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Comparing different biogas upgrading techniques

Final report

J. de Hullu J.I.W. Maassen P.A. van Meel S. Shazad J.M.P. Vaessen L. Bini, M.Sc. (tutor) dr. ir. J.C. Reijenga (coordinator) Eindhoven University of Technology, July 3, 2008

Abstract This report is the result of a multidisciplinary project at the technical university of Eindhoven commissioned by Dirkse Milieutechniek BV. The goal of the project was to research and compare the currently available techniques to upgrade biogas. Upgrading of biogas comprises the removal of CO2 , H2 S and other possible pollutants from biogas. This increases the concentration of CH4 which gives the biogas a higher calorific value allowing for injection in the gas grid or to use as a fuel. H2 S has to be removed because of its corrosiveness. Five techniques have been investigated. Chemical absorption of H2 S and CO2 into iron-chelated cq. amine solutions offers a highly efficient removal of H2 S from a gaseous biogas stream. The catalyst solutions function as a pseudo-catalyst which can be regenerated. The H2 S is removed almost completely and converted to elemental sulphur. The CO2 is removed and is treated as a waste stream. High pressure water scrubbing is based on the physical effect of dissolving gases in liquids. In a scrubber, CO2 as well as the H2 S, dissolve into the water while CH4 does not, because of their difference in solubility. This makes water scrubbing a very simple process. Pressure swing adsorption separates certain gas species from a mixture of biogas under pressure, according to the species molecular characteristics and affinity for an adsorption material. The adsorption material adsorbs H2 S either irreversibly or reversible. Therefore a complex H2 S removal step or regeneration phase is needed for this process. The fourth process separates the components cryogenically. The different chemicals in biogas liquefy at different temperature-pressure domains allowing for distillation. Typically a temperature of -100 ◦ C and a pressure of 40 bars is used. Finally, it is possible to separate CO2 and H2 S from CH4 using a membrane. Because of selective permeation, CO2 and H2 S will pass through a certain membrane while CH4 does not. This is also a very simple technique since only a compressor and a membrane are needed. Each technique is compared on financial feasibility, impact on the environment and ease of operating the process. Furthermore, each technique has its own unique advantages and disadvantages. Table 1 gives an overview of the costs, yield and purity of each technique.

Table 1: Comparison of prices, yield and purity of the different techniques

Technique Chemical Absorption High Pressure Water Scrubbing Pressure Swing Adsorption Cryogenic separation Membrane separation

Price per N m3 of biogas 0.28 0.15 0.26 0.40 0.22

Yield % 90 94 91 98 78

Purity % 98 98 98 91 89

Financial Feasibility Table 1 shows that high pressure water scrubbing seems to be the cheapest technique to upgrade biogas. Also this technique gives quite high yield and purity. Cryogenics is the most expensive way of upgrading biogas but it gives the highest possible yield. Impact on the environment Chemical absorption has several waste streams, one containing CO2 and two different streams containing amines or F e/EDT A complexes.These are the catalysts used in the absorption processes. All streams need to be disposed as chemical waste. High pressure water scrubbing has two waste streams. The water waste stream contains such a low concentration of H2 S and CO2 that it does not need further treatment. The second waste stream is a gas stream which also contains H2 S and CO2 but also some CH4 . Because H2 S is rather poisonous, this stream should be treated and the CH4 should be burned. Pressure swing adsorption and membrane separation both have one waste stream that mostly contains CH4 and has to be burned. Cryogenics has also one waste stream containing mostly CO2 and some traces of H2 S and CH4 . This waste stream needs treatment. Ease of operation The operation of the pressure swing adsorption and chemical absorption process is quite simple. However, the plant needs to shut down several times per year because the catalyst has to be replaced. Membrane separation and high pressure water scrubbing are the simplest processes to operate because they do not need special chemicals or equipment to run. Cryogenics is difficult to operate because it works on high pressure and really low temperatures and therefore need good checking of the insulation. But for scaling up cryogenics seems to be the most suitable technique.

Conclusion It can be concluded that high pressure water scrubbing is performing the best. With the low cost price, high purity and yield it is a promising upgrading technique. Though one waste stream needs treatment, it is a continuous process which operates almost on it self.

Preface
This report presents the results of a multidisciplinary project executed at the Eindhoven University of Technology commissioned by Dirkse Milieutechniek BV (DMT). The results are also presented on a poster and a website (http : //students.chem.tue.nl/if p24/). The aim of such a project is to teach students, by means of real problems, to combine and apply professional knowledge and skills and to integrate these into non-technical aspects of importance and new technical knowledge. The main goals are learning to communicate with colleagues from various fields, and to gain experience in working as a team, executing a research project. DMT solves environmental problems with tailor made solutions and is always seeking new possibilities to do so. DMT offers a wide range of products and services varying from research, development, consultancy and design to rental of equipment, installations service and maintenance. DMT supplies equipment and systems for air treatment, odor abatement, (bio)gas desulphurization, groundwater purification, soil remediation and waste water treatment. This project was focused on the upgrading of biogas. Biogas is a result of anaerobic digestion of organic material, resulting in methane and carbon dioxide gas and some pollutants. The methane gas can be used as a green energy source by upgrading the biogas to natural gas and injecting it into the existing gas grid. Upgrading of biogas signifies removal of the CO2 and pollutants such as H2 S. Currently, several processes are available for the upgrading. Project description DMT has developed a biogas upgrading technology based on high pressure water scrubbing. To get a leading position in the market, it is of most importance to know the advantages and disadvantages of all the different processes available for upgrading biogas and their cost.

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A literature study was conducted to create a clear overview of the present upgrading techniques allowing for an objective comparison. The comparison of the different options was focused on: • chemical absorption • high pressure water scrubbing • pressure swing adsorption • cryogenic separation • membrane separation Firstly, each technique is described shortly including a cost estimate of the cost price per cubic meter of upgraded biogas. Thereafter, a comparison of the advantages and disadvantages of the different techniques is given. These results will help Dirkse Milieutechniek decide which option to upgrade biogas best fits their customers demands.

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Contents
1 Introduction to Biogas 2 Upgrading techniques 2.1 Chemical absorption . . . . . 2.2 High pressure water scrubbing 2.3 Pressure swing adsorption . . 2.4 Cryogenic separation . . . . . 2.5 Membrane separation . . . . . 3 Comparison 4 Conclusions Acknowledgement Bibliography A Alternate cost estimation PSA B Cryogenic equipment C CO2 footprint D Visit to SMB Stortgas BV in Tilburg E Visit to Carbiogas BV in Nuenen . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4 8 8 15 20 23 28 32 35 37 38 41 44 46 49 51

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Chapter 1 Introduction to Biogas
The current use of fossil fuels is rapidly depleting the natural reserves. The natural formation of coal and oil however, is a very slow process which takes ages. Therefore, a lot of research effort is put into finding renewable fuels nowadays to replace fossil fuels. Renewable fuels are in balance with the environment and contribute to a far lesser extent to the greenhouse effect. Biogas is a renewable fuel, an energy source that can be applied in many different settings. It is defined as a combustible gas mixture produced by the anaerobic fermentation of biomass by bacteria and takes only a relatively short time to form. In nature, the fermentation process occurs in places where biological material is fermented in an oxygen deprived environment such as swamps and waterbeds. The two main sources of biogas from human activities are domestic garbage landfills and fermentation of manure and raw sewage. The advantage of processing these waste products anaerobically, compared to aerobically, is the larger decrease in volume of waste product. For this reason, the industry nowadays prefers anaerobic fermentation to process waste streams. Biogas mainly consists of combustible methane (CH4 ) and non-combustible carbon dioxide (CO2 ). Besides CH4 and CO2 , biogas also contains small amounts of hydrogen sulphide (H2 S) and some other pollutants. The composition of biogas strongly depends on its source. Table 1.1 [1] shows the composition of biogas from various sources. It can be seen that biogas from a garbage landfill also contains some nitrogen (N2 ). CH4 combusts very cleanly with hardly any soot particles or other pollutants, making it a clean fuel. But CO2 , the non-combustible part of the biogas, lowers the calorific value of the biogas. Biogas containing 60% CH4 has a calorific value of 21.5 MJ/N m3 while pure CH4 has a calorific value of 35.8 MJ/N m3 .

