 IN THE GAS TO BE TREATED - % molar

Eni S.p.A.
Exploration & Production Division

00342.HTP.PRC.PRG Rev.1 January 2005 Page 21 of 175

FIGURE 2.6.1 –CO2 CONTENT / PURIFICATION ENERGY

Eni S.p.A.
Exploration & Production Division

00342.HTP.PRC.PRG Rev.1 January 2005 Page 22 of 175

GAS COMBUSTIBILE GAS LIQUEFATTO ENERGIA ELETTRICA

30 Lire/Kcal 35 Lire/Kcal 65 Lire/Kcal

OPERATING COST – Lire/1000 Nm3 CO2

MEMBRANE CRIOGENICO

ADDOLCIMENTO FINALE CO2

CO2 IN THE GAS TO BE TREATED - % molar FIGURE 2.6.2 – CO2 CONTENT / OPERATING COST

Eni S.p.A.
Exploration & Production Division

00342.HTP.PRC.PRG Rev.1 January 2005 Page 23 of 175

GAS COMBUSTIBILE GAS LIQUEFATTO ENERGIA ELETTRICA

10 Lire/Kcal 25 Lire/Kcal 65 Lire/Kcal

OPERATING COST – Lire/1000 Nm3 CO2

CRIOGENICO

MEMBRANE

ADDOLCIMENTO FINALE CO2

CO2 IN THE GAS TO BE TREATED - % molar FIGURE 2.6.3 – CO2 CONTENT / OPERATING COST

Eni S.p.A.
Exploration & Production Division 3.

00342.HTP.PRC.PRG Rev.1 January 2005 Page 24 of 175

CHEMICAL AND/OR PHYSICAL ABSORPTION PROCESSES FOR ACID GAS SWEETENING Chemical absorption with DEA and MDEA solutions Physical and chemical properties of amine Processes which use amine solutions have been applied in the chemical, petrochemical and natural gas treatment industries for many decades and have been greatly improved over the years; indeed they are now the most commonly used processes in all possible fields of application such as natural gas and associated gas, purification of synthesis gas, purification of refinery gas, production of technical gas etc.. The growing impact of ecological problems and the development of Claus tail gas treatment units have encouraged the study of selective amines and the development of increasingly interesting processes also from the point of view of operative consumption. At present there are different amine processes on the market which allow for an extremely targeted choice of solution also for very specific problems. All the processes listed are currently used more or less intensively; some specific characteristics of amine processes are indicated in to tables 3.1.1 – 3.1.2 – 3.1.3 and 3.1.4.

3.1 3.1.1

3.1.1.1 Diethanolamine (DEA) Free process, commonly used in refineries. DEA is an averagely reactive, poorly selective secondary amine suitable for absorbing acid gases at a pressure of a few atm. It is not decomposed by COS and CS2. It partially absorbs mercaptans and organic sulphur. SNEA holds a patent for the use of concentrated solutions on the basis of experience on a very large scale at Lacq in France. With this process it is possible to push the pick-up to the maximum compatible with the driving force; more accurate filtering is sufficient to avoid corrosion and remove the products of the degradation of the solution. There is another Union Carbide process (AMINE GUARD-ST)which uses additives also for DEA that allow more economic performance in the sweetening of gas containing both H2S and CO2 by using solutions with a concentration up to 55% in weight.

3.1.1.2 Methyldiethanolamine (MDEA)

Eni S.p.A.
Exploration & Production Division

00342.HTP.PRC.PRG Rev.1 January 2005 Page 25 of 175

Free process, with the possibility of using the patented experience of SNEA, Union Carbide, Parsons, Exxon etc.. Highly selective tertiary amine suitable for absorbing low pressure acid gases; it allows 40–60% of the CO2 contained in the crude gas to be treated not to be absorbed while it absorbs H2S to a few ppm for gas at a pressure of 80 eff. bar It does not absorb but is not degraded by CO2. It partially absorbs mercaptans and organic sulphur. The variant “ACTIVATED MDEA” produced by BASF uses MDEA at 48% weight added in a two-stage plant with flash (also vacuum) of the rich solution. This process is able to greatly limit the consumption of regeneration heat, suitable for the absorption of large quantities of CO2. However, the activator is not used in the case of selective absorption. Another variant (Union Carbide’s UCARSOL, HS/CO2/H2S process) uses MDEA with a concentration of 24% weight in a patented absorber with plates designed to increase selectivity.

Eni S.p.A.
Exploration & Production Division

00342.HTP.PRC.PRG Rev.1 January 2005 Page 26 of 175

PROCESS TYPICAL CONCENTRATION (% weight) SELECTIVITY H2S ON CO2 ABSORPTION FACTOR CO2 MOLECULAR WEIGHT (Kg/Kmol) CORROSION LIMIT (mol AG/mol amine) TYPICAL PICK-UP (mol AG/mol amine) TYPICAL PICK-UP (Nm3 AG/m3 solution) HEAT OF H2S REACTION (Kcal/Nm3) HEAT OF CO2 REACTION (Kcal/Nm3) STEAM FOR REGENERATION (Kg/m3 solution) BOILING POINT AT ATM PRESSURE (C°) SOLUBILITY OF HYDROCARBONS IN AMINE SOLUBILITY OF AMINE IN HYDROCARBONS TABLE 3.1.1 –

DEA 20÷40 LOW 40 105.14 > 0.8 0.5÷0.85 22÷73 432 714 100÷130 268 1 1

MDEA 25÷55 HIGH 10 119.17 0.8 0.1÷0.8 5÷83 370 671 100 247 <1 /

CHARACTERISTICS OF AMINE PROCESSES (SHEET 1 OF 2)

Eni S.p.A.
Exploration & Production Division

00342.HTP.PRC.PRG Rev.1 January 2005 Page 27 of 175

PROCESS DEA SOLUBILITY OF AMINE IN WATER (% at 20°C) 96.4 OPTIMAL OPERATING PRESSURE (abs. bar) >8 FREEZING POINT (°C) 0 NEED FOR RECLAIMING NO RECLAIMING TEMPERATURE (°C) / THERMAL EXCHANGE COEFFICIENT FACTOR AT 65°C 0.87 BOILING CONC./TEMP. AT 1.8 ata (% weight / °C) 21/118 FREEZING CONC./TEMP. (% weight / °C) 21/-5 VISCOSITY FACTOR 1.3 COST OF PURE AMINE FACTOR 1 COST OF THE SOLUTION AT STANDARD 1.4 CONCENTRATION FACTOR EMPIRICAL FORMULA OF AMINE NC4H11O2 TABLE 3.1.1 –

MDEA 100 ALL < -40 NO / 0.85 24/118 24/-6 1.06 2.5 4.0 NC5H13O2

CHARACTERISTICS OF AMINE PROCESSES (SHEET 2 OF 2)

Eni S.p.A.
Exploration & Production Division

00342.HTP.PRC.PRG Rev.1 January 2005 Page 28 of 175

TABLE 3.1.2 – STRUCTURAL FORMULAS OF AMINE

Eni S.p.A.
Exploration & Production Division

00342.HTP.PRC.PRG Rev.1 January 2005 Page 29 of 175

PROCESS

DEA

CONCENTRATION (% weight)

26

40°C (mol CO2 / mol amine) 40°C (Nm3 CO2 / m3 amine)

0.39

31

PROCESS

DEA

CONCENTRATION (% weight)

40

50°C (mol CO2 / mol amine) 50°C (Nm3 CO2 / m3 amine)

0.31

51

TABLE 3.1.3 – THEORETICAL PARTIAL PRESSURE

PICK-UP (85% EQUILIBRIUM) OF CO2 EQUAL TO 1 PSIA

WITH

Eni S.p.A.
Exploration & Production Division

00342.HTP.PRC.PRG Rev.1 January 2005 Page 30 of 175

PROCESS

MDEA

DEA – SNEA

AMINE CONCENTRATION (% weight)

44 – 55

30 – 35

LEAN SOLUTION (mol acid gas/mol amine)

0.004

0.016

PICK-UP OF RICH SOLUTION (mol acid gas/mol amine) STEAM AT BOILER (Kg/m3 solution)

0.1 – 0.9

0.7 – 1.1

100

120

PROCESS

MDEA

MDEA

MDEA

AMINE CONCENTRATION (% weight)

50

50

50

STEAM AT BOILER (Kg/m3 solution)

80

100

120

LEAN SOLUTION (mol acid gas/mol amine)

0.006

0.004

0.003

TABLE 3.1.4 – REGENERATION OF MDEA AND DEA – SNEA

Eni S.p.A.
Exploration & Production Division 3.1.2 Absorption and regeneration mechanisms

00342.HTP.PRC.PRG Rev.1 January 2005 Page 31 of 175

Amines have been used for gas sweetening since before 1930. Refer to table 6.1.1 where some unique characteristics of the amines discussed here are summarized. When H2S and CO2 are dissolved in water they form a weak acid which combines with the amines, which have a weak base, to form a salt which is then decomposed by high temperatures: this absorption mechanism is common to all amines. During absorption the molecules of the acid gases must pass from the gaseous phase, through the gas-liquid interface, to the liquid phase; the H2S reacts immediately with the amine molecules in the interface: its absorption is therefore limited by its transfer from the gas phase. Absorption of CO2 is instead limited also by diffusion in liquid phase as its reaction with the amines is not instantaneous. The amines used in sweetening processes can be primary, secondary and tertiary depending on the number of radicals bonded to the nitrogen. The absorption capacity of acid gases decreases from the primary amines to the tertiary ones because the alkalinity decreases proportionately. Table 3.1.1 shows the empirical formulas of the amines dealt with here; the relative structural formulas are given in table 3.1.2. The reactions which take place during the acid gas absorption and regeneration stages of amine solutions are listed below along with the reaction speed: a) MEA and DGA 2RNH2 (RNH3)2S 2RNH2 (RNH3)2CO3 2RNH2 + + + + + H2S H2S H2O+ CO2 H2O +CO2 CO2 <===> <===> <===> <===> <===> (RNH3)2S INSTANTANEOUS 2RNH3HS INSTANTANEOUS (RNH3)2CO3 FAIR 2RNH3HCO3 FAIR RNHCOONH3R FAIR

b) DEA and DIPA 2R2NH (R2NH2)2S 2R2NH (R2NH2)2CO3 2R2NH + + + + + H2S <===> H2S <===> H2O + CO <===> H2O + CO2 <===> CO2 <===> (R2NH2)2S INSTANTANEOUS 2R2NH2HS INSTANTANEOUS (R2NH2)2CO3 FAIR 2R2NH2HCO3 FAIR R2NCOONH2R2 FAIR

C) TEA and MDEA 2R3N + H2S <===> (R3NH)2S INSTANTANEOUS

Eni S.p.A.
Exploration & Production Division (R3NH)2S + H2S <===> 2R3N + H2O + CO2 <===> (R3NH)2CO3 + H2O + CO2 <===>

00342.HTP.PRC.PRG Rev.1 January 2005 Page 32 of 175

2R3NHHS INSTANTANEOUS (R3NH)2CO3 SLOW 2R3NHHCO3 SLOW

Note that the maximum quantity of H2S that can be absorbed by the amines is equal to 1 mol/mol amine while the maximum quantity of CO2 that can be absorbed is 0.5 mol/mol amine for carbamate to form (only for primary and secondary amines) while it is equal to 1 mol/mol amine for the bicarbonate reaction. The reactions listed take place from left to right during the acid gas absorption stage and from right to left during the solution regeneration stage. Absorption is favoured by low temperature while regeneration takes place at the boiling temperature corresponding to the minimum operating temperature needed for the acid gas produced. In the case of the presence of stronger acid gases than and such as thiosulphate and thiocyanate, the reactions with the amines causes the formation of salts that cannot be regenerated even at high temperature. It has already been mentioned that the reaction of H2S with the amines is controlled by the gaseous film with the consequence that the H2S absorption capacity is similar for all the amines. However, the reaction between CO2 and amine is more complex: CO2 reacts with the primary and secondary amines to form carbamate as these amines have an unstable hydrogen atom which favours the reaction while the tertiary amines, which do not have a hydrogen atom, do not form carbamate. When CO2 dissolves in water it is firstly hydrolyzed to H2CO3 and then reacts to form bicarbonate; as the dissociation of carbonic acid is slow, the entire CO2 absorption kinetics are slow. The above stated reactions of CO2 are exploited when necessary to make a selection, above all using concentrated solutions with low water content which allow the absorption of CO2 to be favourably limited, leaving the H2S absorption capacity unchanged. The primary amines have stronger bases and are not suitable for selective absorption of ; secondary amines are moderately selective: however, DEA has double the CO2 absorption capacity of DIPA which is therefore more selective. Instead, the tertiary amines are selective as the CO2 does not react to form carbamate. However, TEA has too weak a base to offer an acceptable pick-up, at least with moderate partial pressures of H2S while MDEA allows fair pick-ups even with low partial pressures. Note that MDEA and DEA are stable amines with a boiling point and atmospheric pressure of 170°C and 268°C respectively while TEA, which has a boiling point and atmospheric pressure of 180°C, decomposes before reaching boiling point.

Eni S.p.A.
Exploration & Production Division

00342.HTP.PRC.PRG Rev.1 January 2005 Page 33 of 175

This means that this particular amine is not widely used for industrial sweetening purposes even if in some applications with high partial pressures of H2S the absorbing capacity of TEA can be cost-effectively exploited. The selectivity of the amines, above all DIPA and MDEA can be maximized by acting on the time the solution remains in the absorption column and the flow rate of the circulating solution (short time in the column and low circulation rate favour selectivity). The short time in the column can be obtained by reducing the contact volume while the low circulation rate can be obtained with a higher concentration of amine. Figure 3.1.2 shows the effect of the flow rate of the circulating solution and the contact volume on the selectivity and degree of purification that can be obtained with a selective amine. One way of increasing selectivity is to use an absorber which can supply the lean solution at different heights: the correct contact volume is generally decided when the unit is started up. The behaviour of the amines in relation to the absorption capacity of organic sulphur differs greatly: MEA absorbs CO2 and CS2 but it is degraded and only absorbs a few of the lighter mercaptans; DEA and MDEA partially absorb organic compounds such as CO2 and CS2 and do not react in any way with these substances: DGA easily absorbs CS2 but is also easily degraded by it; finally, DIPA absorbs the COS but is degraded by CO2 and by COS and . In the case of the presence of organic sulphur compounds in the gas to be treated, the choice of amine must be carefully considered; if the organic sulphur compounds are present in large doses and are to be removed it is probably better to use a physical absorption system or other more suitable processes such as catalytic hydrolysis of the crude gas before sweetening; on the market there are specific catalysts able to ensure a high conversion of CO2 and CS2 in H2S at temperatures of between 100°C and 150°C in the presence of fairly limited quantities of steam (3%-5% in volume). The presence of NH3 in the crude gas is tolerated by all the amines that are able to ensure their almost complete removal; HCN instead causes the degradation of all the amines. The absorption of H2S and CO2 by the amines takes place due to the so-called driving force of the gas phase to the liquid phase. In the gaseous phase the partial pressure of the acid gas is equal to the total pressure multiplied by the molar fraction of the gas. In the liquid phase the acid gas absorbed exercises a vapour pressure on the solution; the vapour pressure depends on the concentration of the acid gas and the solution temperature. The driving force is the difference between the partial pressure of the acid gas in the crude gas to be treated and the vapour pressure of the acid gas in the absorbing solution; at equilibrium, the two pressures are equal and so the driving force is annulled and the solution cannot absorb any more acid gas.

Eni S.p.A.
Exploration & Production Division

00342.HTP.PRC.PRG Rev.1 January 2005 Page 34 of 175

When designing a sweetening system note that only the partial pressure of the acid gas is not modifiable: the vapour pressure of the acid gas depends instead on the type of amine, temperature, concentration of the amine and concentration of the acid gas in the amine; all these parameters can be modified by the engineer to optimize the sweetening system. The absorption capacity of the various amines as regards acid gas and the vapour pressure of the acid gases on amines are the fundamental parameters for understanding the possibility of using the different amines. Refer to table 3.1.6 which indicates the absorbing capacity of the amines: despite the fact that MEA and DGA are able to chemically absorb very high quantities of acid gases, the table has been drawn up assuming a limit of 0.4 mol acid gas/mol amine considered the maximum possible value if serious corrosion of the plant is to be avoided. The table shows the net pick-up that can be obtained using a lean solution at 20°C, and the consumption of steam for regeneration of the solution for cases of absorption at 15 and 50 eff. bar Examination of the table shows that the best performance from a merely quantitative point of view are those that can be obtained with concentrated DEA and DIPA (MDEA has a similar performance to DIPA). Figure 6.1.4 shows the adiabatic load curves at equilibrium of the various amines assuming a temperature of the lean solution of 40°C, as a function of the partial pressure of the crude gas to be treated; also in this case the maximum concentration of acid gas was limited to 0.4 mol/mol amine for MEA and DGA. The figure shows that the DGA is the most interesting amine on the low partial pressure field for H2S while DIPA and DEA are the most effective amines as the partial pressure rises. An interesting comparison between MEA, DEA and DIPA is shown in figures 6.1.41 and 6.1.42 where the vapour pressures of H2S and CO2 on equimolar amine solutions at a temperature of 40°C are shown. For both acid gases the MEA is the most competitive MEA, followed by DEA and DIPA. Figure 3.1.2 shows the vapour pressures in that can be obtained with the different amines depending on the consumption of steam for regeneration. The figures show that the best results in terms of crude gas purification can be obtained in the following order: TEA, DIPA, DEA, MEA and DGA. MDEA has a similar behaviour to DEA. As can be seen from the data in the figures and tables, it is not possible to identify a single most competitive amine: the total pressure of the gas, the partial pressure of the and of the in the crude gas to be treated, the presence or absence of organic sulphur compounds, the degree of purification and selectivity desired can play a decisive role in the choice of process. Only detailed study of the problem with reference also to the consumption of utilities can allow for the most cost-effective choice to be identified.

Eni S.p.A.
Exploration & Production Division

00342.HTP.PRC.PRG Rev.1 January 2005 Page 35 of 175

The modern approach is to use secondary or tertiary amines when selectivity is required and/or when large quantities of acid gas have to be treated; primary amines are used for fairly small quantities of acid gases when selectivity is not necessary and when the partial pressures of H2S and CO2 are low. The use of anti-corrosion additives can reduce the heat needed for regeneration of the MEA by around 30%; however, the use of additives implies the payment of a license. Anti-corrosion additives are generally poisonous and not biodegradable; despite the fact that their presence in solutions is limited to just 0.5 – 2% in weight, the fact that they are poisonous has limited the development of these types of processes even although performance in terms of cost-effective operations is very high. Another system used to improve the performance of MEA is to add diethylene glycol (DEG) to the watery MEA solutions. At the same operating pressure the addition of glycol provokes a rise in the boiling point of the solution with ensuing improvement in performance in terms of final purification of H2S and CO2 (the residual H2S is less than half that obtainable with MEA alone). The physical characteristics of some lean amine solutions are indicated below. DGA and TEA have not been included as they are not commonly used nor are DIPA solutions which are subject to license: sufficient data is available in any case in past studies (Kohl and Riesenfield - Gas Purification). The physical characteristics of the rich solutions have not been included but are also available from past studies. The figures below give a series of physical data and vapour pressures of acid gases on amine solutions:

Eni S.p.A.
Exploration & Production Division

00342.HTP.PRC.PRG Rev.1 January 2005 Page 36 of 175

PROCESS

ACTIVE AMINE (HOCH2CH2) 2NH M=105 – (HOCH2CH2) 2NH M=105

TYPICAL AMINE CONCENTRATION CONCENTRATION % weight 3 Kmol/m 2 3 21 31

SOLVENT DENSITY AT 25°CKg/m 1020 1035

BOILING POINT AT 1.8 ata °C 118 119

DEA DEA CONC.

M = Molecular weight Kg/Kmol

TABLE 3.1.5 – AMINES – COMPOSITION AND PHYSICAL PROPERTIES

Eni S.p.A.
Exploration & Production Division

00342.HTP.PRC.PRG Rev.1 January 2005 Page 37 of 175

15 eff. bar
NET PICKUP REGENERATIO N STEAM SOLUTION Kg steam m3 solution SWEETENIN G STEAM ACID GAS Kg steam Kmol acid gas NET PICKUP

50 eff. bar
REGENERATIO N STEAM SOLUTION Kg steam m3 solution SWEETENIN G STEAM ACID GAS Kg steam Kmol acid gas

AMIN E

CONCENTR . % weight of amine in water

Kmol Acid gas m3 solutio n

Kmol Acid gas m3 solutio n

DEA DEA (*) –

21 31

1,62 2,16

152 183

94 85

1,84 2,55

99 113

52 44

CONSIDERING A LIMIT OF 0.4 mol acid gas/mol amine MAXIMUM TO LIMIT CORROSION

THE TABLE WAS DRAWN UP CONSIDERING AN H2S SWEETENING FROM 10% vol. TO 4 ppm vol. WITH APPROACH TO EQUILIBRIUM OF 33% AT THE ABSORBER HEAD AND OF 70% AT THE TAIL OF THE ABSORBER

TABLE 3.1.6 – AMINES – ABSORBING CAPACITY

Eni S.p.A.
Exploration & Production Division

00342.HTP.PRC.PRG Rev.1 January 2005 Page 38 of 175

N = NUMERO DI PIATTI

% H2S ABSORBED SELECTIVITY ---------------------------% CO2 ABSORBED

SOLVENT IN CIRCULATION FIGURE 3.1.1 – AMINES – SELECTIVITY EFFECT

Eni S.p.A.
Exploration & Production Division

00342.HTP.PRC.PRG Rev.1 January 2005 Page 39 of 175

PRESSIONE DI FONDO RIGENERATORE: 1.8 bar. ass.

PARTIAL PRESSURE OF H2S IN THE LEAN SOLUTION AT 40°c - ata•10-6

STEAM CONSUMPTION FOR REGENERATION - kg/m3 FIGURE 3.1.2 – AMINES – REGENERATION STEAM

Eni S.p.A.
Exploration & Production Division

00342.HTP.PRC.PRG Rev.1 January 2005 Page 40 of 175

Of the amines, DEA and MDEA are those with least tendency to absorb hydrocarbons; MEA and DIPA have greater solubility while DGA has even higher solubility. Table 3.1.22 shows the solubility of hydrocarbons in water, in DEA and in MEA; despite the fact that solubility depends not only on the temperature but also on the partial pressure and on the concentration of amine and the pick-up of acid gases, the values in the table should be considered fairly precise for the calculation of the global performance of a sweetening plant.

