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Gasp Re Treatment
Gasp Re Treatment
J.M. Klinkenbijl M.L.Dillon E.C. Heyman Shell International Oil Products Research & Technology Centre Amsterdam
1. Introduction
The type of contaminants and their concentration in the natural gas affect the overall LNG production cost. In the past most feed gases for base load LNG plants only contained CO2 (<< 10 mol%) with traces of H2S. This type of gas requires the minimum of pre-treatment. As the market for LNG has expanded and more gas fields become economically viable to develop there has been a need to treat feed gases richer in CO2 , H2S, COS and mercaptans. This naturally increases the cost of the liquefaction pre-treatment, due to larger acid gas removal units and the requirement for a sulphur recovery step. The same economic forces also push the limits of required operating window to for example colder feed gas temperatures and higher operating pressures. The requirement for drying and mercury removal has remained basically constant.
3. Liquefaction Pre-Treatment
3.1. Introduction
Pre-treatment upstream a liquefaction unit traditionally consists of an acid gas removal step, in which CO2 and sulphur compounds (H2S, COS and mercaptans) are removed, a dehydration step and a mercury removal step. Where there are limitations on the SO 2 emissions, the removed sulphur components are recovered as elemental sulphur. Environmental limitations to hydrocarbon emissions can require incineration of CO2 acid gas even in the absence of sulphur compounds. Figure 1 shows a typical block diagram of a base load LNG train. The mercury removal step can be positioned upstream of the acid gas removal or downstream of the dehydration step.
The Shell Sulfinol process is the most widely applied acid gas removal process in the base load LNG industry (~40% of current installed capacity) and has also been chosen for the majority of new projects currently under construction. In total there are about 200 Sulfinol units world wide. The main advantages of the process are: the capability of simultaneously removing H2S, CO2, COS and organic sulphur components, a high reliability, because sulfolane acts as a foam inhibitor resulting in a lower foaming tendency than aqueous amine solvents, and because of the low solvent corrosivity, the low specific energy consumption, the physical character of the solvent can be varied by choosing the relative amounts of water and sulfolane to trim the COS and mercaptans removal [9], a lower water content in treated gas compared to aqueous amines widely available solvent components not restricted to a proprietary supplier. the ability to treat cold, low CO2 gas where rich solvent temperatures approach 20oC the ability to operate at pressures well above 100 bara. A potential disadvantage is the somewhat higher hydrocarbon solubility. However, this solubility is still far less than that of a purely physical solvent and is normally considered acceptable. It is possible to remove H2S, CO2 and mercaptans using molecular sieves, however, this is not economical for large quantities of CO2 [1]. When H2S and mercaptans are removed with molecular sieves, the regeneration gas needs to be treated in a separate H2S and mercaptans removal unit.[17] This generally results in a more complex line-up and higher cost. The Sulfinol technology has recently been enhanced with a new patented technology for solvent reclamation. This process based on two stage wiped film evaporation provides a simple and efficient way to keep solvent in as new condition by separation of degradation products, heat stable salts and fine particulates with 95% recovery of the solvent components.
F e e d G a s S u p p l y G a s R e c e i v i n g & M e t e r i n g
C O 2 S O 2
M e r c u r y R e m o v a l
I n c i n e r a t i o n
A c i d G a s R e m o v a l F u e l g a s
S u l p h u r R e c o v e r y
S u l p h u r D e h y d r a t i o n
D i s p o s a l
U * * * *
tilities H T F Electricity W a t e r N i t r o g e n
M e r c u r y R e m o v a l P r e - T r e a t m e n t S e c t i o n H y d r o c a r b o n S e p a r a t i o n F r a c t i o n a t i o n
L i q u e f a c t i o n
N G L
T r e a t m e n t
L N G
S t o r a g e
N G L
S t o r a g e
L N G
S h i p p i n g
N G L
P r o d u c t s
1000000
100000
10000
15 ton su
1000
gs
ulp
hu
r/
tur ati on
day
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Amine+SulFerox or Thiopaq
unit. When the recovery should be larger than 95 %, a tail gas treating unit is often required. Commonly applied processes are the SuperClaus and sub-dewpoint processes which are generally selected for efficiencies of around 99 %, while the SCOT technology is utilised for more than 99.5 % overall S-removal. When a SCOT process is selected, the absorption section of the SCOT can be easily integrated with the Sulfinol process in the acid gas section. In case the H2S/CO2 ratio in the feed gas is <0.2 mol/mol, the acid gas ex the acid gas removal plant will be difficult to process in a straight through Claus unit. A way to improve the Claus feed gas quality would be to remove CO2 from the acid gas before routing to the Claus unit. Two options to improve the situation exist: include an enrichment step in the acid gas removal scheme. An enrichment step includes a CO2 flash prior to solvent regeneration to reduce the amount of CO2 to the Claus unit. If required an H2S re-contactor is added to fulfil flash gas specifications. enrich the acid gas before sending to the Claus unit in a dedicated system.