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Table 1.1: Overview of compositions of biogas from different sources

Component CH4 (%) CO2 (%) N2 (%) H2 S (ppm)

Biogas factory 60-70 30-40 <1 10-2000

Sewer factory Garbage landfill 55-65 45-55 35-45 30-40 <1 5-15 10-40 50-300

Besides CO2 , biogas also contains small amounts of H2 S. H2 S is poisonous when inhaled. Furthermore, when water is present, H2 S forms sulphuric acid (H2 SO4 ), which is highly corrosive, resulting in extra costs for maintenance when using the biogas. Depending on the source of the biogas, it can contain other pollutants. Common pollutants are water vapor, ammonia (N H3 ) and siloxanes. Water vapor in biogas forms, combined with N H3 or H2 S, a corrosive solvent. Siloxanes are silicate compounds that have oxygen groups replaced by organic groups like CH3 . When this compound is burned, it will form SiO2 (sand) which can cause severe damage to equipment. There are a number of uses for biogas. Currently, biogas which has been stripped of H2 S is mainly used in gas turbines to produce electricity. However, most energy is lost as heat in this process, which results in a low overall efficiency. But biogas can also be used for injection in the gas grid or as a car fuel. The requirements for the end product depend on the final use of the biogas. The average composition of gas in the gas grid for low calorific gas, used in The Netherlands, and high calorific gas, used for example in Canada, are shown in table 1.2 [2]. All of the values mentioned in table 1.2 are averages, except for the Wobbe index. The Wobbe index of the gas should always be in between the mentioned boundaries. To reach the calorific value of Dutch natural gas the methane purity should be increased to a value of 88%. But if Canadian standards must be achieved, as shown in table 1.2, the calorific value of biogas should be increased above the calorific value of methane. This of course can never be reached by increasing the purity of CH4 . Therefore, the purity of CH4 should be as high as possible and some higher alkanes are added to the gas to obtain the required calorific value. For injection of biogas into the gas grid there are some additional requirements. These are shown in table 1.3 [2].

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Table 1.2: Average compositions of gas used in the commercial gas grid in The Netherlands and Canada

Dutch natural gas Canadian natural gas Component (Source: Dutch Gas union) (Source: Uniongas Canada) Volume % Volume % Methane 81.30 94.9 Ethane 2.85 2.5 Propane 0.37 0.2 Butane 0.14 0.06 Pentane 0.04 0.02 Hexane 0.05 0.01 Nitrogen 14.35 1.6 Carbon Dioxide 0.89 0.7 Oxygen 0.01 0.02 Water vapor Unknown Unknown Hydrogen Unknown Traces 3 Density (kg/m ) 0.833 0.7525 Wobbe index (M J/m3 ) 43.1-44.6 50.5-52.5 Calorific value (M J/m3 ) 31.669 37.8 The minimum amount of CH4 required as well as the maximum amount of N2 depends on the Wobbe index. The Wobbe index is defined as follows: W obbe index = calorif ic value(M J/m3 ) √ relative density (1.1)

The Wobbe index is a measurement for the combustion behavior. If this value is too high or too low, the combustion behavior will be disturbed. The values may not deviate from the desired range. Biogas can also be used as a car fuel. However, because of the low energy per volume the biogas must be compressed up to 200 bars. Also, the

Table 1.3: Requirements for injection of biogas into the gas grid

Component CO2 Water Oxygen H2 S

Requirement < 8 vol % dewpoint < -10◦ C < 0.5 vol % < 5 mg/N m3 6

calorific value of the biogas should be at least the value of low calorific gas. Furthermore, there may be no water or heavier alkanes than propane in the biogas because it will form condensate at such a high pressure. Removing CO2 and H2 S from the biogas is not easy. However, the upgrading technology is rapidly evolving, bringing biogas as a reliable energy source in sight. To produce large amounts of upgraded biogas, it is necessary to examine different upgrading methods to see which method might be implemented in the industry. Calculating the so called CO2 footprint of each technique is valuable to determine the durability [3] [4].

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Chapter 2 Upgrading techniques
In this chapter, the five investigated upgrading techniques are explained. For each technique, a short description including a process flow diagram (PFD) is given and the distinctive advantages and disadvantages of each technique are discussed. The environmental impact of the upgrading processes is an important factor to compare the different techniques, so this is discussed for each technique. In order to compare the different techniques, the cost price of the produced upgraded gas must also be taken into account. The cost price per N m3 biogas are calculated using the following formula, in which the interest rate on the investment is taken to be 6%:
investment depreciation period N m3

P rice per N m3 =

+ investment · interest rate + annual cost produced upgraded gas per year

(2.1) For each technique the input flow is taken to be 250 N m3 /h containing 60 % of CH4 . The output is calculated as follows: Output = input · % CH4 · yield (2.2)

The total running costs are determined by the operating costs, the electricity and the water costs. The current electricity price is about 0.10 per kW h [13]. The price of water is 0.92 per m3 [14]. The service costs are 50,000 per year.

2.1

Chemical absorption

Both the chemical absorption of CO2 and H2 S were investigated.

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2.1.1

Chemical absorption of CO2

Multiple theories exist about the removal of CO2 in gas streams. However, these theories are often contradictive. In the following text, CO2 absorption using aqueous amino acid salt solutions will be discussed.
Cooler

Biogas out CO2

Absorption column Regeneration column Heat exchanger Gas stream in

Figure 2.1: Process flow diagram for chemical absorption of CO2

An amino acid dissolved in water exists as a zwitter ion. A zwitter ion can have a positive and a negative charge depending on the pH of the solution. The amino group has to be deprotonated before it reacts with CO2 . This deprotonation is mostly done by addition of an equimolar amount of base, according to the following mechanism [5]:
+ HOOC − R1 − N H3 + OOC − R2 − N H3

OOC − R3 − N H2

(2.3)

These aqueous solutions react with CO2 to absorb this component. In open literature about chemical absorption of CO2 , no reliable information about the reaction mechanism and kinetics is available. Therefore, the assumption is made that the reaction mechanism occurs according to the experimental studies of Kumar, Hogendoorn, Feron and Versteegh, 2002. The main reactions occurring during the absorption of CO2 are the following: 2 RN H2 + CO2
+ RN HCOO− + RN H3

(2.4)

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CO2 + OH − + RN H3 H2 O

− HCO3 RN H2 + H + H + + OH −

(2.5) (2.6) (2.7)

In reaction 2.4, the reaction of CO2 with an amino acid can be seen. The contribution of reaction 2.5 to the conversion of CO2 is not significant, while not much OH − ions are present in the solution because the pH is very low. Since the OH − ions are in equilibrium with the amine molecules, reactions 2.6 and 2.7 have to be taken into account. This study also discusses the Membrane Gas Absorption (MGA) investigated by TNO [6]. Research has been done by TNO at the membrane absorption technique. According to TNO, this is a technique which makes use of porous, water-repelling membranes for transport of components. Currently, new absorption liquids, called CORAL, are developed, which show a stable operation with cheap olefin membranes. According to P.S. Kumar et al. the MGA technique is economically not very attractive in comparison to conventional absorption processes, because of the limited availability of the fibres. The process flow diagram of the CO2 absorption process is shown in figure 2.1.