Eni S.p.A.
Exploration & Production Division

00342.HTP.PRC.PRG Rev.1 January 2005 Page 41 of 175

DENSITY – kg/dm3

TEMPERATURE - °C FIGURE 3.1.3 – DEA – DENSITY OF SOLUTIONS

Eni S.p.A.
Exploration & Production Division

00342.HTP.PRC.PRG Rev.1 January 2005 Page 42 of 175

VISCOSITY – centipoise

TEMPERATURE - °C FIGURE 3.1.4 – DEA – VISCOSITY OF SOLUTIONS

Eni S.p.A.
Exploration & Production Division

00342.HTP.PRC.PRG Rev.1 January 2005 Page 43 of 175

ACQUA

SPECIFIC HEAT – Kcal/Kg •°C

TEMPERATURE - °C FIGURE 3.1.5 – DEA – SPECIFIC HEAT OF SOLUTIONS

Eni S.p.A.
Exploration & Production Division

00342.HTP.PRC.PRG Rev.1 January 2005 Page 44 of 175

TOTAL PRESSURE – mm Hg

TEMPERATURE - °C FIGURE 3.1.6 – DEA – VAPOUR PRESSURE OF SOLUTIONS

Eni S.p.A.
Exploration & Production Division

00342.HTP.PRC.PRG Rev.1 January 2005 Page 45 of 175

PICK-UP SOLUTION – mol CO2/mol DEA

CONCENTRAZION DEA 30% peso

VAPOUR PRESSURE CO2 – mm Hg FIGURE 3.1.7 – DEA – VAPOUR PRESSURE OF CO2

Eni S.p.A.
Exploration & Production Division

00342.HTP.PRC.PRG Rev.1 January 2005 Page 46 of 175

PICK-UP SOLUTION – mol H2S/mol DEA

CONCENTRAZION DEA 30% peso

VAPOUR PRESSURE H2S – mm Hg FIGURE 3.1.8 – DEA – VAPOUR PRESSURE OF H2S

Eni S.p.A.
Exploration & Production Division

00342.HTP.PRC.PRG Rev.1 January 2005 Page 47 of 175

VAPOUR PRESSURE OF CO2-ata

PARAMETRO mol H2S / mol DEA IN FASE LIQUIDA DEA 36% PESO TEMPERATURA 50°C

PICK-UP OF SOLUTION – mol CO2/mol DEA FIGURE 3.1.9 – DEA – VAPOUR PRESSURE OF CO2 – 50°C

Eni S.p.A.
Exploration & Production Division

00342.HTP.PRC.PRG Rev.1 January 2005 Page 48 of 175

VAPOUR PRESSURE OF H2S- ata

PARAMETRO mol CO2 / mol DEA IN FASE LIQUIDA DEA 36% PESO TEMPERATURA 50°C

PICK-UP OF SOLUTION – mol H2S/mol DEA FIGURE 3.1.10 – DEA – VAPOUR PRESSURE OF H2S – 50°C

Eni S.p.A.
Exploration & Production Division

00342.HTP.PRC.PRG Rev.1 January 2005 Page 49 of 175

VAPOUR PRESSURE OF H2S- ata

PARAMETRO mol CO2 / mol DEA IN FASE LIQUIDA DEA 36% PESO TEMPERATURA 70°C

PICK-UP OF SOLUTION – mol H2S/mol DEA FIGURE 3.1.11 – DEA – VAPOUR PRESSURE OF H2S – 70°C

Eni S.p.A.
Exploration & Production Division

00342.HTP.PRC.PRG Rev.1 January 2005 Page 50 of 175

VAPOUR PRESSURE OF CO2- ata

PARAMETRO mol H2S / mol DEA IN FASE LIQUIDA DEA 36% PESO TEMPERATURA 70°C

PICK-UP OF SOLUTION – mol CO2/mol DEA FIGURE 3.1.12 – DEA – VAPOUR PRESSURE OF CO2 – 70°C

Eni S.p.A.
Exploration & Production Division

00342.HTP.PRC.PRG Rev.1 January 2005 Page 51 of 175

DENSITY – Kg/m3

AVERAGE CONCENTRATION - % weight FIGURE 3.1.13 – DEA – DENSITY OF SOLUTIONS

Eni S.p.A.
Exploration & Production Division

00342.HTP.PRC.PRG Rev.1 January 2005 Page 52 of 175

VISCOSITY – centipoise

ACQUA

TEMPERATURE - °C FIGURE 3.1.14 – DEA – VISCOSITY OF SOLUTIONS

Eni S.p.A.
Exploration & Production Division

00342.HTP.PRC.PRG Rev.1 January 2005 Page 53 of 175

(ACQUA PURA)

SPECIFIC HEAT – Kcal/Kg °C

PUNTO DI EBOLLIZIONE

PUNTO DI CONGELAMENTO

TEMPERATURE - °C FIGURE 3.1.15 – MDEA – SPECIFIC HEAT OF SOLUTIONS

Eni S.p.A.
Exploration & Production Division

00342.HTP.PRC.PRG Rev.1 January 2005 Page 54 of 175

VAPOUR PRESSURE – mm Hg

TEMPERATURE - °C FIGURE 3.1.16 – VAPOUR PRESSURE OF PURE MDEA

Eni S.p.A.
Exploration & Production Division

00342.HTP.PRC.PRG Rev.1 January 2005 Page 55 of 175

TEMPERATURA 40°C

THERMAL CONDUCTIVITYKcal/m•h•°C

MDEA CONCENTRATION - % weight FIGURE 3.1.17 – MDEA – THERMAL CONDUCTIVITY OF SOLUTIONS

Eni S.p.A.
Exploration & Production Division

00342.HTP.PRC.PRG Rev.1 January 2005 Page 56 of 175

VAPOUR PRESSURE OF CO2- ata

PARAMETRO mol H2S / mol DEA IN FASE LIQUIDA MDEA 40% PESO TEMPERATURA 40°C

PICK-UP OF SOLUTION – mol CO2/mol MDEA FIGURE 3.1.18 – MDEA – VAPOUR PRESSURE OF CO2 – 40°C

Eni S.p.A.
Exploration & Production Division

00342.HTP.PRC.PRG Rev.1 January 2005 Page 57 of 175

VAPOUR PRESSURE OF CO2- ata

PARAMETRO mol H2S / mol DEA IN FASE LIQUIDA MDEA 40% PESO TEMPERATURA 100°C

PICK-UP OF SOLUTION – mol CO2/mol MDEA FIGURE 3.1.19 – MDEA – VAPOUR PRESSURE OF CO2 – 100°C

Eni S.p.A.
Exploration & Production Division

00342.HTP.PRC.PRG Rev.1 January 2005 Page 58 of 175

VAPOUR PRESSURE OF H2S- ata

PARAMETRO mol CO2 / mol DEA IN FASE LIQUIDA MDEA 40% PESO TEMPERATURA 40°C

PICK-UP OF SOLUTION – mol H2S/mol MDEA FIGURE 3.1.20 – MDEA – VAPOUR PRESSURE OF – 40°C

Eni S.p.A.
Exploration & Production Division

00342.HTP.PRC.PRG Rev.1 January 2005 Page 59 of 175

VAPOUR PRESSURE OF H2S- ata

PARAMETRO mol CO2 / mol DEA IN FASE LIQUIDA MDEA 40% PESO TEMPERATURA 100°C

PICK-UP OF SOLUTION – mol H2S/mol MDEA FIGURE 3.1.21 – MDEA – VAPOUR PRESSURE OF H2S – 100°C

Eni S.p.A.
Exploration & Production Division

00342.HTP.PRC.PRG Rev.1 January 2005 Page 60 of 175

ABSORBING FLUID CH4 C2H6 C3H8 C4H10 C5H12 C6H14 C7H16

WATER 0,021 0,041 0,031 0,020 0,012 0,0024 0,0007

DEA 20% WEIGHT 0,014 0,029 0,021 0,013 0,008 0,0018 0,0005

SOLUBILITIES ARE EXPRESSED IN Nm3/m3•ata AT AMBIENT TEMPERATURE

TABLE 3.1.22 – SOLUBILITY OF HYDROCARBONS IN H2O, MEA AND DEA

Eni S.p.A.
Exploration & Production Division 3.1.3 Column design

00342.HTP.PRC.PRG Rev.1 January 2005 Page 61 of 175

Amine plant absorbers are usually of the plate type; packed columns are used when load flexibility is required or when large quantities of acid gas have to be absorbed: the packing is normally metallic or ceramic. In both cases it is advisable during design to consider that the amines are fluids which can cause foaming and so suitable dimensioning margins must be applied for the plates which must also be suitably spaced, especially in the case of MEA. The typical number of plates in an absorption column is 18-20; even although the number of plates must be calculated on a case by case basis depending on the operating conditions, it is rare that fewer than 18 plates are used; on the contrary, columns with more than 35 plates have been designed and developed. The absorption columns generally have a head demister to contain entrainments and operate with the lowest head temperature compatibly with the need to avoid hydrocarbon condensation during contact between the gas to be treated and the absorbing solution. Ways of avoiding entrainments and hydrocarbon condensation in the column include supercooling the crude gas to be scrubbed, using effective systems to separate droplets in the gas to be scrubbed, insulating the incoming gas lines and the bottom of the column and, finally, working with a temperature of the solution at the head which is more than 10°C higher than the dew point in the hydrocarbons of the gas to be scrubbed. The regenerators are usually plate columns except when large quantities of acid gas have to be treated. Typically 18–20 regeneration plates are used with 2-3 upper plates for scrubbing the acid gases released through the reflux and replenishment condensates. The dimension of the regenerators also takes into account the specific use, with the risk of the formation of foam. Metallic material is preferred for the packing instead of ceramic material, even if ceramic is still fairly widely used; the decision to use metallic packing material is due partly to the undoubted superior ultimate strength under load conditions and during operations, and partly to the instability of some types of ceramics to the alkaline attacks of the amines at the relatively high temperatures of the regenerators with ensuing tendency towards porosity and disintegration. The suitability of the ceramic packing material for use with amines can however be checked in advance by means of simple tests.

Eni S.p.A.
Exploration & Production Division

00342.HTP.PRC.PRG Rev.1 January 2005 Page 62 of 175

The solutions are regenerated almost exclusively using steam supplied by kettle or radiator type boilers; only in very particular cases is direct steam used; however, it is difficult to dispose of because amine plants generally have a fairly limited water balance. Regeneration of the solution with direct flame boilers is used above all in industrial contexts which do not have a heating fluid such as steam or hot oil available. Direct flame boilers should be used with extreme caution in order to avoid thermal degradation of the solutions due to the high temperatures of the heat exchange surfaces. Another limit to the use of direct flame boilers derives from some mechanical calculation codes that make the design impossible when design pressures of 0.5 eff. bar are exceeded. 3.1.4 Design of other main equipment The solution/solution exchangers which in the past consisted of series of pipe bundles are now more frequently plate exchangers which are more compact and efficient; there is a tendency to apply plate exchangers to cool the solution when cooling water is available and application is possible at a fairly low temperature. In any case, the new generation of plate exchangers can be applied also at pressures of 20-25 eff. bar In most cases however, the solution is cooled and the acid gas condensed using air coolants. Turbines to recover energy from the rich solution leaving the absorber are not normally used in amine plants due to the low flow rate of the circulating solution, at least compared to absorption processes for large quantities of acid gas such as hot carbonate plants. However, in the case of two-stage designs with high rates of MDEA or DEA, the use of recovery turbines greatly improves the economic result of the plant. It has already been mentioned that a flash tank for hydrocarbons is needed to recover hydrocarbons dissolved in the solutions (above all DIPA) or in cases where the acid gas has to be supplied to a Claus unit and must therefore contain only minimum quantities of hydrocarbons. The flash tank is dimensioned on the basis of the time of residence which varies from 3 to 6 minutes depending on the hydrocarbon absorbing capacity of the solution. In some case special systems (skimmers) are used to remove gasoline floating on the solution in the flash tank. If the gas released into the flash tanks has to be recovered with low H2S content, it is normal practice to place a small scrubbing tower on top of the flash tank supplied by a small quantity of lean solution.

Eni S.p.A.
Exploration & Production Division

00342.HTP.PRC.PRG Rev.1 January 2005 Page 63 of 175

A mechanical cartridge filter is generally installed on the cold lean solution as well as an activated carbon filter to entrain hydrocarbons. The optimal position of this second filter is the subject of debate: we tend to install it on the rich solution leaving the absorber to block the hydrocarbons before they reach the regenerator. Although it is theoretically possible to regenerate activated carbon, it is preferable to replace it with a new charge when it is rich. Depending on the amine and type of service, the rate of solution to send to the filters varies from a minimum of 5% to a maximum of 100% of the circulating solution. The mechanical filters are usually designed to entrain particles of 50 micron even if filtering to 10-20 micron is preferable and in some cases necessary for the plant to function correctly. Many plants are fitted with injection systems for anti-foam agents to use only in cases of real need. The systems range from manual load tanks to small dosed injection stations. The type of anti-foam to use is not easy to identify in advance but can depend on the operating conditions of the plant: however, the injection of anti-foam agents must be limited over time so as not to exasperate the phenomenon due to the presence in the solution of the degradation substances of the anti-foam agent. The solidification point of pure amines is lower than 0°C; the amines used in accordance with their typical concentrations have solidification points of around -5°C/-6°C except for DGA which solidifies at -40°C/-50°C. However, it is advisable to use heating coils inside the storage tanks or blowdown collection tanks where the solution can remain for long periods of time without agitation. The need to protect the pipes against the risk of freezing (with steam or electric marking) depends on the design temperature of the plant; generally, no protection is needed in Italian coastal areas but the pipes are emptied during the long winter shut-downs. Plants with amine solutions always have an underground blowdown collection tank fitted with booster pump and a solution storage tank. The storage tank must be able to contain all the solution present in the equipment; the blowdown tank generally has a minimum capacity of 2-3 m3 and a maximum capacity of 10% that of the storage tank. A pump conveys the solution from the storage tank to the absorption cycle; all the discharges from the plant equipment are conveyed to the blowdown collection tank. The importance of collecting all solution blowdowns, including accidental blowdowns, lies in the need to completely eliminate any leakage of amines from the plant. Modern amine plants are fitted with solution blowdown

Eni S.p.A.
Exploration & Production Division

00342.HTP.PRC.PRG Rev.1 January 2005 Page 64 of 175

collection systems and are built in such a way as to minimise the risk of accidental leakages (for example, pump stuffing box sealing fluids are not used unless strictly necessary for machines subject to great stress but pumps with self-fluxed mechanical seals are preferred). Plenum in the blowdown collection and storage tanks is obtained with inert or fuel gas to avoid the degradation of the solution in contact with the oxygen: this is preferred also when not strictly indispensable, for example for MDEA and DEA. 3.1.5 Construction materials Mention has already been made of the corrosion caused by MEA, which is more accentuated as the pick-up of the acid gas increases; it has also been mentioned that the pick-up of the MEA can be increased by around 30% by using special patented anti-corrosion additives (manufactured by Union Carbide). Corrosion of carbon steel similar to that caused by MEA is common also to DGA and DIPA while DEA and MDEA have a decidedly less aggressive behaviour. Despite the reduced aggressiveness of DEA and MDEA compared to other amines, nowadays all amines tend to be considered equally corrosive and so the same materials are generally used in amine services. Even if some companies used carbon steel with significant corrosion overthickness for amine services in the past, they now prefer to use stainless steel where there is a statistically high probability of corrosion. However, it should be noted that the parts most subject to corrosion are those in contact with the acid gases, with greater corrosion where only CO2 or mainly CO2 with H2S of not more than 1% vol. is present, followed immediately by the parts in contact with the hot rich solution (temperature of more than approx. 80°C). Note once again that present-day practice is to anneal the weld seams of all the carbon steel parts of the equipment that are in contact with the amines in continuous and dynamic service (therefore not the tanks). The presence of chlorides in the replenishment water is another source of severe corrosion which is difficult to control even when stainless steel is used. The absorption and regeneration column are made of carbon steel with stainless steel interiors (plates or packing). The regeneration columns are generally lined with stainless steel from 2-3 inches below the upper tangency line up to the head. The bottom of the regeneration column is also sometimes lined with stainless steel.

Eni S.p.A.
Exploration & Production Division

00342.HTP.PRC.PRG Rev.1 January 2005 Page 65 of 175

For small columns in contact with particularly aggressive solutions (MEA, MEA-DEG, DGA), it is common practice to use only stainless steel for the entire construction. The solution/solution exchanger is made of stainless steel in the case of plate exchanges and sometimes also, but only for the hottest element, in the case of multiple pipe bundle exchangers. The solution coolant is generally made of carbon steel except for plate type coolants where stainless steel is used. The acid gas coolant is generally made of stainless steel as is the boiler and reclaimer solution side, heads excluded. The flash tank and amine storage and blowdown collection tanks are made of carbon steel as is the body of the solution filters. The reflux accumulator of the regenerator (acid gas separator) is instead made of stainless steel. The solution and acid condensate circulation pumps have stainless steel body and rotors. The other machines in discontinuous service, such as solution blowdown pumps and solution loading pumps are made of carbon steel. The solution pipes downstream of the solution-solution economizer at the regenerator head are made of stainless steel; the hot and cold acid gas pipes and the acid condensate pipes are also made of stainless steel. In the case of acid gas at a temperature of not more than 50°C and with high H2S content it is possible to use carbon steel with steam or electric marking to prevent the steam from condensing. All the other pipes are made of carbon steel even if sometimes the lean solution pipes to the solution-solution exchangers are made of stainless steel to offer better protection. All the solution control valves are made of stainless steel as are the manual regulation valves even if they are assembled on carbon steel pipelines. 3.1.6 Foaming and amine leakage problems Accurate evaluation of the solvent rate and the global thermal balance of an amine plant requires precision calculations above all in the case of simultaneous absorption of H2S and CO2; this section describes valid, rapid methods to make rough evaluations or feasibility assessments.

Eni S.p.A.
Exploration & Production Division

00342.HTP.PRC.PRG Rev.1 January 2005 Page 66 of 175

The evaluation methods refer to MEA, DEA and MDEA solutions; i.e. processes not subject to the payment of a license; calculation methods are not available for solutions subject to license such as DGA and DIPA. Refer to section 3.3. for a description of a rapid method to evaluate the rate of DIPA and Sulfolan based Sulfinol solutions: this method is applicable also to DIPA alone, taking however into consideration that the rates obtained must be increased slightly. A traditional plant lay-out has been assumed for evaluation of the solution flow rate. Calculation with DEA The performance obtained in terms of purification can be inferred from figure 6.1.5. Considering a consumption of regeneration heat of 100Kg/m3, the purification result that can be reached is calculated as follows: ppm of H2S in the sweet gas = 50/(0.33 X P) for DEA 21% weight = 70/(0.33 X P) for DEA 31% weight

where P is the operating pressure of the absorber expressed in abs. bar and 0.33 is a safety coefficient that expresses the ratio of 1 to 3 for the driving force at the absorber head; in practice, it is assumed that the vapour pressure of the acid gas on the lean solution is equal to 1/3 of the partial pressure of the acid gas in the sweetened gas. The quantity of regeneration vapour is usually between 100 and 130 Kg/m3 of solution. The maximum load that can be obtained is deduced using the alignment charts in figures 6.1.38 for H2S and 6.1.39 for CO2. The concentration of the solution can vary from 20% to 35% in weight; the approach to equilibrium is usually around 60%-70%. Also in this case a temperature at the bottom of the absorber which is 15°C40°C higher than that of the lean solution at the head is assumed; 15°C will be used in the case of diluted solution and 40°C in the case of concentrated solutions. The H2S and CO2 load in rich DEA solution can be assumed to be 0.02 - 0.04 mol/mol DEA. There are therefore no limits to the gas load which can be applied up to the maximum amount compatible with the available driving force: loads up to 0.7 – 1 mol/mol DEA can generally be obtained.

Eni S.p.A.
Exploration & Production Division

00342.HTP.PRC.PRG Rev.1 January 2005 Page 67 of 175

Plants which use loads of more than 0.4 mol/mol must however be designed with great care, above all increasing the filtration of the solution; the use of inhibited solutions allows the load limit indicated above to be increased to 0.5—0.55 mol/mol. Calculation with DEA The performance obtained in terms of H2S purification can be inferred from figure 3.1.2. MDEA has an intermediate behaviour between TEA and DEA. The quantity of regeneration vapour is usually between 80 and 120 Kg/m3 of solution (see table 3.1.4). The preliminary calculation can be set assuming the use of a 40% weight solution and a temperature of 10-20°C higher than the temperature of the head solution. Using figures 3.1.18, 3.1.19, 3.1.20 and 3.1.21 the H2S and CO2 vapour pressures can be extrapolated after assuming an absorbing solution rate. The assumed solution flow rate is considered acceptable when the approach to equilibrium is 60%-75%; that is, when the H2S and CO2 vapour pressures in solution are around 1.35 – 1.7 times the partial pressures of H2S and CO2 in the crude gas. In the case of selective absorption it is assumed that it is possible to obtain an acid gas with an H2S/CO2 ratio which is four times more than the same ratio in the crude gas. Other elements used to evaluate the economics of sweetening are the hydrocarbons that are dissolved and then lost in the absorbing solutions and the losses of solvent through degradation, entrainment and evaporation with the sweet gas and acid gas. Hydrocarbon losses can be calculated for MEA and DEA using table 3.1.22. The solubility of hydrocarbons in MDEA is even lower than that in DEA. Losses of amine through degradation cannot be prevented in advance; if there is a risk of degradation due to the presence of reactive products in the gas to be treated, a process which uses non-degradable amine must be chosen. Losses through entrainment are almost always due to the presence of foaming agents (surfactants such as oils, liquid hydrocarbons) in the absorbing solutions: in this case it is necessary to identify and eliminate the cause of the formation of foams and to limit their development by injecting anti-foam substances; however, also in this case the loss of solvent cannot be evaluated.