When an enrichment step is selected, this can be included in the acid gas removal step. A solvent which is selective for H2S is most effective. However, a selective solvent may not be the most appropriate choice for CO2 removal. The H2S/CO2 ratio and process conditions will determine the applicability of this option. Alternatively enrichment is achieved by a dedicated unit selectively absorbing H2S from the acid gas produced by the main CO2 removal unit. In this case a stand alone enrichment system is used. Due to the better selectivity this option may economically be more attractive [16]. When removing organic sulphur, partial mercaptan removal in a mixed solvent can be combined with removal of the rest of the mercaptan a separate molecular sieve bed (integrated in the dehydration unit). The molecular sieve regeneration gas is treated in a dedicated absorber column. This has been described in reference [17]. The regeneration gas may also be recycled to the main acid gas absorber. Optimisation of such a line up is very dependent on the level of organic sulphur in the feed gas and the total sulphur specification for the treated gas. Beside the optimisation in process line-up determined by component removal, optimisation based on energy requirements is possible. As example the use of the steam generated in the Claus unit may be sufficient to supply the regeneration heat to the dedicated tail gas unit. To determine the best line-up and process selection is very much dependent on the initial feed gas conditions, the treated gas specifications and environmental requirements. Before the treating cycle is selected, it is strongly recommended that an optimisation study is carried out to obtain the lowest capex/opex and largest operating window with respect to feed gas composition.
3.6 Incineration
If the acid gas removal off-gas only contains CO2 it can be vented, however if H2S and/or aromatics are present, even in small amounts, the gas must be sent to an incinerator to prevent unsafe situations. The incinerator is normally of the thermal type, operating at about 800 oC, to achieve nearly complete H2S combustion (< 10 ppmv). If a Claus and/or SCOT unit are used the tail gas must also be incinerated. Modern adsorption materials also present the possibility of removing low levels of H2S by fixed beds where it is permitted to vent the balance of the acid gas stream. An interesting recent development is the option of using the hydrocarbon containing CO2 off-gas as fuel in steam boilers or furnaces. This concept can eliminate the need for an incinerator or allow for a considerably smaller incineration unit. With the increasing emphasis on reduction of greenhouse gas emission the option of acid gas recompression and subsequent re-injection is now being considered.
3.7 Dehydration
The sweet gas leaving the acid gas removal step is saturated with water because most sweetening solvents are aqueous solutions. First, the bulk of the water is condensed and separated from the gas stream by cooling. The cooling is limited to temperatures above the hydrate formation temperature (~20 oC). The water content is then further reduced to 0.5 ppmv by drying, normally with molecular sieves (4A-type). At least two of these dryers are required for each train; one is in adsorption service while the other is being regenerated by heated dry gas. The adsorption capacity of the molecular sieve decreases within two to four years to a level where it is necessary to replace the deactivated material. Recent developments have resulted in improved molecular sieves with higher absorption capacity and more resistance to degradation. The latest modelling techniques allow better optimisation of design and operation. Our research work has shown that deactivation is mainly due to a combination of two effects: (a) coke formation in the sieve and (b) caking due to hydrothermal instability of the sieve. Coke reduces the maximum water adsorption capacity, while caking leads to irreversible loss of drying capacity due to an increased residual water load after regeneration. With our specific knowledge on both the adsorption step and the regeneration step and the understanding of the deactivation mechanisms, we can optimise the operation of these units to be more cost effective. The combination of mercaptan removal and de-hydration in one step is discussed in section 3.5.