2.1.2

Chemical absorption of H2 S

In the literature [7] [8] several processes are presented which discuss the removal of H2 S. Many of these processes remove this pollutant only from the gaseous stream, but do not convert H2 S into a more stable or valuable product, or convert it into the elemental form sulphur (S). The conversion of H2 S into S or a valuable compound is an advantage of chemical absorption with respect to other methods. The process of chemical absorption of H2 S into iron-chelated solutions offers a highly efficient H2 S-removal, a selective removal of H2 S and a low consumption of chemicals, because the iron-chelated solutions function as a pseudo-catalyst that can be regenerated. The overall reaction of this purification process is expressed as follows [9] 1 (2.8) H2 S + O2 (g) → S + H2 O 2 In the reaction described above, H2 S is first absorbed into water and then undergoes the dissociation as follows: H2 S(g) + H2 O 10 H2 S(aq) (2.9)

H2 S(aq) HS −

H + + HS − H + + S 2−

(2.10) (2.11)

The formation of S occurs according to the reaction mechanism is described here: S 2− + 2F e3+ S + 2F e2+ (2.12)

By means of oxygenation the aqueous iron-chelated solution will be regenerated. This oxygenation is followed by conversion of the pseudo-catalyst into its active form F e3+ . This mechanism is shown in the following equations: 1 1 O2 (g) + H2 O(l) → O2 (aq) 2 2 1 O2 (aq) + 2F e2+ → 2F e3+ + 2OH − 2 (2.13) (2.14)

In this mechanism, several chelate agents can be used for the specific proposal of the overall reaction, with the EDT A being the most used common chelate [10]. In this process, the sulphur produced can be removed easily from the slurry by sedimentation or filtration operations. Next to that, the whole process can be carried out at ambient temperature.

Figure 2.2: Process flow diagram for chemical absorption of H2 S

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Figure 2.2 shows an overview of the units that are used to remove the H2 S from the biogas stream. The complete system consists of an absorber column, a particle separator or filter, and a regeneration column. Under continuous operating conditions, the biogas is introduced as small bubbles at the bottom of the absorber of the column. These bubbles pass through the F e/EDT A solution flowing downwards to the particle separator. In the absorber column the H2 S will be absorbed and transformed into S. The mechanism of this transformation can be seen in the equations in the former section. In the particle separator, the small particles of S that have formed are separated from the product stream. After this separation, the outgoing product stream is regenerated from F e2+ /EDT A into F e3+ /EDT A in a bubbling air column. The last step in this purification is washing the treated biogas with water in a packed column to remove residual traces of H2 S. The advantages of this absorption process are the almost complete removal of H2 S from the biogas. The removed H2 S is also converted into its elemental form, so it can be sold to other companies. A big disadvantage is that after the absorption process a scrubber is still needed to remove the CO2 . It is not possible with this absorption process to remove the CO2 .

Waste streams
Chemical absorption of CO2 The only process stream next to biogas needed in the absorption process is a liquid water phase in which amines are dissolved. As can be seen in figure 2.1 the biogas flows through a column filled with the amine solution. In this column, the CO2 is split from the biogas and the biogas leaves the absorption column. The amine solution including the captured CO2 leaves the column and will be generated in the generation column. During this process, the CO2 is split off and is emitted in the atmosphere as a waste stream. The amine solution will be regenerated and flows back into the column to capture CO2 again. This solution must be replaced a few times a year and then it becomes a waste stream too. This solution can be separated into a water phase and the amines using a membrane. The clean water phase can then be purged to a river. The only real waste streams are the CO2 stream and the amines. Chemical absorption of H2 S For the H2 S absorption process only the removal of H2 S is taken into account. In figure 2.2 a scrubber is also shown, but since this process is discussed in 12

another part of the report, we will focus only on the H2 S removal. Figure 2.2 shows the process flow diagram. The biogas stream can be seen and in the regeneration part also some other streams are added to the process. The biogas flows through the absorption column and the H2 S is captured in the liquid phase. The liquid phase consists of water in which F e/EDT A is dissolved. The biogas leaves the column containing almost no H2 S. The F e/EDT A solution flows to the regeneration part in which the sulphur is separated from the solution. After this step, the F e is regenerated from F e2+ to F e3+ . This aqueous solution is again used in the absorber column to capture H2 S. The separated elemental sulphur is collected and because it is pure it can be sold to other companies. However, the amount is small and to sell a reasonable amount would take quite a long time to collect. Because of these circumstances, the sulphur is mostly treated as a waste stream and has to be put away as chemical waste. Another waste stream is the F e/EDT A solution. This solution has to be replaced a few times a year. The solution can be filtered using a membrane, to separate the water phase and the F e/EDT A complexes. These components are another waste stream of the absorption process and need to be disposed of as chemical waste. The purity of the obtained biogas is approximately 98%. In both processes the yield for CH4 is 90%. The CH4 waste stream is best handled by sending the stream to a flare. Burning CH4 is better for the atmosphere than emitting the gas. Looking at the two absorption processes the absorption of CO2 seems to have less waste streams than the absorption of H2 S, at least less harmful waste streams.

Cost estimation for chemical absorption
For the absorption process, two cost prices of upgraded biogas are calculated, one for the absorption of CO2 and one for the absorption of H2 S. The price for biogas using both methods at the same time is calculated in the end. Cost estimation chemical absorption of CO2 · · · · · one time per year general inspection in- and outside one time per year general inspection outside if necessary, cleaning of internals maintenance of recirculation pump calibration of instrumentation

Output: 137 N m3 /h, 1,127,000 N m3 per year 90% CH4 yield, purity output: 98% CH4 13

Investment costs Absorber column2 Additional costs6 Pump 3 Heat exchanger4 Cooler1 Regeneration column1

125,000 100,000 5,000 15,000 18,000 90,000

Total investment costs 353,000 Depreciation period of equipment is 10 years. Running costs Energy costs6 Catalyst costs5 Operator Maintenance6 Total running costs 30,000 50,000 50,000 4,500 134,500 0.17

Costs per N m3 biogas without H2 S removal:

After the absorption of CO2 , an amount of 3% H2 S is still present in the biogas. For excellent cleaning of biogas, also the H2 S has to be removed, because the requirements are less than 5 mg/N m3 biogas. Cost estimation chemical absorption of H2 S · · · · · one time per year general inspection in- and outside one time per year general inspection outside if necessary, cleaning of internals maintenance of recirculation pump calibration of instrumentation 125,000 100,000 10,000 90,000 100,000 516,000 14