Eni S.p.A.
Exploration & Production Division

00342.HTP.PRC.PRG Rev.1 January 2005 Page 68 of 175

Losses through evaporation can be calculated assuming that the sweet and acid gas contain evaporated amine in equilibrium at the vapour pressure of the amine on the absorbing solution under set operating conditions (amine concentration, temperature and pressure).

Eni S.p.A.
Exploration & Production Division C T P R

00342.HTP.PRC.PRG Rev.1 January 2005 Page 69 of 175

CONCENTRATION OF DEA % weight TEMPERATURE AT THE BOTTOM OF THE ABSORBER °C H2S VAPOUR PRESSURE ata REFERENCE LINE

PARAMETRO CARICAMENTO CO2 mol CO2 / mol DEA

mol H2S / mol DEA

FIGURE 3.1.2 3 – H2S VAPOUR PRESSURE ON DEA, H2S AND CO2 SYSTEMS

Eni S.p.A.
Exploration & Production Division C T P R

00342.HTP.PRC.PRG Rev.1 January 2005 Page 70 of 175

CONCENTRATION OF DEA % weight TEMPERATURE AT THE BOTTOM OF THE ABSORBER °C CO2 VAPOUR PRESSURE ata REFERENCE LINE

PARAMETRO CARICAMENTO H2S mol H2S / mol DEA

mol CO2 / mol DEA

FIGURE 3.1.2 3 – CO2 VAPOUR PRESSURE ON DEA, H2S AND CO2 SYSTEMS

Eni S.p.A.
Exploration & Production Division

00342.HTP.PRC.PRG Rev.1 January 2005 Page 71 of 175

VAPOUR PRESSURE – mm Hg

TEMPERATURE - °C FIGURE 3.1.25 – DEA VAPOUR PRESSURE

Eni S.p.A.
Exploration & Production Division

00342.HTP.PRC.PRG Rev.1 January 2005 Page 72 of 175

TEMPERATURA 40 °C

VAPOUR PRESSURE OF H2S- ata

H2S LOAD – mol H2S/mol amine FIGURE 3.1.26 –H2S VAPOUR PRESSURE ON AMINE SOLUTIONS

Eni S.p.A.
Exploration & Production Division

00342.HTP.PRC.PRG Rev.1 January 2005 Page 73 of 175

TEMPERATURA 40 °C

VAPOUR PRESSURE OF CO2- ata

CO2 LOAD – mol CO2/mol amine FIGURE 3.1.27 – CO2 VAPOUR PRESSURE ON AMINE SOLUTIONS

Eni S.p.A.
Exploration & Production Division

00342.HTP.PRC.PRG Rev.1 January 2005 Page 74 of 175

3.1.7

Traditional absorption lay-out The traditional lay-out, shown in figure 3.1.28, consists in using a solution with a single regeneration level conveyed to the head of the packed or plate absorption column; the gas to be treated is scrubbed in counter-current; the rich solution leaving the bottom of the absorber passes into a flash tank if the pressure level of the absorber is higher than approx 10 eff. bar or if the lean acid is to be sent to a Claus unit. The flash tanks usually operate at a pressure of 4-6 eff. bar, which is sufficient to send the rich solution to the regenerator head without the aid of a pump. The gas dissolved in the absorber and released into the flash tank is conveyed to the fuel gas network, if envisaged, or is recovered; if necessary the flash gas is scrubbed again with a small amount of lean solution. The solution leaving the flash tank is heated in an economizer, cooling the lean solution, and then enters at the regenerator head at a temperature of between 80 and 110°C. The solution is regenerated by means of indirect heating; the heat required is supplied by a boiler assembled at the base of the regeneration column; this can be a packed or plate column. The boiler can be supplied by steam, hot gas, hot oil or pressurized water; sometimes, in the case of small units, boilers with direct flame in which a gas is burnt in a combustion chamber which directly heats the solution to be regenerated are used. The boiler can be kettle, horizontal or vertical thermosiphon or once through type. Typical regeneration temperatures are between 105°C and 150°C depending on the amine used and pressure reached (typically 0.5-1 eff. bar). The acid gases released at the regenerator head are scrubbed on three scrubbing plates and then sent to a condenser where they are cooled to 35°C-60°C; after being separated from the condensate, the acid gases are sent for further treatment (flare, incinerator, Claus unit). The acid condensate separated in the reflux accumulator is pumped to the regenerator head scrubbing plates; generally the process requires a water makeup prepared with demineralised water supplied to the reflux accumulator or directly to the regenerator. Whenever the system has excess water, the excess acid condensate is collected at the reflux pump delivery. The lean solution taken from the bottom of the regenerator is sent to the heat recovery with the solution to be regenerated and is then pumped to the head of the absorber after being cooled to 40°C-60°C. If necessary a booster pump is installed upstream of the main pump.

Eni S.p.A.
Exploration & Production Division

00342.HTP.PRC.PRG Rev.1 January 2005 Page 75 of 175

The temperature of the head solution is kept at least 10°C higher than the hydrocarbon dew point of the gas to be treated to avoid gasoline condensation in the absorber. A mechanical filter is used for the lean solution and an activated carbon "chemical" filter able to retain the hydrocarbons and organic substances on the rich solution. Moreover, an underground blowdown collection tank with vertical booster pump and storage pump with booster pump are normally envisaged; in both tanks plenum is provided with inert gas or fuel gas; both tanks are fitted with heating coil. The storage tank can be included in the absorption cycle between a booster pump and the main pump. Amines are usually sold in 160 litre drums; due to the high freezing point, if a DEA solution is used, a heating system should be envisaged for the amine drums to cut the loading and top up times during winter. Solution reclaiming plants are envisaged when amines are used in services with a high risk of degradation. The reclaimer functions with heating fluid at high temperature; the reclaiming operation consists in the continuous distillation of the solution with ensuing concentration of high-boiling products of degradation of the amine which will then be evacuated by the system (generally manually). Sometimes sodium has to be used to neutralize any acid products of degradation. The vacuum reclaimer is much more complicated in engineering terms and is operated in continuous mode. Vacuum reclaiming systems are needed for amines such as DGA and DIPA even if the gas to be treated does not contain impurities such as CO2-CS2 or organic sulphur. An important aspect for the efficient performance of the amine processes is to avoid gasoline condensation in the absorber: it is therefore important to use gas which is not saturated with gasoline or at suitable temperature in order not to cause condensation. If the gas to be treated is saturated in hydrocarbons, it is advisable to insulate the bottom of the absorber and maintain the head solution at a higher temperature than that of the gas; moreover, in these cases systems have to be installed upstream of the absorber to separate the gasoline from the crude gas.

3.1.8

Split-Flow Lay-out The split-flow lay-out, shown in figure 3.1.30, is very similar to the traditional lay-out. The difference is that part of the lean solution is conveyed to the head of the absorber at a lower temperature than that of the solution conveyed to the middle of the absorber.

Eni S.p.A.
Exploration & Production Division

00342.HTP.PRC.PRG Rev.1 January 2005 Page 76 of 175

This lay-out has few applications in amine processes but it more widely used in hot carbon ones. In this lay-out operations are possible at higher temperatures with savings as regards the dimensions of the thermal equipment and lower consumption of regeneration heat. The split-flow lay-out is used when large quantities of acid gas have to be sweetened but the two-stage lay-out is generally preferred as it is more efficient in terms of regeneration steam consumption. The intermediate solution coolant can be omitted depending on the type of amine used and the composition of the acid gas. 3.1.9 Two-stage lay-out The two-stage lay-out, shown in figure 3.1.31, uses a solution with two different degrees of regeneration and utilises the regeneration heat more efficiently, markedly reducing the demand for heat. Indeed, part of the steam used for regeneration of the solution in the lower part of the regenerator rises to the upper part which it partly regenerates the rich solution arriving from the regenerator head. This lay-out is not widely used for amines except when gas with high concentrations of acid gas has to be sweetened. The investment required is high. The lay-out, shown in figure 3.1.32 has been applied only in recent years in amine processes and is used to remove large quantities of acid gas. The lay-out is based on the two-stage principle described above and on the flash of hot rich solution leaving the absorber; the flash takes place in the upper part of the regenerator and the temperature needed is sustained by the vapour arriving from the lower part of the regenerator. The thermal equipment is much smaller than the Split-stream flow lay-out while the flow rate of circulating solution is fairly high. However, the global energetic result is much better. The amine which is best suited to this lay-out is activated MDEA: the consumption of heat for regeneration purposes can be up to 1/3 less than that of the traditional lay-out.

Eni S.p.A.
Exploration & Production Division

00342.HTP.PRC.PRG Rev.1 January 2005 Page. 77 of 175

FIGURE 3.1.28 – AMINES – TRADITIONAL LAY-OUT

Eni S.p.A.
Exploration & Production Division

00342.HTP.PRC.PRG Rev.1 January 2005 Page. 78 of 175

FIGURE 3.1.29 – AMINES – VACUUM PRESSURE RECLAIMER

Eni S.p.A.
Exploration & Production Division

00342.HTP.PRC.PRG Rev.1 January 2005 Page. 79 of 175

Eni S.p.A.
Exploration & Production Division

00342.HTP.PRC.PRG Rev.1 January 2005 Page. 80 of 175

FIGURE 3.1.30 – AMINES – SPLIT-FLOW LAY-OUT

Eni S.p.A.
Exploration & Production Division

00342.HTP.PRC.PRG Rev.1 January 2005 Page. 81 of 175

FIGURE 3.1.31 – AMINES – TWO-STAGE LAY-OUT (SPLIT – STREAM FLOW)

Eni S.p.A.
Exploration & Production Division

00342.HTP.PRC.PRG Rev.1 January 2005 Page. 82 of 175

FIGURE 3.1.32 – AMINES – EQUITHERMAL TWO-STAGE LAY-OUT

Eni S.p.A.
Exploration & Production Division 3.2 3.2.1 Physical absorption – Selexol Process Description of the process

00342.HTP.PRC.PRG Rev.1 January 2005 Page. 83 of 175

The SELEXOL process was developed by Allied Chemical and is now under Norton license. The solution used in the SELEXOL process typically comprises 5% weight of H2O and 95% weight of polyethylene dimethylether with molecular weight of 280 Kg/Kmol; the solution’s freezing point is between -22°C and -29°C and its flash point is 151°C. The typical characteristics of the solution are shown in figures 3.2.1 (vapour pressure), 3.2.2 (density), 3.2.3 (specific heat), 3.2.4 (viscosity) and 3.2.5 (thermal conductivity). Table 3.2.6 shows the solubility of Selexol in relation to a number of compounds using the solubility of methane gas as reference parameter. The main characteristics of the SELEXOL process are: - low regeneration cost, this is common to all physical absorption processes. - limited circulation flow rate due to the good load that can be obtained in high partial pressure conditions. - no corrosion problems. - limited losses of solvent through vaporization or degradation. - good dehydrating capacity. Like all physical absorption processes, SELEXOL can be profitably used when the partial pressure of the acid gas is sufficiently high. The solution is conveyed to the absorber also at very low temperature after being cooled. If the total pressure of the gas to treat were high as well, the process would guarantee a high degree of purification. SELEXOL is also suitable in cases where selective absorption of H2S compared to CO2 is required and is also suitable in cases where the gas to be sweetened contains CO2, CS2, mercaptans or other organic compounds. The process is used for sweetening natural gas and for treating synthesis gas. However, it must be borne in mind that, like all physical solvents, SELEXOL absorbs noticeable quantities of hydrocarbons and this can be considered a disadvantage. As in all absorption procedures that use amines, Selexol is also highly sensitive to the presence of liquid hydrocarbons in the gas to be treated; indeed, gasoline provokes severe foaming of the solution with losses of solvent through entrainment. A particular characteristic of the SELEXOL procedure is the possibility of regenerating the absorbing solution for subsequent flashes, followed by

Eni S.p.A.
Exploration & Production Division

00342.HTP.PRC.PRG Rev.1 January 2005 Page. 84 of 175

stripping with air or steam in cases where a high level of purification is required as will be described in detail in the following section. 3.2.2 Lay-outs used Figures 3.2.7, 3.2.8, 3.2.9 and 3.2.10 show four typical lay-outs for the SELEXOL process. Each process can is suitable for a specific sweetening needs. The lay-out in figure 3.2.7 can be used to sweeten natural gas with high CO2 content. Regeneration takes place for flashes only and so does not reach very high levels of regeneration. However, this is acceptable as the sweetened gas does not usually require very high decarbonation levels. Small quantities of H2S are also allowed in the gas to be treated (10-20 ppm) because in this case the CO2 flash has an adequate stripping effect. Final regeneration of the solution with air would be possible in the case of crude gas containing only CO2 (integrating the lay-out in figure 3.2.7) if a fairly high CO2 purification level is required but in the complete absence of H2S in the gas to be sweetened. Regeneration with air of SELEXOL solutions in cases of absorption of gas containing is not possible for the transformation of into sulphur by the oxygen present in the air and the consequent precipitation of metallic sulphur in solution. In cases where crude gas containing is to be treated, the final regeneration could therefore be performed using steam or inert gases. The lay-out in figure 3.2.8 is suitable for sweetening natural gas with a low CO2 content. Indeed, by exploiting the selectivity of the solvent with reference to H2S (see table 3.2.6) all the CO2 acceptable for the specification can be left in the treated gas while the H2S is completely absorbed. A high level of regeneration of the solvent provides a sweetened gas of the required purity in terms of H2S. The solution envisaged in the lay-out in figure 3.2.9 sweetens natural gas with a high CO2 content and marked H2S content. The H2S is absorbed selectively with a part of the solvent deriving from the absorption of CO2. The solution leaving the H2S absorbed is regenerated separately from the rest of the solvent, obtaining in this way an acid gas which is rich in H2S and which can be conveyed to a sulphur recovery unit. The lay-out in figure 3.2.10 is an example of selective absorption and regeneration using stripping gas instead of steam. Note that the stripping gas is generally an inert gas without oxidizing agents to avoid oxidation of H2S to elementary sulphur. Final regeneration with steam would however be possible even in cases of treatment of crude gas containing H2S. 3.2.3 Design and dimensioning criteria

Eni S.p.A.
Exploration & Production Division

00342.HTP.PRC.PRG Rev.1 January 2005 Page. 85 of 175

The absorber generally has a packed column, even if plate columns have been used in some exceptional cases. SELEXOL has not shown a tendency to form foam if used to scrub synthesis gas while foaming phenomena have been note in the case of natural gas sweetening. In this case filters and gasoline elimination systems must be installed at the absorber inlet. The plates or packing material must also be dimensioned with care. The bottom of the absorber is usually designed in such a way as to ensure a residence time of the absorbing solution of less than a few minutes to favour complete absorption of the acid gases by the solution. The correct dimensioning of the absorber bottom is essential to reach the absorption approach to equilibrium set when calculating the solvent flow rate. The regeneration column is generally a packed column. A typical packing consists of 1” or 2” Pall metal rings. The packing height, in some cases where a high level of purification is requested, can be more than 20 metres. The heaters used to heat and cool the solvent can be pipe bundle type. However, it is more cost effective to use plate exchangers for which it is possible to have a pure counter-current flow. The flash tanks are usually very large with residence times of 5-6 minutes to allow good gas/liquid separation. A cartridge solution filter is always used in the absorption cycle, able to treat 210% of the circulating solution and able to entrain particles of up to 5 micron. Plenum for the stored SELEXOL solution is not necessary providing that it has been regenerated first; in general solution storage sections are not planned but, during maintenance jobs, the solution is transferred from one flash tank to another. A collection tank must be envisaged for all continual and accidental blowdowns with a booster pump to convey the blowdowns to the absorption system not only to avoid pollution of the sewers but also because of the high cost of the solution. 3.2.4 Construction materials SELEXOL is a non corrosive solvent which also acts as a corrosion inhibitor when working in a highly corrosive environment like that of a wet gas with high CO2 concentration. Indeed, decarbonation plants are built in carbon steel as are H2S elimination ones. However, some equipment in the regeneration zone where materials come into contact with wet CO2 and H2S must be made of stainless steel.

Eni S.p.A.
Exploration & Production Division

00342.HTP.PRC.PRG Rev.1 January 2005 Page. 86 of 175

This equipment includes the regeneration column (even if in the past they were made of carbon steel with high corrosion reinforcement) with relative packing, the head condenser and the reflux accumulator. It is advisable to use stainless steel also for the lines which convey the vapours arriving from the boiler; a kettle type boiler can be made with carbon steel pipes and skirt. The SELEXOL solution originally contains around 10 ppm of chlorides; it is therefore extremely important to control the chlorides especially if frequent top ups are necessary. It is advisable to use stainless steel for the pipes that convey the preheated solution to the regeneration column head. To assess the effectiveness of a process lay-out first of all it is necessary to define the global energy balance. That is, the thermal energy needed to regenerate the solvent, the energy needed for circulation and the energy needed to cool the solvent must be evaluated. Indeed, gas can be sweetened in certain plants with a wide range of process parameters. For example, the flow rate of solvent can be reduced by increasing the regeneration heat and lowering the temperature of the solvent conveyed to the absorption. See the graphs in figures 3.2.11 and 3.2.12 for a rough assessment of the rate of solvent needed to sweeten a given flow of gas. The graph in figure 6.3.11 can be used to estimate the flow rate of solvent required to absorb the CO2, while the graph in figure 3.2.12 can be used to estimate the flow rate of solvent needed to absorb the H2S. Not taking into consideration the interaction between CO2 and H2S it can be said that the flow rate to assume is the higher value of the two values indicated on the respective graphs. The graph in figure 3.2.11 is used with the molar fraction of the CO2 in the gas to be treated and its pressure, plotted in quadrant number 1. With the calculated parameter move up to quadrant number 2 until intersecting with the value the approach to equilibrium on the bottom of the absorber value; typical approach to equilibrium values for CO2 are 85 % - 90 %. Then move left to the third quadrant until intersecting with the temperature of the solution at the bottom of the absorber and then down to quadrant number 4 until intersecting with the difference in concentration of the CO2 between the gas to be treated and the sweetened gas. This point represents the flow rate of solvent needed in m3/h for a gas rate of 100,000 Nm3/h.

Eni S.p.A.
Exploration & Production Division

00342.HTP.PRC.PRG Rev.1 January 2005 Page. 87 of 175

The graph in figure 3.2.12 is used in the same way; typical approach to equilibrium values for H2S are 70 % - 80 %. The solvent can be regenerated in different ways: - simple flash - stripping with steam - stripping with gas (inert or air) Flash regeneration is used when the solvent load is very high. Stripping agent regeneration is used when a high level of regeneration is requested. Instead, flash regeneration is sufficient when a gas with high CO2 content has to be decarbonated to obtain a CO2 content of 2%–3%. To calculate the regeneration energy balance with direct or indirect steam the heat of the stripping steam and the heat needed to heat the solvent between the inlet temperature at the regeneration column and the outlet temperature has to be taken into consideration, excluding the desorption heat of the released gas. To this end, it can be estimated that the temperature at the bottom of the regeneration column is usually around 125°C, while the inlet temperature depends on the level of thermal recovery in the rich solution/lean solution exchanger. If the inlet temperature is 125°C it can be assumed that a stripping steam rate of 20 Kg of steam per m3 of solution is sufficient. When inert has is used for regeneration a flow rate of 25 Nm3 per m3 of solution is sufficient. If there are no sulphur compounds in the gas to be sweetened, it is possible to regenerate the solvent using air; any sulphur compounds present in the solvent would however be oxidized to elementary sulphur.

Eni S.p.A.
Exploration & Production Division Evaluation of hydrocarbon absorption

00342.HTP.PRC.PRG Rev.1 January 2005 Page. 88 of 175

As stated above, hydrocarbons are soluble in the SELEXOL process solution. Since releasing hydrocarbons along with the acid gas during regeneration of the solvent could represent excessive loss of energy, the hydrocarbons are often recycled in the absorber and separated by flashing the solvent. It is essential to choose the pressure at which the flash is to take place with great care. Indeed, if the flash takes place at high pressure few acid gases would be released and there would be a saving of hydrocarbon recompression energy; instead, if the flash takes place at low pressure, the hydrocarbons would not be lost during the subsequent regeneration stages but many acid gases which should be recycled in the absorber would be lost, with high recompression costs. A pressure is usually chosen where the separated gases can be recycled in the absorber with a single compression stage. For example, if absorption takes place at 70 bar the flash of hydrocarbons could take place at 20 - 25 bar. To make a rough estimate of the amount of hydrocarbons dissolved in the SELEXOL solution the relative solubility data given in figure 3.2.6 can be used, taking as reference data the solubility of the acid gas obtainable from figures 3.2.11 and 3.2.12. The results that can be obtained from decarbonation of a gas at a pressure of 70 abs. bar and a temperature at the bottom of the absorber of 0°C with approach to equilibrium of 85%; a flash of the solution at a pressure of 21 abs. bar has been estimated with recycling of the flash gases in the absorber; the rate of the Selexol solution is 690 m3/h. (Nm3/h) (Nm3/h) (Nm3/h) (Nm3/h) (Nm3/h) (Nm3/h) Crude gas 20,000 60,000 10 ,000 6,000 4 ,000 100,000 Sweet gas 1,300 58,570 4,795 --64,665 Absorbed gas 18,700 1,430 5,205 6,000 4 ,000 35,335

CO2 CH4 C2H6 C3H8 C4H10 Total

Note the large quantities of hydrocarbons absorbed with CO2, above all ethane; this result represents the limit of applicability of the Selexol process.