4. Cost
4.1. Introduction
The capital investment of a treating scheme is, of course, dependent on the type and concentrations of the contaminants in the feed gas and environmental targets. The costs of the dehydration and the mercury removal steps are mainly dependent on the gas throughput. The water content of the feed gas to the dehydration unit will not vary significantly if upstream cooling is applied to say about 20 oC. Dehydration can be significantly cheaper if a nonaqueous solvent can be used. The size of the mercury removal bed is mainly determined by contact time and hence throughput. The H2S, CO2 and mercaptan content of the gas will greatly influence the cost of the acid gas removal and the sulphur recovery units. Apart from the capital investment, the energy consumption,
the operational cost of the unit and the hydrocarbon losses are important parameters. Integration of the processes can contribute considerably to the cost reductions.
In previous work [1] the conclusion was drawn that for large gas volumes containing less than 1520 mol% CO2 the Sulfinol process was more economical than pure physical processes. Since 1996 several cases have been studied for the comparison of Sulfinol-D with alternative amine processes. The alternative processes comprise a representative modified MDEA solvent and an alternative mixed solvent. Results are shown below.
Costs 13 % CO2 removal processes +/- 30%
120 100 Relative costs 80 60 40 20 0 Alt MDEA Alt mixed solvent SulfinolD Capex Opex
The formulated MDEA process figure is based on the most competitive MDEA based process as determined by recently completed process comparison studies. In the selection of the most attractive process, uncertainties in feed gas compositions (e.g. level of sulphur) and future requirements can often shape the ultimate choice.
4.3. Feed Gas with H 2S, CO2 and Organic Sulphur Components
If, as in some recent projects, H2S and organic sulphur compounds are present in the feed gas to the LNG plant the cost of the gas pre-treatment can increase significantly. Where organic sulphur components are present, the Sulfinol process is often the preferred process as it combines H2S, CO2, COS and mercaptans removal in one step. This cannot be achieved with aqueous amines. In recent years this approach has been applied in the Shell Caroline plant [10], the Sexsmith gas plant [9] and the Qatargas LNG plant [13]. If the H2S and CO2 content of the feed gas is high, the mercaptans are removed without any additional cost. Only where the H2S and CO2 concentrations are low, will mercaptans removal determine the size of the acid gas removal unit. If there are restrictions on the SO 2 emissions, a sulphur recovery step is required. From figure 2 it can be concluded that above about 500 ppmv H2S in the feed gas, a Claus unit is almost the automatic choice. For a project producing 3 mtpa LNG, with 2 mol% CO2 and 2 mol% H2S in the feed, the sulphur production is about 400 t/d. In this case the cost of the Claus unit is similar to the cost of the acid gas removal unit. If the SO 2 emission limit cannot be met with just a Claus unit , a SCOT unit can be used to improve the sulphur recovery efficiency to 99.9%. This will obviously increase the overall cost. As a bonus the steam generated by the Claus unit may be sufficient to make the total treating scheme almost self-supporting with respect to energy consumption. As explained before in chapter 3, the cost of a Claus unit increases with decreasing H2S content of the acid gas feed. Figure 3 gives an impression of the capital cost of a sulphur recovery unit as function of the H2S content of the feed [2]. H2S enrichment of the Claus feed gas can be economical, especially if the enrichment is combined with a SCOT unit. The enrichment absorber and the SCOT absorber then share the same regenerator and solvent cascading is possible. This type of enrichment scheme will be applied in a new LNG project. Other enrichment schemes have been discussed before [2] and have been applied in e.g. the NAM Emmen Sulfinol-M plant [11]. It is very important for these applications that already in an early stage a good feed characterisation is made. The lowest foreseen H2S/CO2 ratio in the feed gas and the mercaptan content are critical to the final process selection [9] and developing the most cost effective design.