Investment costs Absorber column2 Additional costs6 2 Pumps3 Regeneration column1 Particle separator1 Total investment costs

Depreciation period of equipment is 10 years. Running costs Energy costs6 Catalyst costs5 Operator Maintenance6 Total running costs 30,000 15,000 50,000 4,500 99,500

The costs per N m3 produced are calculated according to formula 2.1. Costs per N m3 biogas: 0.16 When the price of the complete upgrading process, including both CO2 and H2 S absorption, is calculated, we obtain a price of 0.28 per N m3 upgraded biogas. This price is based on the following values: Investment costs Running costs
1 2 3 4 5 6

869,000 179,500

costs costs costs costs costs costs

from from from from from from

Aspen Icarus Project Evaluator offer of Rootselaar offer of Grundfoss calculation of Mauri excursion to Cirmac offer of E-kwadraat

2.2

High pressure water scrubbing

Water scrubbing is a technique based on the physical effect of gases dissolving in liquids. Water scrubbing can be used to remove CO2 and H2 S from biogas since these components are more soluble in water than in CH4 . This absorption process is a fully physical process. The main parts of the process are shown in figure 2.3. In high pressure water scrubbing, gas enters the scrubber at high pressure. This high pressure increases the dissolubility of gases in water. Then, water is sprayed from the top of the column so that it flows down counter-current to the gas. To ensure a high transfer surface for gas liquid contact, the column is usually filled with a packing material. 15

Figure 2.3: PFD for high pressure water scrubbing

In the flash vessel the pressure is decreased and some traces of CH4 will be regenerated. In the stripper the washing water is regenerated. CO2 and H2 S are stripped by air in this vessel. After a drying step, the obtained CH4 purity can reach 98% using this process and yields can achieved up to 94%. There are two types of water scrubbing [2]: Single pass scrubbing In single pass scrubbing, the washing water is used only once. The advantage of this type of scrubbing is that no contamination in the water occurs like traces of H2 S and CO2 . This gives that the total amount of CO2 and H2 S is at its maximum. The disadvantage of this technique is that it requires a large amount of water. This technique is only feasible when working near a sewer water cleaning plant from which water can be used. Regenerative absorption In regenerative absorption, the washing water is regenerated after washing the biogas. The main advantage of this technique is that the total amount of water required is much lower compared to single pass scrubbing. Water scrubbing requires a large amount of water. For example, the regenerative absorption process from DMT that washes 330 N m3 /h biogas 16

requires approximately 50 l/h of water. So single pass scrubbing is practically impossible in The Netherlands because water is too expensive and the government will have objections against the usage of such large amounts of water. Therefore, the main focus will be on regenerative absorption. When working at high pressure, there are two advantages compared to working at atmospheric pressure. The main advantage is that the dissolubility increases when the pressure is higher. This results in a lower required amount of water per amount of biogas. The total amount of water required will thus be a lot lower. Also, the washing water is oversaturated at atmospheric pressure so regenerating will be a lot faster. The driving force behind the regenerating process is the concentration difference between the oversaturated concentration and the equilibrium concentration. With this being as high as possible, the speed of the process will be highest. For the design of a water scrubber it is rather important to know how much H2 S and CO2 can be dissolved. The increasing dissolubility of H2 S and CO2 with increasing pressure is described by Henry’s Law: Pi = H · Cmax Cmax H Pi Saturation concentration of the component [mol/m3 ] Henry’s coefficient [P a · m3 /mol] Partial pressure of the component [P a] (2.15)

According to Dalton’s law, the total pressure is the sum of all partial pressures. So if the total pressure is increased, the partial pressure increases by the same factor. This means the saturation concentration rises as well. However, when higher pressures are reached, the dissolubility of the components will no longer linearly increase with the pressure. At higher pressures the increase of dissolubility becomes lower. Up to a pressure of 20 bars the dissolubility can be described according to Henry’s law [11]. These calculations are based on the ideal situation so non idealities should be taken into account in the design of a scrubber. Another important factor for the dissolubility of the components in water is the pH [2]. Furthermore, the pH depends on the amount of H2 S and CO2 that has been dissolved into water. Water becomes more acid when more H2 S and CO2 are absorbed. When the pH is decreased, CO2 will dissolve less and the H2 S will dissolve less. At a pH of 1, the dissolubility of H2 S is only half of the dissolubility at a pH of 7. Therefore, a low pH is not feasible because the H2 S removal is important; the stripping process becomes more difficult and acid water damages equipment. Working at a high pH is unfeasible as well because sulphur and carbonate ions will precipitate. It is best to work at a pH of 7. 17

The mass transfer of components from the gas phase to the water phase and vice versa is important to know. When it is known, the dimensions of the reactor can be calculated. Mass transfer occurs when a high concentration difference between two phases is realized. The mass transfer can be described using the double film model. This model is shown in figure 2.4. When two layers with different concentration profiles intersect, the following equations are valid: NAG = kG · a · (CAG − CAGi ) NAL = kL · a · (CALi − CAL ) (2.16) (2.17)

Figure 2.4: Concentration profile in double film model

The mass transfer coefficients, kL and kG , are dependent on a lot of parameters. It is difficult to get a precise measurement of these values. But a rough estimate of these values suffices to design the dimensions of the scrubber. Water scrubbing is a simple process because it only requires water and an absorption column to upgrade the biogas. Scrubbers also have some advantages [12] compared to other devices. Wet scrubbers are capable of handling high temperatures and moisture. The inlet gases are cooled so the overall size of the equipment can be reduced. Wet scrubbers can remove both gases and particulate matter and can neutralize corrosive gases. Furthermore, water scrubbing can be used for selective removal of H2 S because this is more soluble in water than CO2 . The water which exits the column with the absorbed components, can be regenerated and recirculated 18

back to the absorption column. This regeneration can be done by depressurizing or by stripping with air in a similar column. When levels of H2 S are high it is not recommended to strip with air because the water can become contaminated with elemental sulfur which causes operational problems. Also at high levels of H2 S the dissolubility is limited because of decreasing pH.

Waste streams
The water scrubbing process contains two main waste streams. The first waste stream is the exhaust of air which was used to strip the regenerated water. This stream mainly consists of air and a high percentage of CO2 but also contains traces of H2 S. Because H2 S is rather poisonous this stream needs to be treated. Also the stream contains small amounts of CH4 . Because CH4 is far more damaging to the environmental than CO2 the CH4 in this stream should be burned. The second waste stream is a purge of water. To keep the dissolubility as high as possible a part of the washed water is purged and replaced with clean water. In this way the concentration of CO2 and H2 S in the water stream to the scrubber will remain as low as possible and CO2 and H2 S will not accumulate. Because most of the CO2 and H2 S will be absorbed in the gas phase in the stripper the purge stream does not have to be treated.

Cost estimation for high pressure water scrubbing
Output: 144 N m3 /h, 1,215,200 N m3 per year 94% CH4 yield, purity output: 98% CH4 Compressor (10 bars, 250 N m3 /h biogas) 110,000 Columns /> 140.000 Heat exchangers 5,000 Pumps and blowers 10,000 Total investment costs 265,000 Depreciation period of equipment is 10 years. Running costs Energy costs Operator Total running costs Costs per N m3 biogas: 0.13 60,000 50,000 110,000

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This cost price is in close accordance to the costs in Tilburg at the biogas upgrading plant, SMB Stortgas BV. At this upgrading plant the cost price was approximately 0.11 to 0.12 per N m3 .