Eni S.p.A.
Exploration & Production Division

00342.HTP.PRC.PRG Rev.1 January 2005 Page. 89 of 175

VAPOUR PRESSURE– mm Hg

TEMPERATURE - °C FIGURE 3.2.1 – SELEXOL – VAPOUR PRESSURE

Eni S.p.A.
Exploration & Production Division

00342.HTP.PRC.PRG Rev.1 January 2005 Page. 90 of 175

SELEXOL 100%

DENSITY – Kg/dm3

TEMPERATURE - °C FIGURE 3.2.2 – SELEXOL – DENSITY

Eni S.p.A.
Exploration & Production Division

00342.HTP.PRC.PRG Rev.1 January 2005 Page. 91 of 175

SELEXOL 100%

SPECIFIC HEAT– Kcal/Kg•°C

TEMPERATURE - °C FIGURE 3.2.3 – SELEXOL – SPECIFIC HEAT

Eni S.p.A.
Exploration & Production Division

00342.HTP.PRC.PRG Rev.1 January 2005 Page. 92 of 175

SELEXOL 100%

VISCOSITY - centipoise

TEMPERATURE - °C FIGURE 3.2.4 – SELEXOL – VISCOSITY

Eni S.p.A.
Exploration & Production Division

00342.HTP.PRC.PRG Rev.1 January 2005 Page. 93 of 175

SELEXOL H20

95% PESO 5% PESO

THERMAL CONDUCTIVITY– Kcal/m•h•°C

TEMPERATURE - °C FIGURE 3.2.5 – SELEXOL – THERMAL CONDUCTIVITY

Eni S.p.A.
Exploration & Production Division

00342.HTP.PRC.PRG Rev.1 January 2005 Page. 94 of 175

ALL THE SOLUBILITY VALUES REFER TO A TEMPERATURE OF 20 °C, AT A PRESSURE OF 70 bar, WITH MOLAR CONCENTRATION APPROACHING ZERO AND ARE EXPRESSED AS A PARAMETER OF THE SOLUBILITY OF METHANE

COMPONENT H2 CO C1 C2 C2H4 CO2 C3 iC4 nC4 COS iC5 H2S H2S C6 CH3SH C7 CS2 C4H4S H2O

_______________ _______________ _______________ _______________ _______________ _______________ _______________ _______________ _______________ _______________ _______________ _______________ _______________ _______________ _______________ _______________ _______________ _______________ _______________

0.20 0.43 1.0 6.4 7.3 15.0 15.3 28.0 35.0 35.0 67.0 83.0 134.0 165.0 340.0 360.0 360.0 8100.0 11000.0

FIGURE 3.2.6 - SELEXOL – RELATIVE SOLUBILITY OF GAS

Eni S.p.A.
Exploration & Production Division

00342.HTP.PRC.PRG Rev.1 January 2005 Page. 95 of 175

FIGURE 3.2.7 –

NON SELECTIVE SELEXOL– GAS WITH HIGH CO2 CONTENT AND TRACES OF H2S

Eni S.p.A.
Exploration & Production Division

00342.HTP.PRC.PRG Rev.1 January 2005 Page. 96 of 175

FIGURE 3.2.8 –

SELECTIVE SELEXOL FOR H2S – GAS WITH LOW CO2 CONCENTRATION

Eni S.p.A.
Exploration & Production Division

00342.HTP.PRC.PRG Rev.1 January 2005 Page. 97 of 175

FIGURE 3.2.9 –

SELECTIVE SELEXOL FOR H2S – GAS WITH HIGH CO2 CONCENTRATION

Eni S.p.A.
Exploration & Production Division

00342.HTP.PRC.PRG Rev.1 January 2005 Page. 98 of 175

FIGURE 3.2.10 – SELECTIVE SELEXOL FOR H2S – GAS WITH HIGH H2S AND LOW CO2 CONCENTRATION

Eni S.p.A.
Exploration & Production Division
TEMPERATURE OF SOLUTION AT THE BOTTOM OF THE ABSORBER

00342.HTP.PRC.PRG Rev.1 January 2005 Page. 99 of 175
APPROACH TO EQUILIBRIUM

RATE OF SELEXOL FOR 100000 Nm3/H OF CRUDE GAS

CRUDE GAS PRESSURE

INLET-OUTLET MOLAR FRACTION OF CO2

MOLAR FRACTION OF CO2 IN THE CRUDE GAS

FIGURE 3.2.11 – SELEXOL – EVALUATION OF SOLVENT RATE - CO2

Eni S.p.A.
Exploration & Production Division
TEMPERATURE OF SOLUTION AT THE BOTTOM OF THE ABSORBER

00342.HTP.PRC.PRG Rev.1 January 2005 Page. 100 of 175
APPROACH TO EQUILIBRIUM

RATE OF SELEXOL FOR 100000 Nm3/H OF CRUDE GAS

CRUDE GAS PRESSURE

INLET-OUTLET MOLAR FRACTION OF CO2

MOLAR FRACTION OF CO2 IN THE CRUDE GAS

FIGURE 3.2.12 – SELEXOL – EVALUATION OF SOLVENT RATE - H2S

Eni S.p.A.
Exploration & Production Division 3.3 3.3.1 Chemical-physical absorption - SULFINOL Process Description of the process

00342.HTP.PRC.PRG Rev.1 January 2005 Page. 101 of 175

Shell’s SULFINOL process is a chemical-physical process: The first plant went into operation in 1964 and there are now some 150 plants throughout the world. The process is used for the purification of natural gas (around 50% of the operations) and for the purification of synthesis gas (the other 50%). The fluid used for the absorption of the acid gases is a watery solution of physical solvent (tetrahydrothiophene 1-1 dioxide or Sulfolan) and a chemical solvent such as diisopropanolamine (DIPA); other amines can be used such as MDEA in mixture with Sulfolan, as happens in some cases in more modern plants. Sulfolan acts as a physical solvent while the amine’s typical absorbing capacity is the result of a chemical reaction; the typical concentrations of the SULFINOL solution are: Sulfolan DIPA H2O 40 % weight 45 “ 15 “

The SULFINOL solution is ideal in the cases of absorption of COS, CS2 and mercaptans for which its absorbing capacity is extremely high (at 70 abs. bar less than 10 ppm vol. of mercaptans can be reached in the sweet gas); the presence of a physical solvent along with DIPA does not however allow selectivity as regards CO2; if selectivity is necessary than MDEA-Sulfolan mixtures must be used . The optimal field of use for this process is gas with an H2S/ CO2 ratio of more than 1. Consequently, the presence of a physical solvent means that the solution has a high absorbing capacity as regards hydrocarbons which provokes greater absorption of the amines but which is still less than that of the traditional physical processes; a flash tank between the absorber and regenerator is therefore needed to produce an acid gas with hydrocarbon content which is compatible with supply to a Claus unit. As opposed to physical absorbents, SULFINOL solutions are not able to dry the sweet gas except for a slight reduction of the dew point in H2O of not more than 2 - 5°C. Figure 3.3.1 shows the theoretical absorption capacity of Sulfolan, water, MEA 20% weight and typical SULFINOL solutions as a function of the partial pressure of H2S; it is clear how advantageous this solution is as the partial pressure increases.

Eni S.p.A.
Exploration & Production Division Some physical characteristics of Sulfulan: Molecular weight Boiling point Freezing point 120.17 285 27.5 6 0 177 528 52.2 2.7 123 113.9 0.31 0.35 0.40 0.00002 0.00210 0.126

00342.HTP.PRC.PRG Rev.1 January 2005 Page. 102 of 175

100% weight 95% weight 0% weight

Flash point Critical temperature Critical pressure Heat of fusion Heat of vaporization Specific heat

Vapour pressure

Kg/Kmol °C °C °C °C °C °C atm abs Kcal/Kg Kcal/Kg Kcal/Kg Kcal/Kg.°C Kcal/Kg.°C Kcal/Kg.°C Kg/cm2 abs Kg/cm2 abs Kg/cm2 abs

Figures 3.3.2, 3.3.3, 3.3.4 and 3.3.5 show some physical characteristics of standard lean SULFINOL solutions: density, viscosity, specific heat and thermal conductivity. The SULFINOL solution in small quantities is biodegradable in the typical refinery biological treatments; the toxicity of the solution for fish is fairly low (more than 4 - 5 g/litre). The cost of the SULFINOL solution is fairly high; compared to primary and secondary amines the unit cost is around 3 times more; considering the high concentrations of the solutions used it is therefore necessary to note that the investment for the first charge is around 10-15 times higher than that of amines such as MEA and DEA. 3.3.2 Lay-outs used The typical lay-out for the SULFINOL process is the classical one for amine processes shown in figure 3.1.28. However, a vacuum reclaimer must be installed as shown in figure 5.1.2, able to remove the products of degradation such as DIPA-oxozolidone from the solution. The predicted consumption of DIPA due to secondary reactions is fairly important; a plant with a fairly low circulation (30 - 40 m3/h) which treats gas containing H2S, CO2 and other sulphur compounds has an estimated consumption of approx. 1 Kg/h of solution. 3.3.3 Design and dimensioning criteria

Eni S.p.A.
Exploration & Production Division

00342.HTP.PRC.PRG Rev.1 January 2005 Page. 103 of 175

The absorber is generally a plate columns which can sometimes have more than 30 plates as in the case of high level purification of H2S and other sulphur organic substances. The tendency of the solution to foam is limited, so there is no need for high margins in the dimensioning of the columns. Like for most physical solvents, the residence time of the solution must be approx. 6 minutes at the bottom of the absorber and at the bottom of the regenerator in order to approach equilibrium of physical absorption and to move away from equilibrium during regeneration. The bottom of the absorber has a thin layer of packing material to favour the absorption of acid gases. Despite the fact that Sulfulan and DIPA do not have high vapour pressure, it is preferable, to limit consumption, to install a gas cooling or scrubbing system at the head of both columns; the ideal temperature of the sweet gas leaving the absorber or of the acid gas leaving the regenerator is less than 35°C. The tendency of the solution to become dirty is fairly limited; if plate exchangers are used to recover heat between solution/solution it is preferable to increase the capacity of the mechanical filter; in the case of transformation to SULFINOL of a plant previously operating with another solvent is it necessary to clean the plant chemically to prevent the SULFINOL from acting as a pickling agent and removing all the metal scales present in the equipment involved in the circulation. Unlike other amine solutions, SULFINOL does not expand when it solidifies so no special anti-freeze measures are needed. The need for a flash tank between the absorber and regenerator to separate most of the hydrocarbons present in the rich solution; the residence time of the liquid is around 6 minutes. If necessary, an absorption tower can be used to absorb the H2S in the gas leaving the flash tank to limit the H2S concentration; a small quantity of fresh solution is sufficient to ensure good purification. Considering that the SULFINOL solution tends to absorb heavy aromatic hydrocarbons, if a Claus unit is installed downstream suitable acid gas treatment techniques must be used to achieve full combustion (see section 4.3.). The regeneration column is generally a plate column with 15-20 regeneration plates plus 2-3 acid gas scrubbing plates at the head. In general, threaded connection should be avoided, as generally required for physical solvents, to prevent leakage of the solution; however, Teflon seals are suitable for the threaded parts. The seals of pipes and equipment are made of graphite impregnated asbestos; rubber or elastomer seals should be avoided. A mechanical filter is usually installed to entrain particles of up to 50-100 micron; during the pre start-up stage

Eni S.p.A.
Exploration & Production Division

00342.HTP.PRC.PRG Rev.1 January 2005 Page. 104 of 175

of the plant it is common practice to filter the solution through cartridges able to entrain particles of 4-5 micron; after having stabilized the concentration of solids in the solution, the cartridges are replaced with normal ones able to filter up to 50 -100 micron. Plenum in the storage and blowdown collection tanks must be provided using inert gas. The dimensioning of a SULFINOL plant requires detailed calculations and the preparation of a global thermal balance; for a rapid evaluation of the flow rate it is however possible to use the method described below which allows several simplifications but which is sufficiently accurate for a rough feasibility study. The net pick-up of acid gases in the SULFINOL solution varies depending on the concentration of acid gas and on its partial pressure. In general the load that can be obtained is more favourable for H2S than CO2; the pick-ups indicated in figure 3.3.1 refer to H2S but can be considered valid for preliminary dimensioning calculations also in the case of CO2. The pick-ups indicated in the figure are calculated at equilibrium; the flow rate of solution is generally dimensioned by calculating 60-70% of approach to equilibrium. The partial pressure to consider for the calculation is the total of H2S + CO2. The execution of preliminary calculations need not take account of the incoming concentration of sulphur products such as mercaptans, COS and CS2, which are taken into consideration using laws of interaction which cannot be simplified in formulas or diagrams. The result obtainable in terms of purification is however always less than 1% in volume for CO2 (generally 500 ppm) and 20 ppm for total sulphur products when operating at a pressure of approx 70 abs. bar; proportional results can be obtained at different pressures. Refer to figure 3.3.6 for H2S; this figure correlates the consumption of vapour used to regenerate the solution with the partial pressure of H2S at the equilibrium of the lean solution regenerated at 40°C (allowing a difference in temperature of the solution between the regenerator head and tail of not more than 20°C). The consumption of regeneration vapour is however usually not less than 80 Kg/m3 of solution; the approach to equilibrium to be considered in this case is 2535% of the partial pressure of H2S at the equilibrium indicated in figure 3.3.6. An example of use of the diagram. To determine the H2S that can be obtained in an absorber operating at 50 abs. bar, consuming 80 Kg/m3 of regeneration steam and considering an approach to equilibrium of 25%; the allowable parts per million in volume of H2S are:

Eni S.p.A.
Exploration & Production Division

00342.HTP.PRC.PRG Rev.1 January 2005 Page. 105 of 175

ppm H2S =

16 x 10-6 x 106 ------------------- = 1,28 ppm vol. 50 x 0,25

A steam consumption of 80 Kg/m3 of solution is typical when the gas to be treated has a moderate presence of COS and mercaptans; in the case of the presence of COS in quantities of more than 50 ppm in the supply gas, the consumption of steam must be increased even up to 150 Kg/m3 of solution. The quantity of C1-C2-C3 hydrocarbons absorbed by the standard SULFINOL solution is less than half that absorbed by a physical solvent; it is similar to that absorbed by a physical solvent for C4 hydrocarbons; instead, aromatic hydrocarbons are absorbed in a much more massive manner. 3.3.4 Construction materials The solution used in the SULFINOL process has similar corrosion characteristics to primary amines; the level of corrosion is however higher if the gas to be treated contains CO2 with H2S of less than 1%. Cast iron must be not be used. In general, when temperatures are below 80°C, carbon steel is used with corrosion reinforcement of 3mm; the carbon steel parts are generally subjected to annealing to prevent the typical stress cracking phenomena of amines. The absorber is made of carbon steel killed with stainless steel plates; if the bottom temperature is high, the lower part of the absorber can be cladded with stainless steel. It is advisable to avoid the accumulation of chlorides in the solution as these could cause severe corrosion probably because they destroy the protective film created by the SULFINOL solution in the steel; the chlorides are almost always introduced into the system with replenishment water which is not fully demineralised: their content should never exceed 50 ppm. The packing material at the bottom of the absorber is AISI 321 o 347. The solution/solution exchanger is made of stainless steel, except in cases where the temperature is less than 80-90°C; if pipe bundles with several bodies are used, it is more cost-effective to use carbon steel for the pipe side of the first body, which operates at lower temperature. The flash tank, which generally operates at a temperature of less than 80°C, is made of carbon steel. The regenerator is made of carbon steel with stainless steel plates.

Eni S.p.A.
Exploration & Production Division

00342.HTP.PRC.PRG Rev.1 January 2005 Page. 106 of 175

The parts of the boiler in contact with the solution are made of carbon steel if a heating fluid at a temperature of less than 150°C is used, otherwise stainless steel is used. The material used for the acid gas coolant, acid gas separator and relative pipes depends in the type of acid gas: in the past carbon steel was used for H2S and stainless steel for CO2; nowadays stainless steel is preferred for both gases to avoid severe corrosion event after just a few months of operation. The solution circulation pumps are made of stainless steel; carbon steel would have a very short life (even less than one year): stainless steel is used also for the solution recycling pumps from the reclaimer and for the acid condensate pumps. The reclaimer is made of carbon steel, except for the boiler pipes which are generally made of stainless steel. Mention has already been made of rubber seals which must be avoided in operations with SULFINOL solution while the only acceptable elastomero is Ethylene-Propylene-Diene-Monomer EPDM which must be applied without greases. As a rule, carbon steel should be used for solution pipes up to 80°C and stainless steel for higher temperatures; the regulation valves should be made of stainless steel.

Eni S.p.A.
Exploration & Production Division

00342.HTP.PRC.PRG Rev.1 January 2005 Page. 107 of 175

SOLUZIONE MEA 20% PESO

PARTIAL PRESSURE H2S - ata

SULFOLANO ACQUA

SOLVENTE FISICO GENERICO

SOLUZIONE SULFINOL

H2S EQUILIBRIUM LOAD – Nm3 H2S/m3 solution FIGURE 3.3.1 – COMPARISON OF ABSORBING CAPACITY

Eni S.p.A.
Exploration & Production Division

00342.HTP.PRC.PRG Rev.1 January 2005 Page. 108 of 175

SOLUZIONE SULFINOL STANDARD DIPA 45% PESO SULFOLANO 40% PESO H20 15% PESO

DENSITY– Kg/m3

TEMPERATURE - °C FIGURE 3.3.2 – SULFINOL – DENSITY OF LEAN SOLUTION

Eni S.p.A.
Exploration & Production Division

00342.HTP.PRC.PRG Rev.1 January 2005 Page. 109 of 175

SOLUZIONE SULFINOL STANDARD DIPA 45% PESO SULFOLANO 40% PESO H20 15% PESO

VISCOSITY - centipoise

TEMPERATURE - °C FIGURE 3.3.3 – SULFINOL – VISCOSITY OF LEAN SOLUTION

Eni S.p.A.
Exploration & Production Division

00342.HTP.PRC.PRG Rev.1 January 2005 Page. 110 of 175

SOLUZIONE SULFINOL STANDARD DIPA 45% PESO SULFOLANO 40% PESO H20 15% PESO

SPECIFIC HEAT– Kcal/Kg•°C

TEMPERATURE - °C FIGURE 3.3.4 – SULFINOL – SPECIFIC HEAT OF LEAN SOLUTION

Eni S.p.A.
Exploration & Production Division

00342.HTP.PRC.PRG Rev.1 January 2005 Page. 111 of 175

SOLUZIONE SULFINOL STANDARD DIPA 45% PESO SULFOLANO 40% PESO H20 15% PESO

THERMAL CONDUCTIVITY – Kcal/m•h•°C

TEMPERATURE - °C FIGURE 3.3.5 – SULFINOL – THERMAL CONDUCTIVITY OF LEAN SOLUTION

Eni S.p.A.
Exploration & Production Division

00342.HTP.PRC.PRG Rev.1 January 2005 Page. 112 of 175

PARTIAL PRESSURE H2S IN THE SOLUTION REGENERATED AT 40°C - ata •10-6

STEAM CONSUMPTION FOR REGENERATION – Kg/m3 FIGURE 3.3.6 – SULFINOL – STEAM FOR REGENERATION OF SOLUTION

Eni S.p.A.
Exploration & Production Division 4.

00342.HTP.PRC.PRG Rev.1 January 2005 Page. 113 of 175

OXIDATION PROCESSES TO REDUCE HYDROGEN SULPHIDE This classification includes all the oxidation absorption processes in liquid phase and the oxidation processes in gaseous phase; the first include the STRETFORD, SULFINT and LO-CAT processes; the second include the CLAUS units. The processes in liquid phase are selective and directly transform the H2S content in the gas to be treated into sulphur; they can operate at high or low pressure and are limited by the sulphur potential which ranges from several Kg/h to a maximum of around 10 t/d, above which they are no longer economically advantageous.

4.1

SULFINT and LO-CAT processes Refer to figure 4.4.1 for the SULFINT process. The H2S is absorbed by the solution (complex of iron chelates) in a Venturi or an absorption column; the rich solution is oxidised with air in an oxidizer: the finely divided solid sulphur formed during oxidation precipitates to the bottom of a settler. The clear solution collected at the head of the settler is recycled in the absorber. The sulphur mud, at a concentration of 5% in weight, is further concentrated through centrifugation and is then conveyed at a concentration of 30% in weight, for subsequent purification, for example through fusion, to obtain a more easily marketable product. The settled solution, containing secondary compounds formed during the various stages of the process, (mainly sulphates), is sent to permeable membranes which separate the large molecules (iron chelates) from the small molecules (sulphates); the regenerated solution is recycled in the oxidizer while the by-products, which are not harmful, are discharged into a effluent treatment system. In small plants mud treatment can be greatly simplified if the sulphur produced can be discharged directly. If the quantity of H2S in the gas to be treated is high several absorption columns would be needed. LO-CAT Process Refer to figure 4.1.2 for the LO-CAT. The idea is similar to that of the SULFINT process; the solution used is iron chelate based buffered at pH 8 with Na2CO3 and KOH; the H2S is oxidized to sulphur by means of a special non-toxic ethylendiamine tetra-acid based catalyst. The H2S can be absorbed and the solution is oxidized in a single tank when the procedure is used for low pressure exhaust gas; otherwise, a separate packing or bubble absorption column preceded or not be a Venturi can be used.

Eni S.p.A.
Exploration & Production Division

00342.HTP.PRC.PRG Rev.1 January 2005 Page. 114 of 175

The sulphur produced can be sent for further treatment if a high purity product is required; a part of the solution must be evacuated to keep under control the concentration of secondary compounds in the solution.