1.9
1.7
1.6
1.5
1.4
1.3
1.2
1.1
Figure 3. Effect of H2S content of Claus feed on the relative cost of a Claus plant.
To illustrate the effect of H2S on the costs of a pre-treating section, the example represented in table 2 has been used with the addition of a 90 t/sd sulphur removal requirement. The adaptations in the line-up foresee in an enrichment section and a sulphur recovery unit. In view of expected environmental constraints a 99.9 % sulphur recovery has been taken in account. The results are represented in table 3.
Table 3. Capital cost of the pre-treatment section relative to the total cost of the processing units for a typical LNG train (~3 mtpa LNG) with the addition of 90 t/d H2S removal capacity. 2 % CO 2 in feed 11 % CO 2 in feed 14 % CO 2 in feed Mercury Removal (%) 1.1 0.8 0.8 Dehydration (%) 4.3 3.3 3.3 H 2 S/CO 2 removal unit (%) 10.5 17.7 19.3
Comparing table 2 and 3 leads to the conclusion that the cost share for the gas treating step substantially increases with the addition of H2S removal capacity. Contributing factors are the need for enrichment (in this example) and the sulphur recovery. The effect of H2S removal on the gas treating processes is illustrated below for a typical aqueous MDEA (Adip) solvent and a mixed solvent. It should be realised that again the feed gas composition is of major importance.
Costs for low CO2/1.3 %v H2S removal +/- 40 %
120 100 Relative costs 80 60 40 20 0 Alt mixed solvent Aqueous MDEA Capex Opex
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In case the CO2 content is very high (in this example > 20 %v) a specific enrichment of the acid gas ex gas treating section is required to provide an acceptable Claus feed gas. Influence on the costs is represented in the next bar chart. Please note that this is a very severe example.
Costs for high CO2/1.3 %v H2S removal processes +/40 % with and without enrichment
200 180 160 140 120 100 80 60 40 20 0 Alt mixed solvent Aqueous MDEA Alt mixed solvent + enrichment Aqueous MDEA + enrichment
Relative costs
Capex Opex
5. Developments in Pre-Treatment
Membrane separation is based on thin barriers which allow preferential passage of components to separate multi-component feeds. The driving force for permeation is the difference in partial pressure between the feed gas and the permeate side of the membrane. Selectivity is achieved by differences is permeation rates. Membrane units for natural gas processing are commercially being used for CO2 / H2O removal to pipeline specification [15], production of CO2 for Enhanced Oil Recovery (EOR), unloading of existing treating plants, concentration of natural gas liquids. The use of membranes in large volume natural gas applications for e.g. CO2 removal is still restricted by the relatively high hydrocarbon losses and the fact that membranes do not have the same economy of scale as many other processes due to their modular nature. Current developments are therefore in improved permeance, reducing the required membrane area, and in improved CH4/CO2 selectivity to further reduce the hydrocarbon losses with the permeate. Inorganic membranes are an example of recent developments in this area [7]. Membranes can be economically used in the bulk CO2 removal step for natural gases containing high concentrations of CO2. Amine processes using partial flash regeneration, such as Sulfinol-M or MDEA, are the most economical solution for large volumes of natural gas containing less than about 15 mol% CO2 [6]. Above 15 mol%, a bulk CO2 removal step upstream of the amine unit can be attractive. Membranes can also be attractive for debottlenecking of existing CO2 removal plants, as long as the permeate can be used as fuel. Another area of interest is the use of membrane technology for LNG floaters, where movement can be significant. A disadvantage of conventional technology is that the internals, such as acid gas absorber trays and packing are sensitive to movements [8]. Several research institutes, such as GRI (USA) and TNO (Netherlands), are developing membrane alternatives for absorber trays, which are less sensitive to movement. An added advantage of the membrane contactor is the reduction of heavy hydrocarbon co-absorption, while the absence of direct gas-solvent contact removes the risk of foaming.