2.3

Pressure swing adsorption

Pressure swing adsorption (PSA) is another possible technique for the upgrading of biogas. PSA is a technology used to separate certain components from a mixture of gases under pressure according to the species’ molecular characteristics and affinity for an adsorption material. Figure 2.5 shows how the adsorption material selects the different gas molecules. The adsorption material adsorbs H2 S irreversibly and is thus poisoned by H2 S [15]. For this reason, an H2 S removal step is often included in the PSA-process. Disturbances have been caused by dust from the adsorption material getting stuck in the valves. Special adsorption materials are used as molecular sieves, preferentially adsorbing the target gas species at high pressure. Aside from their ability to discriminate between different gases, adsorbents for PSA-systems are usually very porous materials chosen because of their large surface areas (for instance activated carbon, silica gel, alumina and zeolite). The process then swings to low pressure to desorb the adsorbent material [16]. Desorbing the adsorbent material leads to a waste stream, containing concentrations of impurities. The upgrading system consists of four adsorber vessels filled with adsorption material, as can be seen in figure 2.6. During normal operation, each adsorber operates in an alternating cycle of adsorption, regeneration and pressure build-up. During the adsorption phase, biogas enters from the bottom into one of the adsorbers. When passing the adsorber vessel, CO2 , O2 and N2 are adsorbed on the adsorbent material surface. This can be seen in figure 2.5 where N2 , O2 , H2 O, H2 S and CO2 are adsorbed in the adsorber. The gas leaving the top of the adsorber vessel contains more than 97% CH4 . This methane-rich stream is substantially free from siloxane components, volatile organic compounds (VOCs), water and has a reduced level of CO2 . Before the adsorbent material is completely saturated with the adsorbed feed gas components, the adsorption phase is stopped and another adsorber vessel that has been regenerated is switched into adsorption mode to achieve continuous operation. Regeneration of the saturated adsorbent material is performed by a stepwise depressurization of the adsorber vessel to atmospheric pressure and finally to near vacuum conditions. Initially, the pressure is reduced by a pressure balance with an already regenerated adsorber vessel. This is followed by a second depressurization step to almost 20

Figure 2.5: The principle of pressure swing adsorption, picture taken from [17]

atmospheric pressure. The gas leaving the vessel during this step contains significant amounts of CH4 and is recycled to the gas inlet. These significant amounts of CH4 were trapped within the voids of the adsorbent particles. Before the adsorption phase starts again, the adsorber vessel is repressurized stepwise to the final adsorption pressure. After a pressure balance with an adsorber that has been in adsorption mode before, the final pressure build-up is achieved with feed gas. A complete cycle is completed in approximately 3-5 minutes [20]. The advantages of the PSA-process are the high CH4 enrichment of more than 97%, the low power demand and the low level of emission. The waste stream of the PSA-plant consists of N2 , O2 , H2 O, H2 S and CO2 . The main disadvantage is the H2 S-removal step. This is a complex step in the process, which is necessary.

Waste streams
The PSA-plant has a final product stream, the upgraded biogas, which contains more than 97% CH4 . Next to the product stream, a waste stream is produced. The waste stream leaves the adsorber vessels at the bottom and contains all the adsorbed material from the carbon molecular sieves. Also, some significant amounts of CH4 are found in this waste stream (among other 21

Figure 2.6: PFD for pressure swing adsorption [17]

things the remaining 3% CH4 ). CH4 is more damaging than CO2 , so it is of most importance to make sure that CH4 is not emitted into the air. Burning the CH4 is less harmful to the environment in comparison with emitting CH4 directly into the air. Therefore, the waste stream can be led to a gas engine linked to a generator. Increasing the yield of CH4 in the product stream can be achieved by recycling the waste stream. This has also a positive effect on the amount of CH4 in the waste stream, which will decrease.

Cost estimation for PSA
Using the process flow diagram of the PSA-process, gives the following cost estimation. The costs for the removal of H2 S are included in the investment costs as well as in the running costs. The costs of the pressure swing adsorption depend on which type of adsorbent material is used in the columns and the number of units used. The operational costs are influenced by the operating pressure, which on its turn is dependent on the adsorbent material. The compressor needed in the beginning in order to compress the incoming biogas is the last element which contributes to the cost of the whole plant significantly. Compression is expensive and in order to make it profitable, it is needed to recover the required pressure. The pressure recovery can be enabled by several pressure valves. The type of adsorbent material used in the PSA is a carbon molecular 22

sieve. The choice for this adsorbent material can be explained by the ability of removing N2 and O2 from the biogas. The lifetime of the adsorbent material is taken to be 3 to 4 years. Furthermore, there are four adsorber vessels needed in the plant. Figure 2.6 shows the overall scheme of the PSA-plant. The compressor, the four adsorber vessels, the vacuum pump and the H2 Sremoval step are included in the cost estimation. Appendix A shows an alternate way of estimating the cost of a PSA-plant. The equations used, are found in [18, 19]. In this chapter, the cost estimation is adjusted to the cost estimations of the other techniques which are investigated. Output: 139 N m3 /h, 1,176,000 N m3 per year 91% CH4 yield, purity output: 98% CH4 Investment costs CO2 adsorber columns (4) 4 500,000 Additional costs6 70,000 3 Pumps (2) 10,000 Compressors (2) 100,000 Total investment costs 680,000 Depreciation period of equipment is 10 years. Running costs Energy costs Catalyst costs Operator Maintenance Total running costs 33,500 100,000 50,000 3,750 187,250

The costs per N m3 produced are calculated as explained at the beginning of this chapter. Costs per N m3 biogas: 0.25

2.4

Cryogenic separation

The name cryogenic separation already reveals the fact that this technique makes use of low temperatures, close to -90 ◦ C, and high pressure, approximately 40 bars. Because CO2 , CH4 and all other biogas contaminants liquefy 23

at different temperature-pressure domains, it is possible to obtain CH4 from biogas by cooling and compressing the crude biogas to liquefy CO2 which is then easily separated from the remaining gas. Among the existing techniques for biogas upgrading, cryogenic separation of impurities from biogas is still in the early stages of research and development. In order to investigate the feasibility of this technique, in the first designing steps, the focus has been only on the separation under low temperature and high pressure. When the desired purity of the upgraded gas is achieved, the designing of the cooling and compressing unit in this technique can be continued. Finally these two models, for compressing and separating of biogas, is put together to achieve the final separation model which is shown in figure 2.9. Figure 2.7 shows this primary model for the cryogenic separation of biogas. The calculations for this model are based on the crude inlet biogas with an inlet gas flow of 250 N m3 /h. The inlet gas is assumed to be dried, under atmospheric pressure and has an ambient temperature. The composition of the inlet gas is given in table 2.1.
2

1

3

Distillation Column
Figure 2.7: A simple model of cryogenic separation of biogas. Streams 1, 2 en 3 respectively are the crude biogas (inlet gas), the upgraded biogas (product) and the impurities.