Eni S.p.A.
Exploration & Production Division

00342.HTP.PRC.PRG Rev.1 January 2005 Page. 115 of 175

FIGURE 4.1.1 – OXIDATION PROCESSES IN LIQUID PHASE - SULFINT

Eni S.p.A.
Exploration & Production Division

00342.HTP.PRC.PRG Rev.1 January 2005 Page. 116 of 175

FIGURE 4.1.2 – OXIDATION PROCESSES IN LIQUID PHASE – LO-CAT

Eni S.p.A.
Exploration & Production Division 4.2 Monterotondo process with biological oxidation

00342.HTP.PRC.PRG Rev.1 January 2005 Page. 117 of 175

The development of fields with a high rate of H2S has contributed to the study of innovative processes to reduce this dangerous pollutant, with competitive engineering costs compared to traditional technologies. For this reason EniTecnologie is developing a redox system based on a chemical and biological approach in liquid phase, characterized by an almost zero environmental impact considering that the process has been classified “zero discharge”. Redox technologies in liquid phase are advantageous also in reducing H2S in gaseous current with low pollutant content. These technologies are based on two main steps: in the first step the H2S is oxidised to elementary sulphur through reduction of metal ions solubilized in water in free or complex organ; in the second step the reduced ions are re-oxidised generally using the oxygen in the air. The high demand for redox technologies has led to the development of new plants mainly based on the using the Fe2+/Fe3+ [2] redox couple. In recent years much space has been gained by biotechnological processes based on the exploitation of the capacity of Thiobacilli to directly oxidise sulphides to elementary sulphur [3]. An interesting way of combining efficiency of the oxidation reaction of sulphides with the ferrous ions and the oxidation capacity in Thiobacilli acid environment is based on the following pairs of reaction: H2S + Fe2(SO4)3 -> S + 2 FeSO4 + H2SO4 2 FeSO4 + H2SO4 + 0,5 O2 -> Fe2(SO4)3 + H2O_____________________________ H2S + 0,5 O2 -> S + H2O The first reaction takes place spontaneously with high kinetics; the second is catalyzed by Thiobacillus ferrooxidans able to react in a pH range pH (1.4-1.8) in which the iron ion does not precipitate, increasing the natural oxidation kinetics of the ferrous iron some 500,000 fold [4]. The difficulties involved in this process regard the choice of a suitable reactor for the precipitation and separation of the elementary sulphur, the low oxidation efficiency of the biological systems and the limited stability over time of the alignment between the two main stages of the process. During the experimentation stage the data needed to design a preliminary bench-scale plant was collected. In particular, for the chemical section of the process, the mechanisms involved in the formation of crystalline forms of sulphur (more easily separable from the reaction mixture) as a function of the liquid-gas contact system, reaction temperature and reactor configuration were studied. As regards the biological section of the process, aspects related to the multiplication of the micro-organisms were studied in more detail, making the nutritional needs compatible with the need to avoid the formation of nutrient bouillon very low solubility. Moreover, the oxidation capacities with respect to the ferrous ions of a micro organism cultivated in dispersed or adhesive form on inert supports.

Eni S.p.A.
Exploration & Production Division

00342.HTP.PRC.PRG Rev.1 January 2005 Page. 118 of 175

The continuative management of the bench plant for around one year firstly allowed us to define the conceptual diagram of the process, as shown in figure 4.1.3.

BIOLOGICAL AND CHEMICAL REDUCTION OF H2S IN GASEOUS STREAMS CONCEPTUAL DIAGRAM OF THE ENITECNOLOGIE PROCESS

FIGURE 4.1.3 DIAGRAM OF THE ENITECNOLOGIE BIOLOGICAL REDUCTION PLANT.

CHEMICAL

Subsequently the know-how needed to design a prototype plant and to make the first economic estimations was developed. The study also continued with the aim of identifying supports suitable for the biological substratum. The prototype is a skid mounted type with a maximum capacity of 10 kg/day. As can be seen in the figure, the acid gas to be treated is sent to the reaction column into which the acid solution of ferric ions is introduced in a concentration of 0.3 M. The slurry obtained in this way (density of 1.2-1.4 g/l) is conveyed to a filtering system, which separates the ferrous sulphates from the sulphur. Then, this current is fluxed with water in a fluxing reactor and then vacuum filtered, to obtain a cake with 40-60% in weight of sulphur. The filtered current is then sent to the biological reactor following replenishment of the ferric ion solution and the introduction in the system of the nutrients needed for the growth of the bacteria. The redox reaction to restore the original solution takes place in the reactor. The bacteria possess the energy needed for the growth from oxidation of the ferrous ions. As stated, continuative operations in conditions which simulate those existing in production plants has verified that the new process can be considered “zero discharge” and does not generate effluent or waste of any type. The use of an autotrophic micro-organism such as T. ferrooxidans allows even a small portion of carbon dioxide (15 kg per ton of sulphur produced) to be eliminated. The elementary sulphur produced contains good commercial characteristics, and is particularly suited for use in agriculture in terms of purity (~ 99%), dispersion in water, iron ion content and requires modest consumption of chemicals and energy.

Eni S.p.A.
Exploration & Production Division

00342.HTP.PRC.PRG Rev.1 January 2005 Page. 119 of 175

Gaseous currents of different origin (excluding those containing SO2 in a concentration > 2 mM) can be treated with hydrogen sulphide at concentrations ranging from just a few ppm up to more than 70% in volume, demonstrating marked operative flexibility. It should also be noted that the plant operates at pressures and temperatures close to environmental values. Comparative evaluations to date show how the new chemical-biological process is competitive an economic point of view and as regards environmental impact compare to competitors’ processes based exclusively on chemical approaches. These considerations have led to the inclusion of this process among the future hydrogen sulphide reduction options. 4.3. Claus process and variants The CLAUS process which transforms H2S directly into sulphur is applied to acid gases produced in the sweetening plants and to the gaseous effluents arriving from production units containing high concentrations of H2S or other substances, sulphides such as CO2, CS2, mercaptans or other sulphur compounds. 4.3.1 General description of the process, reactions involved and catalysts involved The CLAUS process is based on a technology used since 1883 and which consisted in burning the H2S with air in the presence of a catalyst to obtain sulphur. Already in 1932 the IG CLAUS process was based on the combustion with SO2 of a third acid gas to be treated; the products of combustion of the acid gas are combined with the remaining part of the gas and sent to a catalytic converter which operated at 200 - 300 °C; the sulphur was therefore produced only in the catalytic conversion stage (see conversion reactions on the following pages) with fairly modest performance. In 1936 K. Braus developed the so-called MODIFIED CLAUS process which envisaged the combustion of all the H2S contained in the acid gas with the stoichiometric air for the transformation of the H2S into sulphur; this discovery allowed for marked simplification of the technology and above all allowed high levels of H2S /sulphur conversion to be reached through exploitation of the heat conversion reactions during the combustion stage (see below) besides the catalytic reaction which took place downstream of the combustion of the acid gas. At present the technology uses the MODIFIED CLAUS process as it was developed by several US and European companies immediately after the war and its ongoing improvements made possible by in-depth investigation of various aspects of the process. The best materials available for the construction and above all the use of particular instrumental components have resulted in the very high level of reliability of these processes above all if compared to the operative and maintenance situations in the early Seventies which were certainly not optimal.

Eni S.p.A.
Exploration & Production Division

00342.HTP.PRC.PRG Rev.1 January 2005 Page. 120 of 175

The cost of CLAUS units has dropped greatly since the “package” concept was introduced on an industrial scale at the end of the Fifties; this concept envisages gathering together the equipment needed for the process in a few multi-purpose components (2 or 3) with a marked saving in cost and without operative and management constraints. The concept of “package” construction is economically advantageous for units with dimensions of up to 60 t/d of produced sulphur even it is applied in part also for higher potential. The basic criterion of the MODIFIED CLAUS process therefore implies the full combustion with SO2 of a third of the H2S contained in the supply acid gas. The combustion reaction takes place in a single stage, burning the acid gas substoichiometrically with the quantity of air needed for the transformation of H2S into sulphur; that is, using a half mole of oxygen per mole of H2S. The SO2 produced in the combustion reacts with the H2S which has not reacted forming sulphur in the form of vapour and water vapour according to the following simplified reactions: H2S + ½O2 2 H2S + SO2 === === H2O + SO2 oxidation 3S + 2H2O conversion

The sum of the two reactions can be expressed as 3 H2S + 1½O2 === 3S + 3H2O

or better, the simplified reaction can be expressed as H2S + ½ O2 === S + 3 H2S

It has already been mentioned that the various reactions take place in different stages: first of all there is a thermal reaction in which the H2S is burned in an environment with very small oxygen content; then there are two or more stages of catalytic conversion in which the process gas is subject to subsequent conversion reactions in such a way as to obtain the almost complete conversion of the H2S into sulphur. The catalytic conversion reaction is exothermal so greater efficiency can be obtained operating at lower temperature, compatibly with the dew point, of the sulphur produced in the reacted gas. Any condensation of the sulphur on the catalyst would drastically limit the activity of the catalyst itself; in this case it would be lost most of the contact surface that would be blocked by the sulphur. Each conversion stage, whether thermal of catalytic, is followed by a cooling stage of the process gas to condense the sulphur produced which is separated from the gas and recovered in liquid form; the elimination of the sulphur produced during previous the conversion stage obviously maximizes conversion in the subsequent

Eni S.p.A.
Exploration & Production Division catalytic stage.

00342.HTP.PRC.PRG Rev.1 January 2005 Page. 121 of 175

The two base variants of the modern CLAUS process are the “straight-through", which envisages combustion of all the acid gas with all the stoichiometric combustion air and the "Split-flow" which envisages the combustion of only a part of the acid gas with all the stoichiometric combustion air. The first variant is used on acid gas with a H2S content of more than 60% in volume and allows high levels of global conversion of H2S into sulphur. The "split-flow" variant instead is used on acid gas with an H2S content of between 20% and 60% in volume; the conversion efficiency is less than the "Straightthrough" method with a plant which a little less complex but more problematic to manage. The principle on which the split-flow variant is based is to reach a sufficiently high flame temperature to allow stable acid gas combustion; this cannot be obtained with H2S poor supply currents and with high quantities of diluents (almost always CO2). A flame temperature of less than 1000°C is considered the minimum acceptable to have a stable flame; this temperature can be obtained only with H2S concentrations in the acid gas of around 60% in volume. However, if only a part of the acid gas is reacted with the air needed for the CLAUS reaction, the flame temperature increases proportionately to the quantity of bypassed acid gas. The other part of the acid gas is sent into the system downstream of the combustion. The acid gas not by-passed therefore is subjected to combustion with higher quantities of O2 than the stoichiometric for the CLAUS reaction (O2/H2S = 0.5), but never higher than the quantity corresponding to the complete combustion of H2S to SO2 (O2/H2S -1.5); the by-passed acid gas cannot therefore be more than 2/3 of the total acid gas. The acid gas supplied to the CLAUS plants must have typical pressures of 0.3 – 0.7 eff. bar; therefore, the acid gas arriving from the regeneration of absorption sweetening plants has a suitable pressure: if it were necessary to have another tail gas treatment plant with additional load loss, the pressure needed could easily be reached during regeneration of the sweetening solution in most of the commonly used processes by increasing the solution regeneration temperature slightly. Even if it is theoretically possible, it is not advisable to use blowers to increase the pressure of the acid gas, given the highly dangerous nature of the fluid to be compressed and the difficulty of developing machines with perfect seal; it is always preferable to increase the pressure of the gas by acting on the operating parameters of the sweetening plants upstream. The reaction heat developing in the heat and catalytic conversion stages is recovered for use as steam in multi-passage or single-passage boilers, depending on the potential of the plant. In plants with high potential steam sometimes needs to be produced at different pressure levels.

Eni S.p.A.
Exploration & Production Division

00342.HTP.PRC.PRG Rev.1 January 2005 Page. 122 of 175

Plants with a potential of less than 20 t/d of sulphur generally recover steam at a single pressure level (3-5 eff. bar); plants with greater potential produce steam at two pressure levels (10 - 60 eff. bar and 3 - 5 eff. bar); if conversion has to be maximized, steam will have to be produced at a lower pressure level (1 – 1.3 eff. bar). In the case of the production of steam at two levels, 70% - 80% of the steam produced can be at the higher pressure. Besides H2S, the acid gas supplied to a CLAUS plant can also contain hydrocarbons, CO2, H2O, NH3, HCN, CO2, CS2, mercaptans, N2, and other gases. In general H2O and N2 act like simple diluents; that is, they do not take part in the reactions even if their presence reduces the efficiency of the conversion into sulphur. Instead, CO2, besides the diluent effect, reacts with the sulphide products, forming CO2 and CS2 with further reduction of the conversion. The hydrocarbons have an even more negative effect because they consume oxygen for combustion and, besides the dilution effect, they react with the sulphide products to form CO2 and CS2; the quantity of hydrocarbons present in the acid gas must not be greater than set ratios so as not to compromise the quality of the sulphur produced. In "straight-through" type plants in general light hydrocarbons such as C1, C2 and C are tolerated in the acid gas also at a concentration of a few percent while C4+ hydrocarbons are not tolerated except in concentrations of more than 1% volume. The tolerability evaluation criteria indicated are drastically reduced in the case of "split-flow" type plants. Ammonia and HCN present in the acid gas burn, consuming oxygen and diluting the process gas but if they are not completely destroyed during the combustion stage, they can form solid by-products inside the plant such as sulphate and ammonium bisulphate when the temperature is less than 147°C, which tend to block the plant. The composition of the acid gas therefore plays a decisive role in the plant’s conversion efficiency; other factors affecting the conversion efficiency include the number of catalytic reactors, the possibility of producing a part of steam at the lowest pressure level and the gas heating system at the catalytic reactors. The efficiency of conversion into sulphur of a CLAUS unit varied from less than 90% in the case of simple units which treat an H2S poor incoming gas containing impurities to a maximum of 98.5% for plants with three reactors and H2S rich gas. At present in Italy for the treatment of refinery acid gases conversion levels of 95% to 96% of the supplied sulphur are required; the Italian authorities tasked with controlling atmospheric pollution are however tending to set higher conversion degrees, of nearly 98% as is already envisaged in some other European countries, especially in units with higher capacity.

Eni S.p.A.
Exploration & Production Division

00342.HTP.PRC.PRG Rev.1 January 2005 Page. 123 of 175

In any case, other treatment plants (Tail Gas Clean Up) are available for installation downstream of the CLAUS units which are able to increase the efficiency of global recovery of the supplied sulphur up to 99.9%; the cost of these plants can vary from 30% to more than 100% of the cost of the CLAUS unit, depending on the efficiency requested. The potential of the CLAUS units can vary from less than 1 t/d up to 1500 and more t/d per line; in Italy units are installed with a potential of between 1 and 300 t/d per line; the largest units are installed in France and in Canada downstream of the large natural gas desulphurization units. The sulphur produced in the CLAUS units is of excellent quality with purity of up to 99.95% in weight; the sulphur is generally stored in liquid form and transported in truck-tanks if the destination is within a radius of a few hundred kilometres from the site of production; however, it is possible to solidify the liquid sulphur for shipment in flakes or capsules, both in bulk and in sacks. The sulphur produced by the CLAUS units is an excellent raw material for the production of sulphuric acid and for agricultural and pharmaceutical uses. The tail gas leaving the CLAUS plants is incinerated by means of combustion at a temperature of 650-900°C to obtain full oxidation of the sulphide compounds; the combustion fumes are discharged into the atmosphere through chimneys of a suitable height. The treatment of gas with very low H2S contents (less than 20%) is possible taking measures to maintain the required flame temperature; these measures range from preheating the combustion air and the acid gas to be treated to the use of oxygen enriched air. Direct catalytic oxidation processes allow acid gases with H2S content of less than 5% to be treated. Other engineering solutions such as supported of the acid gas allow the acid gases to be treated in the entire concentration range of 5% to 20% of H2S; however very low concentrations of H2S correspond to limited efficiency with recoveries that in the worst case scenario may not even exceed 50%. Supported combustion of acid gas allows the required flame temperature to be reached, burning the fuel case with more equivalent air than that required in stoichiometric combustion of the acid gas the subsequently injecting the acid gas in the combustion products of the fuel gas; this technique is applicable in the case of acid gas with a wide variation in H2S content in low concentration ranges (5 - 20% in volume). The CLAUS process is based on the combustion of H2S in sub-stoichiometric conditions in order to maximize the transformation of H2S into sulphur. The conversion of the H2S takes place in two distinct stages: the first is essentially thermal and takes place during the combustion of the H2S, the second is catalytic

Eni S.p.A.
Exploration & Production Division

00342.HTP.PRC.PRG Rev.1 January 2005 Page. 124 of 175

and takes place in two or three serial reactors with cooling of the gas between each reactor and removal of the sulphur produced in the previous stage. The main reactions taking place during thermal conversion of H2S are: H2S H2S + ½O2 H2S + 1½O2 ==== ==== ==== H2 + H20 + H2O + ½ S2 ½ S2 SO2 905 + 1674 + 5531 Kcal/Nm3 H2S Kcal/Nm3 H2S Kcal/Nm3 H2S

During thermal conversion the hydrocarbons present in the acid react as follows: CH4 + C2H6 + C3H8 + C4H10 + 1½O2 2½O2 3½O2 4½O2 === === === === CO 2CO 3CO 4CO + + + + 2 H2O 3 H2O 4 H2O 5 H2O + + + + 5538 9190 12743 16277 Kcal/Nm3 Kcal/Nm3 Kcal/Nm3 Kcal/Nm3 CH4 C2H6 C3H8 C4H10

The reactions of the other components of the acid gas are: H2 2NH3 CO2 CO2 + + + + ½O2 1½O2 H2S 2H2S === === === === H2O N2 + CO2 + CS2 + + + 2579 3379 321 359 Kcal/Nm3 Kcal/Nm3 Kcal/Nm3 Kcal/Nm3 H2 NH3 H2S H2S

3H2O H2O 2H2O

The main reaction which takes place during catalytic conversion is: 2H2S + SO2 === 2H2O + 3S + 557 Kcal/Nm3 H2S

Catalytic conversion takes place in a temperature range of 220 to 260°C for the first converter, 200 to 240°C for the second and 180 to 220°C for the third converter. In the first converter, if the reaction temperature exceeds 250°C, hydrolysis reactions of CO2 and CS2 also take place with the formation of H2S; the hydrolysis of CO2 and CS2 is favoured by the high temperature. Note that all the sulphur produced in the thermal and catalytic conversion stages is present in gaseous form as S2-S4-S6 and S8 according to equilibriums which depend on the temperature; the sulphur is liquefied as S1 in the condensers located downstream of the single reaction stages. The conversion reactions are accelerated on synthetic alumina based catalysts; in the past bauxite was widely used but its performance from the point of view of load losses was less constant due to the load losses given the inconstant particle size of the natural product. Catalysts with well defined grain size and characteristics are available on the market: from typical alumina catalysts specifically for the CLAUS reaction those with activators to favour hydrolysis of CO2 to CS2, to those most suitable for working in slightly oxidizing atmospheres.

Eni S.p.A.
Exploration & Production Division

00342.HTP.PRC.PRG Rev.1 January 2005 Page. 125 of 175

Catalysts for Claus units are manufactured by European companies such as Rhone Poulenc and US companies such as Kaiser and ALCOA. Despite the differences claimed by the manufacturers the performance of homogeneous types of catalysts are fairly similar and in any case are not decisive in appreciably modifying the result of global conversion. 4.3.2 Equipment Thermal conversion takes place by means of combustion of H2S with air in special burners, studied ad hoc, reaching temperatures in the reaction products which depend on the composition of the acid gas and the presence or absence of products such as NH3 or HCN; the development of precise residence times of the products of combustion is essential to achieve good levels of conversion. The burners are generally of a combined type, able to operate with acid gas during normal operations and with fuel gas during plant start-up and shut-down. In the case of the presence in the acid gas of ammonia, HCN, mercaptans, large quantities of hydrocarbons or in case for high potentials (more than 60 - 70 t/d of sulphur) it is necessary to have residence times of the combustion products at the flame temperature in a refractory muffle to ensure complete combustion of all the components of the acid gas, an essential condition if the plant is to operate correctly. If the acid gas is NH3, HCN and mercaptan free and contains limited quantities of hydrocarbons combustion is possible in a submerged or fire tube combustion chamber, thus obtaining the required residence time of the flame at a lower temperature. The submerged or fire tube combustion chamber allows a more compact and economical plant to be used with shorter start-up and shut-down times even of the result of the global conversion into sulphur is slightly less than plants with refractory muffle. The various systems used to heat the gas sent to catalytic reactors are worthy of mention. The most efficient systems in terms of management and of the result of the conversion into sulphur are the indirect heating types (with steam, hot oil, heating elements): however, it is not always possible to have fluids at the required heating temperature (preferably 300°C and more for the first reactor) and therefore direct heating systems have to be used with hot process gas (reheat gas) taken from strategic positions downstream of the thermal conversion equipment (see 4.3.4.1) or burning fuel gas or part of the acid gas in inline heaters (see 4.3.4.2). Management of the direct heating systems, above all inline heaters, makes the investment higher and plant management fairly complex; the use of inline heaters should therefore be avoided when alternative systems can be used.