6. Technology Selection
Simple rules for the selection of the most effective LNG pre-treatment technology are difficult to arrive at given the array of possibilities in feed gas conditions and resultant requirements for one or
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more of : one or two stage gas treatment, acid gas enrichment, mercaptan removal, sulphur recovery technology, Claus tail gas treatment, high pressure operation, low temperature operation etc. Added to this are other considerations such as reliability record, corrosion performance, quality of process guarantees and availability of professional after sales technical service. Given the magnitude of the investment in an LNG facility it is appropriate to carry out a rigorous treating process selection study to identify the most cost effective and fit for purpose treatment package. The consultant chosen to do the study must be experienced in the field of LNG gas pretreatment design, familiar with all the technologies available, able to discern effective integration options and ideally be able to draw upon actual operating experience to identify a robust operating line up. The investment in a high quality consultant to provide process selection will be well rewarded with a reliable, fit for purpose and cost effective treatment package.
7. Conclusion
Up until recently the levels of CO2 and sulphur encountered in most LNG developments have allowed a fairly open selection of solvent based pre-treatment technology although preference has most often been given to well proven technologies. However with increased sulphur levels, mercaptans and more extreme operating requirements the available choices for a cost effective integrated treating package narrow dramatically. Use of the Shell Sulfinol technology can be the decidedly more attractive option in these cases. It is critical that each new gas development undergo a rigorous selection study to identify the most cost effective and fit for purpose treating package.
8. References
[1] Klein, J.P., Verloop, J., The purification of Natural Gas prior to liquefaction, Paper presented at the Second Iranian Congress of Chemical Engineering, Tehran, 11th-14th May 1975 [2] McEwan, M.C., Marmin, A., Developments in LNG Treating, Proceedings of LNG-6 Kyoto April 1980 Vol.II Appendix Paper 3. [3] Peebles, M.W.H., Natural Gas Fundamentals, Shell International Gas Limited, 1992 [4] Avidan, A.A., et al., LNG links remote supplies and markets, Oil & Gas Journal, June 1997,pp 54-59 [5] Bellow, E.J., et al., Technology advances keeping LNG cost-competitive, Oil & Gas Journal, June 1997, pp 74-78. [6] McKee, R.I., et al., CO2 removal: membrane plus amine, Hydrocarbon Processes, April 1991, pp 63-65 [7] Minutes Gas Utilisation Research Forum, June 1997, Copenhagen, Denmark. [8] Naklie, M..M., Design advanced for large-scale economic, floating LNG plant, Oil & Gas Journal, June 1997, pp 66-69 [9] Johnston, A.L., Moore, B.K., Balancing cost with process, resident and regulatory needs, Laurence Reid Gas Conditioning Conference paper, March 1997. [10] Cheng, N. et al., Shell Canadas Caroline Gas Plant reaches smooth operation, Laurence Reid Gas Conditioning Conference paper, March 1997 [11] Taylor, N.A., et al., Gas-desulfurisation plant handles wide range of sour gas compositions, Oil & Gas Journal, August 1991, pp 57-59 [12] Wetzels, M.L.J.A., et al., The SCOT Process: still very much alive nearly twenty years after its first introduction, Western Research Seminar, November 1990, Budapest. [13] Oil & Gas Special: Natural gas in the Middle East, February 1997, pp 49-64 [14] Holmes, E.S. et al., Process Improvements in acid gas and mercury removal, AIChE 1994 Spring National Meeting, Atlanta, April 1994 [15] Cook, P.J., Losin, M.S., Membranes provide cost-effective natural gas processing, Hydrocarbon Processing, April 1995, pp 79-84 [16] Abdul Redha Abdul Rahman, Qatar Liquefied Gas Co., Doha, Qatar & Masayuki Ishikura, Chiyoda Corp., Yokohama, Japan, 1LNG from giant North field: Qatar Gas LNG, 1998 presented LNG 12 conference, Perth, May 1998 [17] Clarke D.S., Sibal P.W., Gas Treating Alternatives for LNG Plants, GPA, March 16-18, 1998, Dallas Texas
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