The model in figure 2.7 has been created by using the Aspen Plus software package. In this model, the impurities from crude biogas are separated using a distillation column which operates at a temperature of -90 ◦ C and a pressure of 40 bars. The results of the modeling are summarized in table 2.2. As can be seen in table 2.2 the product stream, upgraded biogas (stream 2), has a CH4 purity of 91%. Again it should be mentioned here that this purity is based on the model made in Aspen Plus. However, according to [31] it should be possible to upgrade biogas to a higher purity of CH4 . Another demand for the upgrading of biogas is the reduction of H2 S quality with a 24

Table 2.1: The average biogas composition assumed for use in the model [21]

Biogas component CH4 CO2 CO N2 H2 H2 S Oxygen, Siloxane

Volume % 60 35 0.15 3 1.55 0.3 traces

Table 2.2: The results of the modeling for the cryogenic separation

Stream Temperature (◦ C) Pressure (bar) Vapor Fraction Mole Flow (kmol/h) Mass Flow (kg/h) Volume Flow (m3 /h) Enthalpy (M M kcal/h) Mass Fractions CH4 CO2 CO N2 H2 H2 S

1 25 1 1 10.11 263.42 250 -0.44 0.369 0.591 0.001 0.032 0.001 0.004

2 -91 40 1 6.48 105.63 1.26 -0.11

3 1.4 40 0 3.63 157.78 0.17 -0.34

0.91 0.006 0.00014 0.98 0.004 1.91E-09 0.08 2.29E-08 0.003 4.23E-15 Trace 0.006

factor 1000 which is achieved as well. Knowing these demands are achieved, the second step in the process design will be designing of the cooling and compressing units. Figure 2.8 shows these process units. In these process units the crude inlet biogas goes through the first heat exchanger in which it is cooled down to -70 ◦ C. This heat exchanger uses the product stream as a cooling medium, which has the advantage of preheating the upgraded biogas before leaving the plant as well as the energy efficiency benefit of the process. The first cooling step is followed by a cascade of compressors and heat exchangers which cool the inlet gas down to -10 ◦ C and compress up to 40 bars before entering the distillation column. To defrost 25

Biogas

1

2

3

4

5

Cooler

Compressor

Cooler

Compressor

Cooler

Figure 2.8: Cooling and compressing units in cryogenic separation

frozen water each heat exchanger needs a parallel heat exchanger. Table 2.3 shows the stream conditions through this process unit.
Table 2.3: Stream conditions through the cooling and compressing process units

Stream Temperature (◦ C) Pressure (bar) Vapor Fractions Mass Flow (kg/h) Volume Flow (m3 /h) Enthalpy (M M kcal/h)

Inlet gas 25 1 1 177.70 168.64 -0.29

1 2 3 4 5 -70 207 -10 54 -10 1 21 20 40 40 1 1 1 1 1 177.70 177.70 177.70 177.70 177.70 114.21 12.89 6.81 4.27 3.07 -0.30 0.28 -0.30 -0.29 -0.30

Figure 2.9 shows the complete PFD for the cryogenic separation process

Waste streams
The fact cryogenic separation uses no chemicals makes of this separation an environmental friendly technique. The only waste stream is stream 8 shown in figure 2.9. (The same as stream 3 in figure 2.7) This stream mainly consists of a high percentage of CO2 but also contains traces of H2 S and CH4 . Because H2 S is rather poisonous and CH4 is more damaging to the environment comparing CO2 , this stream needs to be treated.

Cost estimation for cryogenic separation
The cost analysis for the final designed process is estimated using quotations from DMT, the Matches process, a cost engineering website (appendix B) and Aspen Icarus process evaluator. Output: 161 N m3 /h, 1,228,500 N m3 per year 98% CH4 yield, purity output: 91% CH4

26

Biogas 25 oC 1 bar 37 % CH4 58 % CO2 5 % other

Recirculation of product stream as cooling agent

-70 oC 1 bar Cooler

207 oC 21 bar

-10 oC 21 bar

54 oC 40 bar

-10 oC 40 bar

-90 oC 40 bar

Compressor

Cooler

Compressor

Cooler Distillation Column

Product 91 % CH4 8 % N2 1% other

Waste 0.6 % CH4 98 % CO2

Figure 2.9: PFD of the cryogenic separation of biogas

Investment costs Heat Exchanger 1 Heat Exchanger 2 Heat Exchanger 3 Compressor1 Compressor2 Separation train

10,300 26,500 21,700 200,000 250,000 400,000

Total investment costs 908,500 Depreciation period of equipment is 10 years. Running costs Energy costs Operator Maintenance Total running costs Costs per N m3 biogas: 343,000 50,000 4,500 397,500 0.44

27

2.5

Membrane separation

CH4 and CO2 can also be separated using a membrane. Because of the difference in particle size or affinity, certain molecules pass through a membrane whilst others do not. The driving force behind this process is a difference in partial pressure between gases. The properties of this separation technique are highly dependent on the type of membrane used. Many different membranes are available each with its particular specifications [26]. The general principle however is basically the same and is explained below on the basis of a membrane from the Natcogroup [22]. The Natcogroup use membrane gas separation modules which operate on the basis of selective permeation [22]. The technology takes advantage of the fact that gases dissolve and diffuse into polymeric materials. If a pressure differential is set up on opposing sides of a polymeric film, a membrane, transport across the film (permeation) will occur. The rate of permeation is determined by the product of a solubility coefficient and a diffusion coefficient. Very small molecules and highly soluble molecules (such as He, H2 , CO2 and H2 S), permeate faster than large molecules (such as N2 , C1 , C2 and heavier hydrocarbons including CH4 ). When a biogas stream containing CO2 is fed to a membrane, the CO2 will permeate the membrane at a faster rate than the natural gas components. Thus, the pressurized feed stream (coming from below in picture 2.10) is separated into a CO2 rich, low pressure permeate stream on the right hand side and a CO2 -depleted, high pressure CH4 gas stream.

Figure 2.10: Schematic representation of membrane separation

Any polymeric material will separate gases to some extent. Proper selection of the polymeric material comprising the membrane is extremely impor28

tant. It determines the ultimate performance of the gas separation module. Membranes made of polymers and copolymers in the form of a flat film or a hollow fibre have been used for gas separation. Several different membranes have been found in literature. The Natcogroup use cellulose acetate as a base membrane material [22]. Cellulose acetate is very inert and stable in CO2 /hydrocarbon environments. Application of polyimide membranes has also been found [23]. For this type of membrane a single stage unit is sufficient to achieve 94% enrichment from gas with a common concentration of CH4 . Using a liquid as a membrane is also possible making it possible to replace the membrane in situ by circulating the liquid [24]. The permeation of H2 S depends on the choice of membrane. If H2 S permeates only partly both exit streams contain H2 S. Either the input stream or the output streams can be cleaned. Since the CO2 rich stream still contains a relatively high concentration of CH4 ( 10-15%) this stream is best used in a gas engine to produce electricity or heat. For that, the H2 S does not have to be removed. This will result in more wear of the engine but maintaining an engine is cheaper than the removal of H2 S. The cheapest option therefore is only cleaning the CH4 stream which constitutes a significantly smaller amount of gas than the input. A membrane which fully removes the H2 S from the biogas would be a great improvement. The need for other pre-treatment such as drying or heating is fully dependent on the membrane used. A higher pressure gives a higher gas flux through the membrane. However, the maximum pressure is determined again by the membrane. For this reason, high strength hollow fibre membranes have been developed. Overall, the efficiency of the entire process mainly depends on the membrane used. Its selectivity towards the gases having to be separated, membrane flux or permeability, lifetime, operational temperature and humidity range, maintenance and replacement costs are all factors that determine the overall performance of such a biogas upgrading technique. It is therefore difficult to judge this technique in total. Some main characteristics can be given; it is a proven technology. It has been applied for many years to extract nitrogen from ambient air. It has also already been used to upgrade biogas; experimentally [27] as well as commercially. Membranes, especially hollow fibre membranes, are very compact, light weight and allow for a modular design making expansion and replacement very easy. However, well maintained membranes hardly need any maintenance and can last as long as 10 to 15 years. Other equipment such as the compressor and pumps do need maintenance but this is also true for the other techniques. The total energy needs are very low since the membrane itself is passive. Because the membrane is passive the entire process is easy to operate and simple to understand. 29