Eni S.p.A.
Exploration & Production Division

00342.HTP.PRC.PRG Rev.1 January 2005 Page. 126 of 175

Another possible way of heating the gas at the reactors is to use indirect systems which use the hot gases leaving the first reactor to heat the gas entering the following reactors: these systems (gas/gas exchangers) are fairly cheap even if they lengthen the plant start-up and shut-down times, due to the high inertia during the reactor heating stages. Incineration of tail gas The tail gas leaving the CLAUS units is incinerated before being discharged into the atmosphere; the most commonly adopted practice is to have a thermal incinerator which operates at high temperature (650-900°C) and which generates fumes with a residual oxygen content of 1.5% - 2% volume. Almost total oxidation of the H2S still contained in the tail gas to a residual content of even less than 10 ppm is possible with high flame temperatures. Alternatively, catalytic incinerators which operate with striking temperature of around 300°C and which have much lower fuel gas consumption can be used; the management of this equipment is more expensive and more complex especially in the case of deviation from normal the normal operating parameters of the CLAUS unit; other negative factors of catalytic incinerators are the additional load losses and the need to operate with close control of the excess of combustion oxygen, with ensuing risk of forming noticeable quantities of SO3 in the case of great excess and incomplete combustion of the H2S in the case of scarcity. The use of catalytic incinerators also rules out the possibility of direct incineration of part of the acid gas as sometimes required for thermal incinerators. The catalysts used in the past for catalytic incineration were based on bauxite (the same used for the CLAUS reaction): nowadays there are specific catalysts with special activators; these catalysts have a high activity and more suitable mechanical characteristics for the service. Heating stages A final aspect to be taken into consideration in order to fully understand how a CLAUS unit works regards the heating of the unit before it begins operating with acid gas and after the shut-down of the acid gas. Indeed, before introducing the acid gas and start producing sulphur, all the equipment which comes into contact with process gas must be heated to a temperature of more than 120°C; i.e. the temperature at sulphur solidifies. To this end fuel gas is burned and the hot products of the combustion are circulated through the unit until they reach the necessary heat level; the fuel gas is burned in the same burner by the acid gas is a special nozzle. Immediately after the gas shut-down all the sulphur in the unit (as liquid absorbed by the catalyst or accumulated at some points of the unit) has to be eliminated; this is done by burning the fuel gas in the combined burner and evaporating the sulphur with the hot products of the combustion. This is the most delicate stage of operations using a CLAUS unit; indeed, it is necessary to have stoichiometric combustion of the fuel gas to avoid the formation

Eni S.p.A.
Exploration & Production Division

00342.HTP.PRC.PRG Rev.1 January 2005 Page. 127 of 175

of gas black in the case of scarcity of oxygen as well as uncontrolled combustion of sulphur present in the unit in the case of excess of oxygen in the products of combustion which pass through all the equipment of the unit. In the case of units with muffle, a further complication during heating operations is the need to send a cooling fluid (inert gas or steam) to the products of combustion to lower the flame temperature to values which are compatible with the refractory materials used. 4.3.3 Treatment and use of the sulphur produced The sulphur produced in the various condensers located downstream of the thermal and catalytic conversion is sent to an underground cement tank and from there it is transferred to tanker trucks, to other storage tanks or for solidification. The modern plants are fitted with degassing sections for the sulphur produced to eliminate the dissolved H2S, which can be dangerous especially during liquid transport; the H2S contained in the sulphur tends to degas during transport, creating a poisonous atmosphere which is potentially explosive in the vapour phase above the level of the liquid in the tankers. Sulphur degassing processes are able to reduce the H2S to 10 - 15 ppm in weight and can be either catalytic (SNEA – EXXON processes) or mechanical (SHELL – AMOCO processes); however, in all cases the H2S is removed in an air current which is sent to the incinerator along with the tail gas for oxidation of the H2S content. In the CLAUS units the equipment containing liquid sulphur is heated using steam powered coils while the pipes and valves are lined with vapour; even if electrical heating is theoretically acceptable, it is rarely used, above all in Europe, in liquid sulphur lines. The steam generally used to heat the lines and equipment containing liquid sulphur must have a pressure of 2.5 - 5 eff. bar; higher pressures are not acceptable because they can generate high temperatures of the liquid sulphur such as to result in very high viscosity of sulphur with ensuing difficulty in its transport, as shown in figure 4.3.1.; it is generally preferred to use saturated steam at a pressure of 2.5 – 3.5 eff. bar to heat the sulphur. 4.3.4 Basic layout of a plant It has already been mentioned that CLAUS units can be "straight through" and "split flow" depending on the H2S content in the acid gas. Figures 4.3.2 and 4.3.4 show the typical layouts of the two processes. Refer to figure 6.6.2. The acid gas arriving from the regeneration section of the sweetening unit, with an H2S concentration of more than 60% in volume, is sent to a burner positioned in

Eni S.p.A.
Exploration & Production Division

00342.HTP.PRC.PRG Rev.1 January 2005 Page. 128 of 175

front of a muffle where it is burnt with the amount of air needed to develop the CLAUS reaction; the air is provided by a blower. The products of the reaction, at a temperature of 1000 -1350°C depending on the composition of the acid gas, remain in the muffle for the time needed to complete the reaction and are then sent into the boiler pipes where they are cooled, in one or more steps, to approximately 250 - 350°C. The boiler can produce vapour at a pressure of 4 - 60 eff bar, depending on the factory’s needs. The gas leaving the boiler is sent to the first sulphur condenser where it is cooled to 160 - 200°C; part of the sulphur contained in the gas is condensed, separated and sent to the buried tank after being passed through a Livesey seal. The Livesey seal consists of a container lined with liquid sulphur saturated steam; the height (head) of the sulphur in the Livesey seal applies a counter-pressure on the process gas which is higher than the maximum operating pressure of the process gas inside the plant equipment. The sulphur produced in the condenser firstly passes through the Livesey seal and is then conveyed to the liquid sulphur storage area. The gas leaving the condenser is heated to the incoming temperature of the first reactor (160 -200°C) by heating it directly with hot gas at 600 - 650°C, taken from the first passage through the recovery boiler. In the first reactor about 60 - 70% of H2S and SO2 present in the process gas is transformed into sulphur; moreover, most of the CO2 and CS2 is converted into H2S in the lower part of the catalyst which operates at a higher temperature; due to the exothermic nature of the reaction, the gas leaves the reactor at a temperature of 280 -320°C. Part of the sulphur produced in the first reactor is recovered in the second condenser where the process gas is cooled to 150 - 190°C; the condensed sulphur is separated and transferred for storage using a Livesey seal. The process gas is then heated to 200 - 240°C in a preliminary heater and enters the second catalytic reactor where around 60 - 70% of the H2S and SO2 content is transformed into sulphur. The gas leaving the second catalytic reactor at a temperature of 230 - 270°C us conveyed to the third condenser where it is cooled to 140 -180°C; the condensed sulphur is separated and sent for storage using a Livesey seal. The process gas is heated in a final heater to 180 - 220°C and then enters the third catalytic reactor where 40 -60% of the H2S and SO2 is converted into sulphur; the gas leaving the third catalytic reactor at a temperature of 190 - 220°C is sent to the fourth condenser where it is cooled to 130 - 150°C.

Eni S.p.A.
Exploration & Production Division

00342.HTP.PRC.PRG Rev.1 January 2005 Page. 129 of 175

The condensed sulphur is separated and sent for storage using a Livesey seal; the tail gas is incinerated. Most CLAUS units existing in Italy and Europe have only two reactors; depending on the potential of the first, the second and sometimes the third condenser are closed in a single piece of equipment able to produce steam at 3 - 5 eff. bar; the final condenser is a dedicated boiler which produces low pressure steam (1 – 1.5 eff. bar) only if maximization of the conversion into sulphur is required. Figure 4.3.3 indicates the vapour tension of the liquid sulphur as a function of temperature; it is clear that boosted cooling of the tail gas (to 130°C for example) can markedly increase the quantity of sulphur recovered in the plant . However, since such boosted cooling implies being able to produce steam up to a maximum pressure of 1 – 1.5 eff bar, 130 - 135°C is generally reached only for tail gas arriving from the final reactor and if high conversion is required. In cases where the steam at very low pressure produced in the final condenser cannot be disposed of at the factory, it could be condensed with an air cooler or refrigerating water condenser and the condensation produced could be recycled for use in the low pressure boiler, thus cooling the tail gas as required although to the detriment of the economics. The blowers used to compress the combustion air can be volumetric with rotating reels or centrifugal with multi-rotors. As stated above, various systems are used to heat the gas in the reactors: the most common are the direct heaters (reheat gas) for the first reactor and indirect (gas/gas or with external heating fluids such as steam, electricity) for the second and third reactor. The best conversion result is obtained using indirect heating systems; indirect heating systems provide excellent results in terms of management. 4.3.5. Variations of the process See figure 4.3.4. The basic concept of the "split-flow" process is the combustion of part of the H2S contained in the acid to SO2 to reach a minimum flame temperature to ensure operating stability. The combustion of H2S to SO2 involves a higher reaction temperature. The remaining H2S is sent to the combustion products to satisfy the H2S/SO2=2 ratio in the tail gas. Since in the Clause reaction around 1/3 of H2S is transformed into SO2 theoretically it is not possible to bypass more than 2/3 of the acid gas; to operate safely, besides making a careful control of the H2S/SO2 value in the tail gas, it was therefore necessary to limit the quantity of bypass acid gas to the maximum value of 66% of the total.

Eni S.p.A.
Exploration & Production Division

00342.HTP.PRC.PRG Rev.1 January 2005 Page. 130 of 175

The "split flow" process is applied to acid gas with an H2S content of between approx 20 and 60%; part of the acid gas is supplied to the muffle burner with all the air needed for the conversion of all the H2S present in the acid gas into sulphur. The products of the combustion, which must have a minimum flame temperature of 1000°C to avoid problems of instability, after recovering the heat in the boiler, are sent to the first condenser for condensation of the sulphur produced during the thermal reaction; in cases of the treatment of acid gas with low H2S concentration (20 - 40 % vol.), the condenser is not needed because the formation of sulphur in the thermal reaction is very limited or even zero. The remaining acid gas is mixed with the process gas arriving from the boiler or from the first condenser and the mixture is sent to the first reactor; from this point on the process is the same as that described for the "once through" case; the differences are simply due to the different thermal level of the gas entering the catalytic reactors needed to maximize the conversion; the thermal level depends on the concentration of H2S concentration of the acid gas and on the presence or absence of impurities in the acid gas. However, an acid gas with a high content of C2+ hydrocarbons cannot generally be treated in a "split flow" plant because with this lay-out total combustion of the hydrocarbons is not possible with the risk of coking on the catalytic reactors and the ensuing formation of plugs which prevent the correct operations of the plant. One variant of the "split-flow" lay-out is to send the acid gas in by-pass to the muffle downstream of the combustion; in this case it is possible to partly mitigate the problem of the presence of hydrocarbons in the acid gas: this stratagem can only be applied in the case of acid gas which can reach a final adiabatic temperature downstream of combustion of not less than 950 - 1000°C. The combustion temperature can be increased by re-heating the combustion air and the acid gas supplied to the burner. This chapter briefly describes the most commonly used lay-outs for "straight through" processes only. "Split-flow" processes with all variants needed to treat acid gas with a low concentration of H2S, are not considered of interest for the purposes of this report. The wider use of package plants allows grouping together in a single apparatus the acid gas combustion chamber (fire tube), the heat recovery system from the combustion fumes and sulphur condensers with relative separation chambers; the catalytic reactors are grouped together in a single shell. This layout is applicable in its entirety up to a potential of 50 - 60 t/d of sulphur, provided that the acid gas does not contain NH3 or HCN or large quantities of hydrocarbons. For higher potential it is necessary to have a combustion chamber with relative heat recovery system separate from the sulphur condensers.

Eni S.p.A.
Exploration & Production Division

00342.HTP.PRC.PRG Rev.1 January 2005 Page. 131 of 175

The lay-out cannot be applied for potential of approx 100 t/d and a combustion chamber separate from the fume heat recovery system. Figure 4.3.5, which shows a package plant with direct heating of the gas at the first catalytic reactor and indirect heating of the gas at the second reactor; the minimum flexibility of a plant of this type is around 4 to 1; note that in the case of direct heating of the gas at both catalytic reactors, the minimum flexibility would drop to 3 to 1. The acid gas from the sweetening plant’s regeneration sector passes into the V-1 separator where it releases any condensation which are recycled to the absorption unit (through gravity, with a pump or blowing with inert material or steam), and then enters the combined burner assembled on the front of the recovery boiler; the rate of acid gas is regulated automatically; the entire gas load arriving from the sweetening section is sent to the CLAUS plant. The combustion air is supplied by the K-1 blower – centrifugal or volumetric depending on the potential. The air rate is controlled in two ways: approximate regulation depending on the flow rate of the acid gas while fine regulation is based on the analysis of H2S/SO2 in the tail gas. Both regulations have a dedicated control valve. The products of combustion remain for the time needed to complete the reaction in the combustion chamber submerged in boiler B-1 and then cooled to around 600 700°C in a second passage through the boiler. Boiler B-1 has 5 passages and produces steam at a pressure of 1.5 - 5 eff bar; the supply water flow rate is controlled automatically by a level meter; a pressure metre regulates the rate of steam produced. A small part of the hot gas at 600 - 700°C (reheat gas) leaving the second passage of the boiler is used to heat the gas sent to the fires catalytic reactor (about 3-5% of the total flow rate), while the rest of the hot gas is sent to the third passage of the boiler which acts as first sulphur condenser; most of the sulphur contained in the process gas in gaseous phase is condensed and separated by the gas in a preliminary separation chamber fitted on the front of the boiler. The liquid sulphur produced is sent to the TK-1 storage trench using a hydraulic V2 Liveley seal; the cooled gas, at a temperature of 160 - 200°C is mixed with the hot gas leaving the first passage of the boiler so as to obtain the desired catalyst temperature, which is generally 220 - 260°C, and is then introduced into the first catalytic reactor R-1. Catalytic conversion, taking place on alumina, results in an increase in temperature of 40-80°C depending on the concentration of acid gas; the converted hot gas is sent to the E-1 gas/gas exchanger where it is cooled, heating the supply gas to the second reactor; the gas leaving the E-1 enters the fourth passage from boiler B-1 (second condenser) where most of the sulphur contained in the process gas is condensed;

Eni S.p.A.
Exploration & Production Division

00342.HTP.PRC.PRG Rev.1 January 2005 Page. 132 of 175

after separation in a chamber on the back of boiler B-1, the sulphur is sent to the TH-1 storage trench using the V-3 Liveley seal . The gas leaving the fourth passage of the B-1 boiler at a temperature of 150 - 180°C is heated in E-1 to catalyzing temperature, generally 200 - 240°C and is then supplied to the second reactor R-2. Catalytic conversion generates an increase in temperature of 20 - 40°C; the converted gas enters the final passage of the boiler B-1 (third condenser) where most of the sulphur contained in the gas is condensed. After separation of the sulphur in a chamber on the back of boiler B-1, the sulphur is sent to the TK-1 storage trench using a V-4 Liveley seal. The tail gas leaving the final passage of boiler B-1 is sent for thermal or catalytic incineration; the incineration reaction is supported by the combustion of fuel gas. The sulphur produced, collected in the TK-1 trench, is loaded onto tanker trucks or sent for solidification using the upright pump P-1 assembled above the trench; the trench operates with a slight vacuum, preferably directly connected to the combustion chamber of the thermal incinerator to avoid leakage of sulphur vapours of the H2S dissolved in it. Before sending the acid gas to the plant the entire plant has to be heated to set minimum temperatures: for this purpose the fuel gas is burnt in the combined burner on the front of boiler B-1. The products of hot combustion ensure the necessary heating and are then discharged into the atmosphere through the incinerator. In plants with fire tube it is not necessary to lower the flame temperature of the fuel gas during the unit heating stage; the heat exchange between the reaction tube and water in the boiler is sufficient to obtain a temperature of the metal which is not dangerous. The combined burner has a pilot light with electric spark ignition; some plants have graphite ignitions for the direct ignition of the fuel gas burner; in all cases one or two photoelectric cells monitor the presence of the flame. A logic (relay, solid state or with PLC) governs the combined burner ignition; ignition is based on semi-automatic sequences. The plant is protected by a safety system which intervenes in the absence of the flame, low boiler level, high acid gas separator level, high pressure on the boiler front, low rate of acid gas and combustion air, low (and sometimes high) pressure of fuel gas to the pilot light when envisaged and no flame at the incinerator; of the safety system intervenes the supply of acid gas, combustion air and main fuel gas (and pilot light when envisaged) will be interrupted. The air blowers have an independent automatic protection system and an antipumping system for centrifugal machines or, for volumetric machines, machines to discharge the excess air into the atmosphere.

Eni S.p.A.
Exploration & Production Division

00342.HTP.PRC.PRG Rev.1 January 2005 Page. 133 of 175

There are also protection systems for the incinerator and for the sulphur pumps on the storage tank. If necessary, it is possible to increase the flexibility of the plant from 4 - 1 to 5 - 1 by adding an electric heater to be used only at minimum charges on the gas entering the second reactor; in this case however a suitable flow rate measuring system is needed on the combustion air and acid gas (dual flow rate transmitter, dual measuring flange, high precision flow rate transmitter, etc.). If flexibilities of more than 5 - 1 are required, besides using indirect heating systems for the reactor gas, also use the simultaneous combustion of fuel gas but in a separated combustion chamber: the reason why supported combustion is necessary is because it is necessary to operate with mass velocities above certain limits so as not to cause the uncontrolled entrainment of sulphur by the condensers (sulphur mist). To this end it is possible to prepare a boiler with two separate combustion chambers to which fuel gas and acid gas are sent during minimum load operations and only acid gas with load of more than 20% above the nominal load. Each combustion chamber must have a burner with pilot and similar equipment to that described above. The maximum flexibility reached with these systems is greater than 60 - 1, therefore practically without limits. The minimum mass velocities to be maintained in the sulphur condensers to avoid the risk of the formation of sulphur mist are around 5 Kg of gas/m2 sec. Considering that with nominal loads mass velocities of 20 - 25 Kg/m2 sec are generally envisages in the condensers, supported combustion is necessary for loads from minimum to around 20% - 25% of the nominal load. Mention has already been made of the fact that indirect heating systems (electric, steam, hot oil) are preferred to maximize conversion into sulphur; besides this, it should be noted that these are also more suitable to ensure maximum flexibility of the plant. Plant with muffle The lay-out of the plant with muffle is needed when products are contained in the acid gas which cannot be easily destroyed in a plant with fire tube, such as NH3, HCN or massive doses of hydrocarbons and in any case for units with a potential of more than approx. 100 t/d of sulphur; however, some users tend to use plants with muffle irrespective of the capacity and purity of the acid gas in order to tackle future situations of higher load than those envisaged at project stage. Despite the fact a muffle plant can be dimensioned according to some principles of the package plant, such as the collection in a single container of the heat recovery system from the fumes with the sulphur condensers and relative separation chambers and catalytic reactors, different boilers are often envisaged which meet the steam production needs of the factory even to the detriment of the initial investment cost.

Eni S.p.A.
Exploration & Production Division

00342.HTP.PRC.PRG Rev.1 January 2005 Page. 134 of 175

Figure 4.3.6 shows a plant with a single zone muffle with three recovery boilers and indirect heating of the gas at the reactors; the proposed lay-out can treat gas with an ammonia content of less than 1% in vol. with a flexibility of 5 to 1. The plant description is similar to the one in the previous chapter; the difference consists in the development of the heat reaction in the H-1 refractory muffle, able to develop the residence time needed to complete the combustion of the acid gas at a very high temperature and therefore with greater H2S conversion into sulphur than that obtainable with combustion in “fire tube”. The steam can be produced in the B-1 recovery boiler at a pressure of more than 60 eff. bar; a production of 10-20 eff. bar is generally required and the process gas leaves the boiler at a temperature of 280 - 350°C. The first and second sulphur condenser are installed in a second boiler which produces steam at 3-5 eff. bar, while the third condenser is a low pressure steam generator able to cool the tail gas to 135°C, thus allowing an increase in conversion efficiency of 0.8 – 1.5% compared to a steam production boiler at 3 - 5 eff. bar. The gas to the reactors is heated using easy operating electric heaters with continual thyristor regulation; in Italy electric heaters have been used up to a potential of 50 t/d of sulphur. During the plant heating stage before going into operation, the flame temperature reached in the stoichiometric combustion of the fuel gas would be such as to damage the refractory materials used in the muffle: to limit its value, quench steam is added to the combustion products in quantities which lower the flame temperature to 1300 - 1350°C. The heating times of a plant with muffle are more than double those of a plant with fire tube, because the increase in temperature of the muffle’s refractory materials has to be gradual. The temperature of the muffle, between 1000 and 1400°C, is measured using special Platinum-Rhodium thermo-couples or optical pyrometers which are more reliable and last longer; it is not necessary to measure the flame temperature in fire tube plants. If acid gas containing ammonia is to be treated (typical example is the gas from the Sour Water Stripper in refineries) two-zone muffles have to be used, adopting the split flow lay-out principle. See figure 4.3.7. The acid gas containing ammonia is supplied to the burner along with all the air needed for the Claus reaction to take place and the part of the acid gas not containing ammonia needed to reach a flame temperature of approx. 1400°C; the rest of the acid gas not containing ammonia is sent to the second zone of the muffle where it reacts with the reaction products arriving from the first zone.

Eni S.p.A.
Exploration & Production Division

00342.HTP.PRC.PRG Rev.1 January 2005 Page. 135 of 175

The effect of the high temperature and the presence of a high concentration of SO2 in the first zone, along with an adequate residence time of the fumes, results in the total destruction of the ammonia. Incomplete combustion of ammonia could cause the precipitation of ammonium salts in the colder parts of the plant with the formation of plugs which are difficult to remove. In units with muffles, in the case of emergency shut-down, the unit must be fluxed for a few minutes with inert gas to prevent damage caused by thermal radiation from the hot refractory materials. The use of a two-zone muffles allows very high, almost unlimited, turn downs, designed with a single burner supplied with fuel gas needed to produce fumes in suitable quantities to guarantee the minimum mass velocities to avoid the formation of sulphur mists; the combustion air of the acid gas is supplied along with the fuel gas in the first zone of the muffle. The acid gas is instead applied to the second zone where it reacts with the air contained in the fumes of the first zone. The gas at the reactors is heated using an indirect method using external heating fluids. Of course, for operations with a load of more than 20% higher than the nominal load, the acid gas is sent only to the first zone which operates in a traditional way while the second zone is not supplied. The two zone muffle technique with very high turn downs cannot however be applied for acid gas containing NH3 in a concentration of more than 1% Vol. unless controls are made on a case by case basis. Another way of heating the gas at the reactors for muffle plants and fire tube plants consists in installing inline heaters; that is, combustion chambers with burner supplied with fuel gas or acid gas installed in a container where the gas is heated to the desired temperature, mixing it with the combustion products; the inline heaters allow flexibilities of 8 - 10 to 1 but are more expensive than the other systems described and more difficult to manage; moreover, only in the case of heaters supplied with fuel gas, they can cause operating problems such as poisoning of the catalysts through plugging with lampblack in the case of combustion with scarcity of oxygen or sulphation in the case of incomplete combustion and the presence of oxygen in the products of combustion. The use of inline heaters should therefore be limited to cases where alternatives are not viable. 4.3.6 Construction materials The main construction material in CLAUS units is carbon steel; the muffles, boilers, condensers, reactors and heaters are made of carbon steel; a corrosion reinforcement of 3 mm is generally envisaged for all parts in contact with process fluids and this is sufficient for a long industrial life of the plant. All the parts in contact with the liquid sulphur are made of carbon steel, including the heating coils immerged in the storage tank.

Eni S.p.A.
Exploration & Production Division

00342.HTP.PRC.PRG Rev.1 January 2005 Page. 136 of 175

Only minimum parts such as those in contact with the air in the sulphur storage tank, the catalyst containment networks in the reactors and the pipes of the hot gas at a temperature of more than 600°C are made of stainless steel; sometimes the catalyst support grids and the flux ejectors of the sulphur tanks in the sulphur degassing systems are also made of stainless steel. The hoses of the combined acid/fuel gas are made of stainless steel and the heads of the acid gas and fuel gas burners are made of chromium refractory steel. Mention should be made of the internal refractory linings of the equipment which have the aim of protecting the metal surfaces from the high process temperatures (muffle and incinerator) and from corrosion. The parts generally lined with refractory materials are: - muffle, lined with refractory materials with a high alumina content for the parts in contact with the flame and with intermediate and wall insulation; the lining can be made of bricks or casting. - recovery boiler, lined with casting on all parts in contact with process gas with a temperature of more than 300 - 350°C. - sulphur condensers, lined with casting on all parts in contacts with process gas with a temperature of more than 300 - 350°C. - catalytic reactors, lined with casting from the upper level of the catalyst to the gas outlet. - incinerators and relative exhaust chimneys, lined with refractory material with medium alumina content; the combustion chambers are generally lined with bricks and the chimneys with casting. - in some cases also the gas pipes with operating temperatures of more than 300 350°C are internally lined with casting of refractory cements. The sulphur pumps are generally built with rotors in cast iron while the body is made of cast iron or carbon steel. The air blowers have a cast iron body if they are volumetric and cast iron or aluminium with rotors in aluminium if centrifugal; some centrifugal machines can also be built with body in stainless steel and with rotors in stainless steel too. The sulphur storage tanks are made of anti-acid cement and are sometimes internally lined with special anti-acid materials; the anti-acid casting is made with a high degree of thermal insulation and is completely impermeable.

Eni S.p.A.
Exploration & Production Division

00342.HTP.PRC.PRG Rev.1 January 2005 Page. 137 of 175

VISCOSITY - centipoise TEMPERATURE - °C FIGURE 4.3.1 – VISCOSITY OF LIQUID SULPHUR

Eni S.p.A.
Exploration & Production Division

00342.HTP.PRC.PRG Rev.1 January 2005 Page. 138 of 175

FIGURE 4.3.2 – CLAUS: STRAIGHT THROUGH LAY-OUT – THREE REACTORS

Eni S.p.A.
Exploration & Production Division

00342.HTP.PRC.PRG Rev.1 January 2005 Page. 139 of 175

VAPOUR PRESSURE – ata TEMPERATURE - °C FIGURE 4.3.3 – VAPOUR PRESSURE OF LIQUID SULPHUR AS S1

Eni S.p.A.
Exploration & Production Division

00342.HTP.PRC.PRG Rev.1 January 2005 Page. 140 of 175

FIGURE 4.3.4 – CLAUS: SPLIT FLOW LAY-OUT– THREE REACTORS

Eni S.p.A.
Exploration & Production Division

00342.HTP.PRC.PRG Rev.1 January 2005 Page. 141 of 175

FIGURE 4.3.5 – CLAUS: PACKAGE (FIRE TUBE) UNIT

Eni S.p.A.
Exploration & Production Division

00342.HTP.PRC.PRG Rev.1 January 2005 Page. 142 of 175

FI GURE 4.3.6 – CLAUS – LAY-OUT WITH SINGLE ZONE MUFFLE

Eni S.p.A.
Exploration & Production Division

00342.HTP.PRC.PRG Rev.1 January 2005 Page. 143 of 175

FIGURE 4.3.7 – CLAUS – LAY-OUT WITH TWO-ZONE MUFFLE

Eni S.p.A.
Exploration & Production Division 4.3.7 Further developments of the process

00342.HTP.PRC.PRG Rev.1 January 2005 Page. 144 of 175

Processes below dew-point. This class of processes extends the Claus reaction below the dew point of the sulphur. Sulphur recovery it increased by the more favourable equilibrium reaction. One of these processes is Amoco’s Cold Bed Adsorption (CBA), comprising a pair of catalytic reactors operating at a temperature below the sulphur dew point. Considering that the sulphur condenses on the catalyst, regeneration is necessary to avoid a reduction in the catalytic activity. The catalyst is restored by injecting hot tail gas in the reactor to vaporize the condensate (this sulphur is then recovered in a condenser). Two catalytic reactors in parallel are required, one in active mode and the other in regeneration mode. The sulphur recovery with this system is 98.5-99%. Along these lines other processes have been developed with three or four Claus reactors and CBA lay-out, or completing eliminating the incoming water vapour (the water reduces the catalytic activity as it adsorbs). Another type of plant belonging to this class is the Claus processes. In these plants the outgoing gas of a normal Claus process is contacted in a fixed bed with polyethylene glycol at around 120°C. Sulphur dioxide and hydrogen sulphide are absorbed by the organic solvent and react in a reactor with a sodium organic salt based catalyst. The liquid glycol and glycol are practically insoluble; the two stages are then separated. The sodium salt is however low-boiling and its evaporation provokes a reaction with the anhydride the precipitation of insoluble sulphate and the formation of organic acid. The salt tends to accumulate in the column; this means that the plant has to be shut-down periodically for cleaning operations. In this way sulphur recovery reaches up to 99.7%. SuperClaus process. This is a selective oxidation process comprising a normal twostage Claus unit followed by a SuperClaus catalytic stage. However, in this plan the Claus unit operates in a slightly different way to the standard one. In fact, the supply air is injected to have an H2S/SO2 ratio of more than 2 and to have a total consumption of anhydride in the two stages of the process. The acid still has a concentration of 09%. The gas leaving the second stage is heated to around 300°C and mixed with a preheated current of air. The supply obtained in this way is sent to the SuperClaus reactor where a patented catalyst is used to oxidize the hydrogen sulphide. An oxidation level of 85% can be reached. Total sulphur recovery is 99%. Other processes. Besides the above, other processes have been patented which allow sulphur purification and recovery of more than 99.99%. These processes are often very expensive (even more than double the costs of a traditional dual stage Claus unit) and for specialist use with cases limited to contingent cases. For further information see the report OKIOC - PROCESS STUDY (Sulphur recovery and disposal).

Eni S.p.A.
Exploration & Production Division 5.

00342.HTP.PRC.PRG Rev.1 January 2005 Page. 145 of 175

CRYOGENIC PROCESSES TO REDUCE THE CARBON DIOXIDE The cryogenic processes are based on the use of an additive such as oil or butane or LNG for the separation by means of distillation of CH4 and CO2 from the other hydrocarbons; the separation columns operate at temperatures of between -50°C and -90°C with pressures of around 40 - 80 abs. bar.

5.1

Ryan-Holmes process Figure 5.1.1 shows the base lay-out of an acid gas separation plant according to the Ryan-Holmes process applied to EOR. The crude gas to be treated, containing H2S and up to even more than 90% of CO2, is compressed, dehydrated, cooled and sent to the head of the CH4-CO2 separation column demethanizer. In this case the additive is the recovered LNG. The gas leaving the head of the column can be sent to the gas pipeline, after the heat has been recovered. The LNG - CO2 solution and the heavier hydrocarbons leaving the bottom of the demethanizer is sent to the CO2, separation column at a higher temperature and lower pressure; the additive LNG which allows separation of the CO2 from the hydrocarbons and the H2S is supplied also to this column. The CO2 leaving the head contains up to around 100 ppm of H2S depending on the concentration of H2S in the crude gas to be treated; the solution leaving the bottom is sent for recovery of the additive by means of adjustment. The additive is recycled to the columns while the light hydrocarbons leaving the head of the last column are sent to a sweetening system with amine for final conditioning. The acid gas separated in the amine regenerator is sent to a Claus unit for sulphur recovery. The diagram does not indicate the various heat recoveries that are usually activated for the energy optimization of the process.

Eni S.p.A.
Exploration & Production Division

00342.HTP.PRC.PRG Rev.1 January 2005 Page. 146 of 175

FIGURE 5.1.1 – CRYOGENIC - RYAN HOLMES PROCESSES

Eni S.p.A.
Exploration & Production Division 5.2 5.2.1 CRYOFRAC Process Process description

00342.HTP.PRC.PRG Rev.1 January 2005 Page. 147 of 175

The CRYOFRAC process was developed by SnamProgetti to allow natural gas with a high CO2 content (more than 30 - 35% vol.) to be produced. The procedure is based in the absorption at low temperature with a selective physical solvent (Cryosol) for acid gas. The typical working range is -30 – -50°C at a pressure of around 40 bar. At present the process has been intensively and positively tested in a pilot plant but operative industrial plants are still not available. Natural gas with a high CO2 content can be purified using a cryogenic separation process; however, the thermodynamic behaviour of methane-CO2-H2S mixtures at low temperature is complicated by the fact that the CO2 can solidify and the H2S can involve immiscibility problems. In the phase diagram of a methane- CO2 system (Figure 5.2.1) two zones can be distinguished: a) a zone above 49 abs. bar where the CO2 cannot crystallize as at this pressure, greater than the critical pressure of the methane (46.4 abs. bar), it is not possible to obtain pure methane. b) a zone below 49 abs. bar where the formation of a solid phase is possible in a wide concentration range. This behaviour is also complicated by at least another two phenomena: - Nitrogen, a compound frequently present in natural gas, widens the field of composition in which the CO2 can solidify. - The methane-H2S system has a wide field of immiscibility. From the above it is clear that cryogenic distillation provides natural gas which is almost completely free of acid gas but with a plant with great regulation difficulties to avoid crystallization risks. The solvent used in the CRYOFRAC process, called Cryosol, is a mixture of polar organic compounds with patented compositions and property and of which it is possible to give only qualitative information. The main characteristics of Cryosol are: - Stability and non-corrosivity under operating conditions - Low fusion point (lower than -100°C) - Low vapour pressure under operating conditions.

Eni S.p.A.
Exploration & Production Division

00342.HTP.PRC.PRG Rev.1 January 2005 Page. 148 of 175

In the natural gas-CO2 system, the solvent has good selectivity characteristics during the acid gas absorption stage without causing problems of crystallization of CO2 and immiscibility of H2S. From a purely qualitative point of view, it can be said that, conditions being equal, Cryosol absorbs 400% of the CO2 absorbed by the methanol and 10% less of methane. The possibility of having a high load of solvent allows a flat vaporization curve in wide range of enthalpy so most of the cooling is obtained at a (low) almost constant temperature; see figure 5.2.2 The regeneration of the solvent through flash represents one of the unique aspects of the process with the possibility of recovering the cooling. The low thermal level of the cooling also allows the surface to be reduced as well as the cost of the exchangers. 5.2.2 Lay-outs used The CRYOFRAC process uses the typical lay-out of the physical absorption processes; the acid gas is absorbed at low temperature while regeneration takes place in flash stages in series, with the final flash in vacuum. If it is also necessary to remove the H2S to the levels required by the natural gas specifications, the solution should be regenerated also by means of distillation. Two diagrams are shown below of the application of the process on gas containing H2S and CO2 and CO2 alone. Figure 5.2.3 shows the most common case of application, assuming the treatment of a natural gas containing H2S and CO2. Before treatment with the CRYOFRAC, the gas must be dehydrated and separated from the heavy hydrocarbons which should be almost completely removed from the solution. The first acid gas absorbed in the CRYOFRAC process is H2S, given its selectivity compared to CO2; the current without H2S is then cooled, part of the CO2 is condensed while the remaining part is absorbed in a second absorption column. The two acid gases are absorbed with a completely regenerated solution for the CO2 and a partially regenerated solution; that is, still containing CO2 and methane for the H2S. The solvent is regenerated by means of multi-stage flashes the last of which is generally under vacuum while the current which absorbs the H2S requires further regeneration by means of distillation. The H2S rich current (distillation head) can be sent to a sulphur recovery plant.

Eni S.p.A.
Exploration & Production Division

00342.HTP.PRC.PRG Rev.1 January 2005 Page. 149 of 175

As the absorption of CO2 takes place at a very low temperature (-30 – -50°C), cooling recovery has to be optimized. This takes place recovering the cooling developed by the flash of the CO2 rich solution during cooling: if the content of CO2 in the gas is more than 35%, the cooling produced is such as to make the process self-cooling and consumption is consequently reduced. A small scale cooling cycle will be sufficient to cool the plant. The following product specifications can be obtained with this type of process: Scrubbed gas H2S 1-4 ppm volume. CO2 50 ppm vol. - 3% volume. Recovered CO2: H2S 1 - 100 ppm volume. The process described can be simplified if the gas to be treated does not contain H2S, or if the H2S in the scrubbed gas is not very severe. In this case absorption can take place in a single column and final distillation to eliminate the H2S from the solvent can be avoided. Figure 5.2.4. shows a process in which only CO2 is removed from the already dehydrated and degasolinized natural gas containing a CO2 concentration of 35% vol. The gas to be treated is cooled in the crude gas cooler E-2 to approx. -60°C by a current of solvent arriving from the second V-2 flash tank and enters the C-1 plate absorption column which operates at around 40 abs. bar. The Cryosol solution leaving the bottom of the column is regenerated in four flash stages, one of which under vacuum. The gas freed from the first flash tank V-1 at approx. 10 abs. bar is still rich in methane and is then recycled at the absorption column by the K-1 compressor. The gas freed during the next three flashes are rich in CO2, and are the coolants obtained from the expansion of the freed CO2 which are then used to make the process self-cooling. Indeed, the solvent leaving the second flash tank V-2 transfers coolants to the gas scrubbed in the E-4 cooling system and to the already mentioned coolant gas to be treated E-2. The gas leaving the third flash tank V-3, which operates at atmospheric pressure, cools the recycled methane at the absorption column C-1, in the coolant E-1. From the vacuum flash tank V-4, the solvent regenerated at a temperature of -50°C is pumped by the P-1 recirculation pump and, mixing with the scrubbed gas leaving the head of the absorption column C-1, scrubs the gas of the last traces of CO2. The pressure in the vacuum flash tank V-4 is maintained by the vacuum pump K-2.

Eni S.p.A.
Exploration & Production Division

00342.HTP.PRC.PRG Rev.1 January 2005 Page. 150 of 175

The sweet gas/solution mixture is separated in the separator V-5, from whose bottom the solvent s pumped by pump P-2 to the head of the absorption column C1. If necessary a part of the solvent is conveyed to a reclaimer to avoid accumulations of water or light hydrocarbons still present in the crude gas to be treated. The figure shows the main controls carried out on the various currents; these controls are usual also in other physical absorption processes. 5.2.3 Design criteria of the main equipment The design criteria of the equipment are similar to those adopted for other physical processes. The absorber is preferably a plate column, which must however be preceded by units upstream able to remove the humidity of the gas to be treated and the fractions of heavy hydrocarbons. The various flash tanks must be dimensioned with residence times which censure complete separation of the gas from the liquid. 5.2.4 Construction materials From an engineering point of view, Cryosol being a non-corrosive solvent, the materials are chosen on the basis of the design temperatures of the various pieces of equipment; i.e.: carbon steel killed for temperatures to -50°C, as in the case of the hotter flash separators. alloys at 3.5% Ni for temperatures to -100°C, for example for the absorption column, the circulation pumps and the colder separators. alloys at 9% Ni and stainless steel for lower temperatures.

-

-

5.2.5

Other applications of the process An interesting application of CRYOFRAC consists in using it in Enhanced Oil Recovery (EOR) processes where CO2 is used a miscible agent for the recovery of crudes from fields nearing depletion. Indeed, CO2, modifies the flow characteristics of the oil, facilitating production. In this application the CO2 has to be separated from the methane and the same CO2 has to be reinjected into the reservoir at pressure of between 60 and 200 bar.

Eni S.p.A.
Exploration & Production Division

00342.HTP.PRC.PRG Rev.1 January 2005 Page. 151 of 175

If the CO2 content in the methane is high, and in some cases it can reach 80% vol. of CO2, it would be advisable to combine the CRYOFRAC process with low temperature distillation upstream to separate a certain quantity of CO2, which will separate in liquid state at the bottom of the fractioning column while at the head the methane and the rest of the CO2 to be supplied to the CRYOFRAC would be obtained at the head. Also in this case the global energy efficiency of the process (cryogenic distillation + CRYOFRAC) is interesting as it is self-cooling. Indeed, the liquid CO2 from the bottom of the distillation column, expanding, provides coolant to the head condenser and is then compressed before being reinjected into the reservoir. Figure 6.5.5. shows the percentage of CO2 typically removed from a natural gas current by means of cryogenic distillation. However, the economic feasibility of this installation has to be carefully assessed in relation to the price of oil. Another application of CRYOFRAC could be to remove acid gas in the ammonia synthesis gas or oxo-gas preparation line starting from carbon or oil fractions when the acid gases are in a sufficiently high concentration.

Eni S.p.A.
Exploration & Production Division

00342.HTP.PRC.PRG Rev.1 January 2005 Page. 152 of 175

PRESSURE – abs. bar TEMPERATURE - °C FIGURE 5.2.1 – METHANE – CO2 SYSTEM

Eni S.p.A.
Exploration & Production Division

00342.HTP.PRC.PRG Rev.1 January 2005 Page. 153 of 175

TEMPERATURE ENTHALPY FIGURE 5.2.2 – CRYOFRAC – CHARACTERISTICS OF THE SOLVENT

Eni S.p.A.
Exploration & Production Division

00342.HTP.PRC.PRG Rev.1 January 2005 Page. 154 of 175

FIGURE 5.2.3 – CRYOFRAC – ABSORPTION OF CO2 ALONE

Eni S.p.A.
Exploration & Production Division

00342.HTP.PRC.PRG Rev.1 January 2005 Page. 155 of 175

FIGURE 5.2.4 – CRYOFRAC – ABSORPTION OF H2S + CO2

Eni S.p.A.
Exploration & Production Division

00342.HTP.PRC.PRG Rev.1 January 2005 Page. 156 of 175

CO2 REMOVED THROUGH DISTILLATION AT LOW TEMPERATURE - % of the total CONCENTRATION OF CO2 IN THE GAS TO BE TREATED - % vol. FIGURE 5.2.5 – CRYOFRAC – EFFECT OF CO2 REMOVAL

Eni S.p.A.
Exploration & Production Division 6 APPENDIX- PROCESSES NO LONGER USED

00342.HTP.PRC.PRG Rev.1 January 2005 Page. 157 of 175

In the past processes were used on an industrial scale which have now become obsolete for different reasons such as environmental protection, efficiency, management or maintenance. This paragraph gives a brief overview of these processes. 6.1 Non-regenerative processes These processes are only selective in terms of hydrogen sulphide, and can offer a high level of purification. They were used with small quantities of pollutant and can be divided into two categories: with solid adsorbent (iron and zinc oxides) or with solutions (permanganates, dichromate and lead acetates). In this type of procedure the operating pressure does not play a decisive role. Solid adsorption plants usually had two reactors which were used in alternation: one operating, one in maintenance with the removal of the degraded product and its substitution or in some cases, its regeneration. For example, with iron oxides the sulphides formed were re-oxidized at high temperature with air. Liquid absorption plants were used for small production units and were usually with closed cycle. These processes were gradually abandoned over time due to environmental problems due to the disposal of the solid mass or the rich solution. 6.2 Chemical absorption with alkaline carbonates These processes are based on similar mechanisms to those discussed for processes with amine solutions. One of the most important at an industrial level was the BENFIELD process belonging to Union Carbide. The absorbing solution was a water solution, with K2CO3 at 20-40% in weight, DEA at 3% in weight and traces of V2O5. Carbonate was the absorbing solution and amine the activator of the process. Vanadic anhydride was used as corrosion inhibitor. The reactions (all at equilibrium point) can be represented as K2CO3 + H2O + CO2 -» 2 KHCO3 K2CO3 + H2S -> KHCO3 + KHS The reactions are exothermic but their kinetics are favoured at high temperatures; therefore, even if the conversion is depressed, it is preferable to work in this way. The pressure favours the reaction kinetics. DEA has the role of favouring absorption kinetics and of modifying the liquidvapour equilibrium. During regeneration the operating temperature must be as low as possible, so as to shift the equilibrium of the above-stated reactions to the left. Determining the pressure logically establishes also the temperature of the regeneration column. The reactions of the process are highly selective as regards acid gases. The schemes allow for outgoing impurities of 20 ppm for CO2 and 1 ppm for H2S. The heat required by the process is around half that required for a normal amine process.

Eni S.p.A.
Exploration & Production Division

00342.HTP.PRC.PRG Rev.1 January 2005 Page. 158 of 175

The lay-outs used are similar to those used in DEA and MDEA plants (classical, split-flow, two-stage...). The main problem of this type of plant is the danger factor of vanadic anhydride; moreover, the major corrosion problems caused by the carbonates make the use of amine solutions more recommendable. 6.3 Absorption with MEA and MEA-DEG solutions

This type of plant (to which the Cupello plant belongs) has been abandoned due to the excessive foaming problems of the solutions. 6.4 Other processes A range of other processes have been used and then abandoned for the reasons illustrated above. These plants belong to all types of process such as amine, absorption with ammonia solutions, physical absorption, absorption on fluid bed and oxidation processes in liquid phase. Mention should be made of the molecular sieve processes to purify solely CO2, used more recently but which have not given satisfactory results. These types of plants are no longer designed but they can still be found in plant already in construction.

Eni S.p.A.
Exploration & Production Division 7 GLOSSARY

00342.HTP.PRC.PRG Rev.1 January 2005 Page. 159 of 175

SWEETENING – Process aimed at removing acid gas such as CO2 and H2S from gaseous or liquid currents. APPROACH TO EQUILIBRIUM – Percentage ratio between the vapour pressure of the acid gas in the absorbing solution and the partial pressure of the acid gas in the gas to be treated. ABSORPTION – Operation aimed at removing the acid gas from the crude gas to be treated. PICK-UP – Specific quantity of acid gas absorbed chemically or dissolved in the absorption fluid; it is expressed in Kmol of Acid gas/Kmol of solution, in Nm3 GA/m3 Solution or in other suitable engineering units. NET PICK-UP – Difference in pick-up between the lean solution and rich solution; it expresses the actual absorbing capacity of the solution. DEGRADATION OF THE SOLUTION – Irreversible transformation of one or more components of the absorbing solution with the formation of secondary reaction products. DRIVING FORCE – Difference between the partial pressure of H2S (or CO2) in the crude gas and the vapour pressure of H2S (or CO2) in the absorbing solution. The driving force measures the tendency of the acid gas to be absorbed by the solution. ACID GAS - H2S and CO2 to be removed or H2S and CO2 freed during the regeneration stage of the regeneration procedures. SWEET GAS - Gas produced by a sweetening procedure. CRUDE GAS - Gas entering the sweetening unit. TECHNICAL GAS - Gas of not high purity used industrially as inert, oxidizer, reducer or for other uses; it is sold in cylinders or other pressurised containers. Technical gases are oxygen, hydrogen, nitrogen, helium, argon, carbon dioxide and acetylene. INCINERATOR – Equipment in which sulphide components contained in a gaseous current are completely oxidized to SO2; it can be thermal and thus based on oxidation at a temperature of 600 - 1000°C or catalytic with an operating temperature of 300 - 450°C. HYDROLYSIS – Reaction of CO2 and CS2 with H2O with the formation of CO2 and H2S; hydrolysis can take place in liquid and gaseous phase. In the gaseous phase the hydrolysis must be carried out on specific catalysts which operate at temperatures of between 100 and 400°C.