Membranes however can be expensive and also very fragile. Certain solvents or fine colloidal solids such as graphite can permanently destroy or foul the membrane.

Waste streams
A major disadvantage of this technique is the low methane yield. The waste gas still contains CH4 which is highly polluting. Part of it can be fed back into the inlet or, as mentioned above, the waste gas can be burnt in a gas engine linked to a generator. Using a multistage setup also increases the yield. Positive results have been found using an internally staged permeator [25], depicted in figure 2.11. Electrical costs are low since only a compressor has to be powered. The generator can power the compressor which results in an even higher CH4 efficiency. The CO2 stream is then of no further use. If the waste stream is not burned in an engine it is very polluting since CH4 is far more harmful than just CO2 .
CH4 + CO2

mainly CO2 + small amount of CH4

mainly CH4 + small amount of CO2

Figure 2.11: Schematic representation of an internally staged membrane separator

Cost estimation membrane separation
To prevent damage to the membrane, intensive pre-treatment might be necessary. This could be quite expensive. However, it is not taken into account in this report. · Without H2 S removal · 150 hours of maintenance per year · Flare recommended (especially during start-up)

30

Output: 130 N m3 /h, 1,002,400 N m3 per year 78% CH4 yield, purity output: 89.5% CH4 Investment costs Additional costs Pumps (2) Compressor (5-10 bar) Membrane2 100,000 10,000 100,000 23,000

Total investment costs 233,000 Depreciation period of equipment is 10 years. Running costs Energy costs (41 kW h) Operator Maintenance1 Total running costs 28,000 50,000 3,750 81,750

The costs per N m3 produced are calculated as explained at the beginning of this chapter. Costs per N m3 biogas without H2 S removal: 0.12

To remove H2 S the process described in 2.1.2 is added to these costs. This results in a total cost price for upgraded biogas of 0.22. This price is calculated from the following values: Investment costs Running costs
1 2

749,000 126,750

Estimate E-kwadraat Estimate from Cirmac

31

Chapter 3 Comparison
This chapter will compare the five different techniques which are investigated for biogas upgrading. The techniques will be compared on a couple of factors. Of course, every technique has its own advantages and disadvantages, but there is more than that. The techniques will be compared on the price per N m3 upgraded biogas; how easy or hard the process runs looking at maintenance and scale up; and the impact on the environment by examining the waste streams. The cost estimate is used to calculate the price of one N m3 of upgraded biogas. Also, there are the costs of investment and the operating costs. The consideration to be made is the best combination of advantages and disadvantages, the cost for operating and investment and finally, the price which has to be paid for the upgraded biogas, the waste streams and maintenance. The table at the end of this chapter gives an overview of this comparison. Furthermore, appendix ?? gives the advantages and disadvantages of each technique in the current opinion of DMT [29]. These are compared to the findings presented in this report. Finances Looking at the price of the upgraded biogas, it can be seen that high pressure water scrubbing is the cheapest. This can be linked to the investment costs which also are the lowest. Cryogenic separation sticks out of the list with the highest investment cost and also the cost price is with 0.44 the highest. While the investment costs of pressure swing absorption are also quite high, the cost price is the average compared to the other four techniques. Impact on the environment Looking at the amount of waste streams, it can be easily seen that pressure swing adsorption and membrane separation have only one waste stream, where chemical absorption and high pressure water scrubbing have two waste 32

streams. But it does not automatically mean that chemical absorption and high pressure water scrubbing are a bad technique. Not only the amount of waste streams has to be noticed, also the content of the waste streams have to be determined. The waste stream produced with pressure swing absorption and membrane separation both will be led to a gas engine linked to a generator. This is the best solution, because CH4 is more harmful when emitted into air compared to burning a waste stream containing CH4 . Chemical absorption has two real waste streams, namely a stream containing CO2 and a stream periodically catalyst stream. High pressure water scrubbing has a waste stream containing CO2 and some traces of H2 S. The last component is poisonous, which result in the fact that this waste stream needs waste treatment. The second waste stream is a water stream containing CO2 and H2 S. Because the amount of CO2 and H2 S is rather small, this stream does not need any treatment. Cryogenic separation has one waste stream containing a high percentage of CO2 and some traces of H2 S and CH4 . This waste stream needs treatment. High pressure water scrubbing and membrane separation are the only two techniques that don’t produce pure CO2 . Ease of operation Not each technique requires the same amount of maintenance, materials, catalyst and operators. Therefore, a distinction between this has to be made. Looking at chemical absorption, an expensive catalyst is used in order to absorb CO2 and H2 S. This catalyst has to be changed twice a year, which leads to a shut down. The same is partly true for pressure swing adsorption. High pressure water scrubbing however is a very simple process. The only separation parameter is the pressure of the water scrubber and this can be easily kept under the desired condition. Because of this easiness, there is still an operator needed to check if everything goes well, which is there all the time. Another advantage is the absence of using special chemicals or a catalyst, which makes that the process can run continuously without a periodic shut down. Since membrane separation only needs few equipment and makes no use of chemicals, no operator is needed which is constantly at the plant. However, in order to check the running process, one operator is needed. Another consequence is the simple process, which makes it an easy running process. At last, cryogenic separation is looked at. Because of the large amount of equipment needed, it is a complex process. Furthermore, the high pressure and very low temperature makes it a dangerous process, which has to be controlled. Operators are certainly needed therefore.

33

Table 3.1: An overview in order to compare the different techniques on our criteria, without H2 S removal. Only for PSA, an H2 S removal step is needed as pre-treatment. For the other processes, H2 S can be removed in advance or afterwards.