Eni S.p.A.
Exploration & Production Division

00342.HTP.PRC.PRG Rev.1 January 2005 Page. 160 of 175

SOLID BED – Absorbing mass, or molecular or activated carbon sieve used in the sweetening process. MAKE-UP – Replenishment; top up: refers to the absorbing fluid lost through degradation, vapour pressure, entrainment, etc., and to the solution water of the absorbing fluid lost through evaporation with the sweet gas or with the freed acid gas. In some cases the excess condensate has to be removed when the sweetening plant is supplied with gas at high temperature and saturated with water vapour. PERMEABLE MEMBRANES – These are permeable fibres able to operate at very high pressures and able to separate, through permeation, some compounds of from gaseous currents; the permeated gas (acid gas) is rendered at low pressure while the non-permeated gas (sweet gas) is rendered at high pressure. MUFFLE – Combustion chamber internally lined with refractory material where the sub-stoichiometric combustion of the acid gas takes place in Claus units; it operates at high temperature (1000-1420°C) and can have one or two reaction zones depending on the composition of the acid gas to be treated and on the flexibility of the plant. In two-zone muffles there is an internal wall which separated the zones. OPTICAL PYROMETER – Instrument used to measure temperature base on the measurement of the intensity of electromagnetic intensity (or radiant energy); it is used to measure high temperatures (1000-1600°C), especially in ovens which treat extremely aggressive fluids. PARTIAL PRESSURE – The product between total absolute pressure of a gas and the molar fraction of a component. ABSORPTION PROCEDURE – Based on the polar affinity between the solid absorbing bed and the acid gas to be removed. CHEMICAL ABSORPTION PROCEDURE – Based on the reaction of the absorbing fluid with the acid gas to be removed. CHEMICAL-PHYSICAL ABSORPTION PROCEDURE – Based on the use of absorbing fluid able to absorb the acid gas through chemical reaction or physical solubility. PHYSICAL ABSORPTION PROCEDURE – Based on the solubility of the absorbing fluid with regard to the acid gas to be removed. CLAUS PROCEDURE – Oxidation process in gaseous stage to transform H2S into sulphur which is recovered as a liquid with high purity. CRYOGENIC PROCEDURE – Based on fractioning the gas at low temperature.

Eni S.p.A.
Exploration & Production Division

00342.HTP.PRC.PRG Rev.1 January 2005 Page. 161 of 175

NON-REGENERATIVE PROCEDURE – Based on the reaction of the absorbing fluid with the acid gas to be removed; the product formed must be expelled from the system. OXIDATION PROCEDURE – Based on the direct transformation of H2S into sulphur; it can operate in gaseous phase through sub-stoichiometric combustion of H2S or in liquid phase using oxidation air of the absorbing solution with an oxygen carrying agent; in the latter case it is also a regenerative procedure. REGENERATIVE PROCEDURE – Procedure based on the continual regeneration of the absorbing fluid with release of the absorbed acid gas or removal of the produced sulphur. SELECTIVE PROCEDURE – Able to preferentially absorb H2S instead of CO2. SECONDARY REACTION PRODUCTS – These are sub-products which are inevitable formed by reaction of absorbent fluids with some gaseous components present in the crude gas to be treated (degradation of the solution). RECLAIMING – Operation to condition the degraded solution: it consists in removing the secondary products of degradation with the re-use of the solution in the acid gas absorption cycle. CONVERSION YIELD – Expresses the percentage of H2S present in the crude gas to be treated which has been transformed into sulphur. THERMOSIPHON BOILER – This is based on the circulation of the absorbing solution, pipe side or sleeve side, due to the difference in specific weight between the inlet and outlet of the boiler; the circulation ratios are higher for upright boilers than for horizontal ones; the mixed phase freed at the outlet of the boiler is conveyed to the solution regeneration column. KETTLE BOILER – This is based on the passage of all the solution to be regenerated in the boiler; the vapour freed is supplied to the solution regeneration column while the lean solution is conveyed to the column itself or directly to the circulation pump. ONCE THROUGH BOILER – This is based on the passage of all the solution to be regenerated through the boiler; the mixed phase freed (solution and vapour) is supplied to the bottom of the solution regeneration column. REGENERATION – Operation aimed at regenerating the rich absorbing solution; it is performed through flashes, stripping with transport gas, stripping with direct vapour, indirect heating, etc., depending on the process. TWO-STAGE ABSORPTION LAY-OUT – Envisages the use of solutions with different regeneration degree, besides different temperature; the regenerator is twostage: the lean solution leaves the regenerator at the bottom and is sent to the head of the absorber.

Eni S.p.A.
Exploration & Production Division This lay-out allows savings of regeneration heat.

00342.HTP.PRC.PRG Rev.1 January 2005 Page. 162 of 175

CLASSICAL ABSORPTION LAY-OUT – This envisages using a lean solution supplied at the head of the absorber; the regenerator is single-stage. SPLIT-FLOW ABSORPTION LAY-OUT – This envisages the use of lean solution supplied at the head of the absorber at different temperature levels; the regenerator is single-stage. SULPHATION – Reaction of the transformation of a salt into sulphate; in Claus catalysts sulphation provokes the transformation of alumina (A1203) into aluminium sulphate through reaction of the catalyst with a gas containing SO2 and oxygen or containing only several tens of ppm of SO3; a sulphate catalyst loses its activity proportionately to the entity of the sulphation. RICH SOLUTION – Solution produced by absorption and therefore rich in acid gas. REGENERATED OR LEAN SOLUTION – Solution used for absorption and therefore with little acid gas. VAPOUR PRESSURE – This is the absolute pressure applied by a component of a solution in set temperature and concentration conditions. THYRISTOR – Electronic continuous modulator of energy flow; a typical application of a thyristor is to continuously regulate the temperature of the outgoing fluids to be heated using electrical resistances.

Eni S.p.A.
Exploration & Production Division 8. BIBLIOGRAPHY

00342.HTP.PRC.PRG Rev.1 January 2005 Page. 163 of 175

The name of the author, the name of the publication, the title of the article or publication or notes to identify the contents are given for each bibliographic reference. 1926 Speer Gas Age Record Ferrox-Koppers Process Gluud-Schoenfelder Chem. & Met. Eng. (12) Gluud Process Mueller Gas U. Wasserfach (28) Fisher Electrolytic procedure Bottoms US Patent 1.783.901 Using MEA Gollmar Ind. Eng. Chem. (2) Thylox-Koppers Procedure Baehr-Mengdehl US Patent 1.990.217 Alkazid Process Baehr Chem. Fabrik (11) Catasulf Process Hutchinson Us Patent 2.177.901 Using MEA-TEG Gollmar-Lowry-Wiley Chemistry of Goal Utilization Oxidation in liquid phase Shreve The Chemical Process Industries/Edit. McGraw Hill Phenolate procedure Pieters-Van Krevelen Elsevier Amsterdam Staatsmijnen/Otto Procedure

1927

1931

1933

1934

1935

1938

1939

1945

1945

1946

Eni S.p.A.
Exploration & Production Division

00342.HTP.PRC.PRG Rev.1 January 2005 Page. 164 of 175

1948

Sands-Wainwright-Schmidt Ind. Eng. Chem (4) Soda Iron Process Kohl Petrol Processing – January Using MDEA Sherwood-Pigford Absorption and Extraction - McGraw Hill General interest Griffith Industrial Engineering Chemistry (5) Tames North Board Gas Process (Sulphite oxidation) Terres Gas U. Wasserfach (9) Polythionate solutions Benson-Field-Jimeson Chemical Engineering Progress - July CO2 Absorption with Hot Potassium Carbonate Solutions. Jegorov-Dimitriev-Sikov Hoepli Processes with arseniate for desulphuration Blohm - Riesenfeld US Patent 2.712.901 Using DGA Polderman-Dillon-Steele Oil Gas Journal - May - 16 Degradation of MEA in Natural Gas Treating Service Benson-Field-Haynes Chemical Engineering Progress - 52 Improved Process for CO2 Absorption uses Hot Carbonate Solutions Polderman-Steele Oil Gas Journal - July - 30 Degradation of DEA in Gas Treating Service Guntermamm-Schnurer Gas U. Wasserfach (25) Oxidation towers

1951

1952

1952

1953

1954

1954

1955

1955

1956

1956

1957

Eni S.p.A.
Exploration & Production Division 1958 Davis-Mills-Rydem Gas Council/GB Methylene blue procedure Reid-Towsend Oil Gas Journal - October - 13 Oxidation with SO2 in TEG solution Palo Petroleum Refinery - December Alkaline solutions – foaming agents Liedholm Shell Develop. C. - February Shell K3P04 Process Riesenfeld-Mullowney Petroleum Refinery - May Giammarco-Vetrocoke Process

00342.HTP.PRC.PRG Rev.1 January 2005 Page. 165 of 175

1958

1958

1958

1959

1959

Powdrill The Institution of Gas Engineers Operation of Liquid and Gastechink Purification Plants at Cardiff Leuhddemann-Noddes-Schwartz Oil Gas Journal - August - 30 Alkazid Process Sexauer Gas U. Wasserfach (27) Silos system with regeneration Benson-Field Petroleum Refinery - April Benfield Process Bienstock-Field Corrosion - July - 17 Alkaline solutions - corrosion Eickmeyer Chemical Engineering Progress - April - 22 Catacarb Procedure Nicklin-Holland European Symposium on Cleaning Coke Oven Gas - Saarbrucken Stretford Procedure Dingman

1959

1959

1960

1961

1962

1963

1963

Eni S.p.A.
Exploration & Production Division

00342.HTP.PRC.PRG Rev.1 January 2005 Page. 166 of 175

Hydrocarbon Processing How Acid Gas Loading Affects Physical Properties of MEA Solutions 1963 Zapfe Oil Gas Journal - August - 19 Procedure with activated carbon Williams Hydrocarbon Processing - July How To Remove Mercaptans from Natural Gas Ludwig Allied Process Design for Chemical & Petrol-chemical Plants - Vol. III General information Dunn-Freitas-Hill Hydrocarbon Processing - April First Plant Data from Sulfinol Process Duckworth-Geddes Oil Gas Journal - September - 13 Absorption on solid bed with continuous regeneration Blake Oil Gas Journal – January - 9 How Acid Gas Treating Processes Compare Buttwell Hydrocarbon Processing - April How to Maintain Effective MEA Solutions Dingman-Moore Hydrocarbon Processing - July Using DGA Deavon Oil Gas Journal - April Purisol Removes CO2 from H2, NH3 Syn Gas Hochgesand Industrial & Engineering Chemistry (7) Rectisol and Purisol Swaim Hydrocarbon Processing - March Gas Sweetening Process of the 1960s Dailey Oil & Gas Journal - May - 4

1964

1965

1965

1965

1967

1968

1969

1969

1970

1970

1970

Eni S.p.A.
Exploration & Production Division Animine – concentrated DEA – SNPA Process 1970 Franckowiak Hydrocarbon Processing - March Estasolvan: New Gas Treating Process Hasebe Chem. Econ. & Eng. Review (J) - March Takahax Procedure Guyot-Martin Canadian Gas Processors Association Meeting Sulfreen Process Hawkes - Mago Hydrocarbon Processing - August Stop MEA CO2 Corrosion

00342.HTP.PRC.PRG Rev.1 January 2005 Page. 167 of 175

1970

1971

1971

1971

Ludberg 64th Meeting of Air Pollution Control Association Removal H2S from Coke Oven Gas by Stretford Process The Benfield Corporation The Way to Low Cost Scrubbing of CO2 and H2 S from Industrial Gas Barthel-Bistri-Renault Hydrocarbon Processing - May IFP Process: Oxidation with SO2 in solvent at high temperature Livingston Hydrocarbon Processing – January Pretreat Syn Gas Feeds (ZnO) Nonhebel Edit. Newness-Butterworths-London Gas Purification Processes for Air Pollution Control Barry Hydrocarbon Processing - April Reduce Claus Sulphur Emission Martin Hydrocarbon Processing - April Plant Peaks Sulphur Recovery Butwell-Hawkes- Mago Chemical Engineering Progress - February Corrosion Control in CO2 Removal Systems

1971

1971

1971

1972

1972

1973

1973

Eni S.p.A.
Exploration & Production Division 1973 Ranke Linde Reports (18) Rectisol Procedure Ruziska Chemical Engineering Progress - 69 Packings for Hot Carbonate Systems Scheirman Hydrocarbon Processing - August Filter DEA Treating Solutions Moyes-Wilkinson Chemical Engineering – February Development at the Holmes - Stretford Process Kohl-Riesenfeld Gas Purification General Information Goar Hydrocarbon Processing - July Impure Feeds Cause Claus Plant Problem Bratzler-Doeges Hydrocarbon Processing - April Amisol Procedure Maddox Gas and Liquid Sweetening General information Kasay Hydrocarbon Processing - February Konox Process Removes H2S Baker Hydrocarbon Processing - April Corrosion Free Gas Sweetening

00342.HTP.PRC.PRG Rev.1 January 2005 Page. 168 of 175

1973

1973

1974

1974

1974

1974

1974

1975

1975

1975

Strelzoff Chemical Engineering - September Choosing the Optimum CO2 Removal System utilization Anon Natural Gas Processing Conference - Dublin SULFINOL PROCESS Kent-Eisendef

1976

1976

Eni S.p.A.
Exploration & Production Division Hydrocarbon Processing – February Better Data for Ammine 1976

00342.HTP.PRC.PRG Rev.1 January 2005 Page. 169 of 175

Schianni Natural Gas Processing & Utilisation Conference - Dublin Cryogenic Removal of Carbon Oxide from Natural Gas Raney Hydrocarbon Processing - April Remove CO2 with Selexol Archibald Hydrocarbon Processing - March Process Sour Gas Safely Vidaurri-Kahre Hydrocarbon Processing - November Recover H2S Selectively from Sour Gas Streams Tennyson-Schaaf Oil Gas Journal – January - 10 Guidelines Can Help Choose Proper Process Gas Treating Kelly Hydrocarbon Processing - July How Ammine Guard Saves Energy Vasan Oil Gas Journal - 1978 Holmes-Stretford Process Offers Economic H2S Removal Judd Hydrocarbon Processing - April SELEXOL Procedure Klein Oil & Gas International - September - 10 DIPA/Sulfinol Processes Christensen-Stupin Hydrocarbon Processing – February Merits of Acid Gas Removal Processes Rayan-Loiselle Hydrocarbon Processing - November Make Sulphur from Lean Acid Gas Ouwerkerk Hydrocarbon Processing – April

1976

1977

1977

1977

1977

1978

1978

1978

1978

1978

1978

Eni S.p.A.
Exploration & Production Division Design for Selective H2S Absorption 1978 Judd Hydrocarbon Processing - April SELEXOL Unit Saves Energy Palm-Caruthers Oil Gas Journal - November Guidelines Aid Control of SRU Tail-gas Emissions

00342.HTP.PRC.PRG Rev.1 January 2005 Page. 170 of 175

1978

1978

Pagani-Guerreri-Peri USA Patent 4.097.257 Natural Gas Having High Content of Acidic Gases Purification Method Grancher Hydrocarbon Processing - September Advances in Claus Technology Gas Processors Association Oil Gas Journal - July - 24 H2S Removal with MDEA Wright-Strauge Oil Gas Journal - February Modified Sulphur Recovery Process Meets Air Quality regulation Manning Oil Gas Journal - October - 15 Chemsweet Process Kennard-Meisen Hydrocarbon Processing - April Control DEA Degradation Henderson-Hudson-Kimble SPE of AIME Conference - September Jay and Flowation Fields Sulphur Plant Operations Holmes-Ryan-Price-Styring GPA Pilot Test Prove Ryan/Holmes Cryogenic Acid Gas/Hydrocarbon Separation Meissner World Oil - October Purifying CO2 for use in EOR Blanc-Elgue-Lallemand Hydrocarbon Processing - August

1978

1978

1978

1979

1980

1980

1980

1980

1981

Eni S.p.A.
Exploration & Production Division MDEA Process Selects H2S 1981

00342.HTP.PRC.PRG Rev.1 January 2005 Page. 171 of 175

Keaton Hydrocarbon Processing – August Activated Carbon System Cuts Foaming and Amine Losses Parnell Hydrocarbon Processing - April General information Sigmund-Butwell-Wussler Hydrocarbon Processing - May Ucarsol Process Zawacky-Duncan-Macriss Hydrocarbon Processing - April Process Optimized for High Pressure Gas Clean-up Kresse-Lindsay Oil Gas Journal - January - 12 Stretford Process Vaz-Mains Hydrocarbon Processing - April Ethanolamines Process Simulated by Rigorous Calculation Huval-Van De Venne Oil Gas Journal - August - 17 Fluor Econamine/DGA Process Meisen-Kennard Hydrocarbon Processing - October DEA Degradation Mechanism Holmes-Ryan-Price-Styring Hydrocarbon Processing - May Process Improves Acid Gas Separation Blanc-Grall-Demarais University Oklahoma Conference Degradation Products and Corrosion of Plants Using DEA/MEA Goodin Hydrocarbon Processing - May Pick Treatment for High CO2 Removal Mackinger-Rossati-Schmidt Hydrocarbon Processing - March Sulfint Process

1981

1981

1981

1981

1981

1981

1982

1982

1982

1982

1982

Eni S.p.A.
Exploration & Production Division

00342.HTP.PRC.PRG Rev.1 January 2005 Page. 172 of 175

1982

Kaplan Chemical Engineering - November Cost-saving Process Recovers CO2 from Power-plant Flue Gas Brown Unido Tech. Conference-Peking Giammarco (with glycine)/Criteria for Selecting CO2 Removal Processes Hass-Fenton-Gowdy-Bingham Sulphur Conference Selectox and Unisulf: New Technologies for Sulphur Recovery Butwel-Kubek-Sigmund Hydrocarbon Processing – March Alkanolamine Treating Woelfer Hydrocarbon Processing - November Sepasolv Process Villa Air Pollution Seminar-Kuwait IGI Experience of Modified Claus Process Jarett Hydrocarbon Processing - April Fundamentals of Acid Gas Fractionation Nicholas-Wilkins-Li Hydrocarbon Processing - September Optimize Acid Gas Removal Russel Hydrocarbon Processing-August Field Tests for Delsep Permeators (Membrane) Goldstein-Edelmann-Beisner-Ruziska Oil Gas Journal - July - 16 Flexsorb Process/Hindered Amines Yield Improved Gas Treating Parro Oil Gas Journal - September - 24 Membrane CO2 Separation Stanbridge-Hefner AICHE Meeting Anaheim-California Recent Developments in BASF Activated MDEA Process

1982

1982

1982

1982

1983

1983

1983

1983

1984

1984

1984

Eni S.p.A.
Exploration & Production Division 1984 Sulphur - November - December Catalyst and the Claus Process

00342.HTP.PRC.PRG Rev.1 January 2005 Page. 173 of 175

1984

Price Oil Gas Journal - December Looking at CO2 Recovery in Enhanced Oil Recovery Projects Gazzi-D’Ambra-Rescalli Hydrocarbon Processing - July Cryofrac Procedure Mortko Hydrocarbon Processing - June Selexol/Remove H2S Selectively Bucklin Schendel Energy Progress - September Comparison of Fluor Solvent and Selexol Anon Chemical Processing - November - 15 Non Toxic Catalytic Reagent Converts H2S in Sulphur Daviet-Sundermann-Donnelly Hydrocarbon Processing - May Switch to MDEA Raises Capacity Clem 35th Annual Gas Condition Conference Flexsorb Process Pearce-Du Part Hydrocarbon Processing - May Amine Inhibiting Netzer Hydrocarbon Processing - April Randall Process: Process Designed to Recycle CO2 Thomason Hydrocarbon Processing - April Reclaim Gas Treating Solvent Byeseda-Deetz-Manning Oil Gas Journal - June - 10 Optisol: a New Gas Sweetening Solvent Hardison Hydrocarbon Processing - April

1984

1984

1984

1984

1984

1985

1985

1985

1985

1985

1985

Eni S.p.A.
Exploration & Production Division Lo-Cat Process 1986 Schillmoller Hydrocarbon Processing - June Amine Stress Cracking: Causes and Cures Lath-Herbert Hydrocarbon Processing - August Amisol Solvent

00342.HTP.PRC.PRG Rev.1 January 2005 Page. 174 of 175

1986

1986

Riesenfeld-Brocoff Oil Gas Journal - September - 29 Proc. MDEA/Tertiary Ethanoloammines More Economical for H2 S/CO2 Removal King-Stanbridge Oil Gas Journal - September - 8 Rigorous Screening Selects Sour Gas Plant Process Maddox-Morgan Hydrocarbon Processing - August Select E.O.R. Processes for CO2 Bradley Oil Gas Journal - March - 17 CO2 E.O.R. Requires Corrosion Control Program in Gas Gathering Bianco Oil Gas Journal - August Calculation Methods Simulates LPG H2S MEA Carnell Oil Gas Journal - August New Fixed-bed Adsorbent for Gas Sweetening Heisel-Masold Hydrocarbon Processing - April New Gas Scrubber Removes H2S (Sulfolin) Marsh Oil Gas Journal - August Michigan Plant Opens up Nearby Sour-gas Field Chowdhury Chemical Engineering - September Membranes Set to Tackle Larger Separation Tasks Kresse Oil Gas Journal - October

1986

1986

1986

1986

1987

1987

1987

1987

1987

Eni S.p.A.
Exploration & Production Division

00342.HTP.PRC.PRG Rev.1 January 2005 Page. 175 of 175

CO2 Removal Reduces Pipeline Corrosion at Two Storage Sites 1987 Goar Chemical Engineering - December Claus Oxygen - Based -Process Expansion (COPE) Youn-Poe-Sattler-Inlon Oil Gas Journal - November CO2 Recovery EOR SAGA - Ryan Holmes

1987

Sign up to vote on this title
UsefulNot useful