Technique

Investment cost

Running cost

Advantages

Disadvantages

Chemical sorption 0.13 94 98 · Removes gases and particulate matter · High purity, good yield · Simple technique, no special chemicals or equipment required · Neutralization of corrosive gases

ab-

353,000

134,500

Cost price Maximum upgraded achievable biogas yield 3 /N m biogas % 0.17 90

Maximum achievable purity % 98

· Almost complete H2 S re- · Only removal of one compomoval nent in column · Expensive catalyst · Limitation of H2 S absorption due to changing pH · H2 S damages equipment · Requires a lot of water, even with the regenerative process

High pressure water scrubbing

265,000

110,000

Pressure swing adsorption

680,000

187,250

0.25

91

98

· More than 97% CH4 enrich- · Additional complex H2 S rement moval step needed · Low power demand · Low level of emissions · Adsorption of N2 and O2 · Can produce large quantities · A lot of equipment is required with high purity · Easy scaling up · No chemicals used in the process

Cryogenic separation

908,500

397,500

0.44

98

91

Membrane separation

233,000

81,750

0.12

78

89.5

· · · ·

Compact and light in weight Low maintenance Low energy requirements Easy process

· Relatively low CH4 yield · H2 S removal step needed · Membranes can be expensive

Chapter 4 Conclusions
Comparing the five techniques for the upgrading of biogas with the goal of injecting it into the commercial gas grid is done in the previous section. From that, it can be concluded that looking only at the cost price, high pressure water scrubbing is the best option. But there is more than only cost price to make a process succeed or fail. Therefore, some other criteria are set up. The waste stream inventory gives another picture. Pressure swing adsorption and membrane separation are the only two techniques which have only one waste stream, which can be cleverly used by driving a generator. The other techniques have waste streams which need some waste treatment, which also have to be taken into account looking from an environmental and economical point of view. Furthermore, the yield and purity is of great importance. The purity of the upgraded biogas is comparable for most of the techniques, but membrane separation has the lowest purity of 89.5% CH4 . The other techniques have a purity of 98% CH4 . The yield of methane achieved with chemical absorption is the highest with 98%. Pressure swing adsorption, chemical absorption and cryogenic separation are at average, where membrane separation is the lowest with 78% CH4 yield. Membranes in series increase the yield, but this results also in an increase in costs. Considering the ease of operation of each process, membrane separation and high pressure water scrubbing are the easiest processes to operate. No catalysts or chemicals are needed. Cryogenic separation has the problem of the need to work at very low temperatures and high pressures. Therefore, it needs to be controlled by an operator and some safety restrictions have to be set, because of the high possibility of explosion. Chemical absorption and pressure swing adsorption both need a catalyst in order to upgrade the biogas. This catalyst has to be changed twice a year which leads to a shut down. 35

From this all, it can be concluded that high pressure water scrubbing performs the best. With the low cost price, high purity and yield it is a promising upgrading technique. Though one waste stream needs treatment, it is a continuous process which operates almost on it self.

Recommendations For further investigation we recommend the following subjects: • The waste stream treatment is not considered in our investigation and can influence the price of the upgraded biogas. • For a better cost investigation more quotations should be acquired and mass balances should be made. Then, a more precise estimation of the cost per N m3 biogas can be made. • The CO2 footprint is mentioned in the report but not calculated. When mass balances are made the CO2 footprint can also be calculated. • For chemical absorption it could be useful to look for more types of catalyst. • The performance of the membrane separation is highly dependent on the type of membrane used. An investigation of more types of membranes can be useful. • Cryogenics is only investigated at one pressure and temperature. We do not know if this is the optimal condition and therefore the cryogenics process should be investigated on a range of temperatures and pressures.

36

Acknowledgement
During our Multi Disciplinary Project we received help from may people. Without their help we would not have been able to successfully finish this project. Therefore our gratitude goes out to the following people. First of all we want to thank Laura, our tutor. We greatly appreciated Laura’s presence during our weekly meetings. Her input was always insightful. Although she was rather quiet, the things she said were well worth listening to. We would like to thank the people at Dirkse Milieutechnology, in particular Robert Lems, Déborah Felisoni and Pieter-Durk van Jaarsveld for making this project possible and receiving us at DMT in Joure. We gathered lots of useful information and had some good fun during our overnight stay in Joure. Furthermore we thank René van den Kieboom for making the excursion to Tilburg possible and thank Maarten van der Heuvel and Olivier Kuijer for arranging the excursion to Nuenen. Both excursions were a real addition to our project and gave us a good understanding of the reality of upgrading biogas. Also, we would like to thank Jetse Reijenga, our project coordinator, for always being attentive to our work and his interest in our progress. The short introduction into building websites was quite helpful and resulted in an awesome website for our project.

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Bibliography
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[13] Eneco, http : //mkb.eneco.nl/productene nt arieven/tarieven/ tarieven.asp [14] WMD, http : //www.wmd.nl/M ijnW M D/T arief N ota/ T arievenGrootverbruik.html [15] http://www.biotech-ind.co.uk/Methane-RGP-Process.htm, visited at the 24th of February 2008 [16] O. Jönsson, M. Persson, Biogas as transportation fuel, Swedish Gas Centre, 2003 [17] Dr. Alfons Schulte-Schulze Berndt, Intelligent Utilization of Biogas Upgrading and Adding to the Grid, Jonköping, May 2006 [18] O. Smith, A. Westerberg, The optimal design of pressure swing adsorption systems, Chemical engineering science, Vol. 45, No. 12, pp. 2967 2976, 1991 [19] P. Cruz, J. Santos, F. Magalhães, A. Mendes, Cyclic adsorption separation processes : analysis strategy and optimization procedure, Chemical engineering science, 58 (2003) 3143 - 3158 [20] Information from excursion to Cirmac in Nuenen [21] http://www.kolumbus.fi/suomen.biokaasukeskus/en/enperus.html, visited at the 8th of May 2008 [22] Natcogroup, Acid Gas (CO2 ) Separation Systems with Cynara Membranes, July 2007. [23] M. Harasimowicz, P. Orluk, G. Zakrzewska-Trznadel, A.G. Chmielewski, Application of polyimide membranes for biogas purification and enrichment, Journal of Hazardous Materials 144 (2007) 698-702. [24] Asim K. Guha, Sudipto Majumdar and Kamalesh K. Sirkar, A largerscale study of gas separation by hollow-fiber-contained liquid membrane permeator, Journal of Membrane Science 62 (1991) 293-307 [25] K. Li and W.K. Teo, Use of an internally staged permeator in the enrichment of methane from biogas, Journal of Membrane Science 78 (1993) 181-190 [26] Danial L. Ellig, Joseph B. Althouse and F.P. McCandless, Concentration of methane from mixtures with carbon dioxide by permeation through polymeric films, Journal of Membrane Science 6 (1980) 259-263 39

[27] S.A. Stern, B. Krishnakumar, S.G. Charati, W.S. Amato, A.A. Friedman, D.J. Fuess, Performance of a bench-scale membrane pilot plant for the upgrading of biogas in a wastewater treatment plant, Journal of Membrane Science 151 (1998) 63-74 [28] Carbon Trust, Carbon footprint measurement methodology, version 1.3, march 2007 [29] R. Lems, Upgrading biogas, 2008 [30] Brochure Biogas CHP, The use of biogas in Tilburg The Netherlands, 2000 [31] Myken A., Jensen J., Dahli A., Final report, Adding Gas from Biomass to the Gas Grid, Contract No: XVII/4.1030/Z/99-412; Danish Gas Technology centre a/s, Swedish Gas Center

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Appendix A Alternate cost estimation PSA
The costs of the pressure swing adsorption depend on which type of adsorbent material is used in the columns and the number of units used. The operational costs are influenced by the operating pressure, which on its turn is dependent on the adsorbent material. The compressor needed in the beginning in order to compress the incoming biogas is the last element which contributes to the cost of the whole plant significantly. Compression is expensive and in order to make it profitable, it is needed to recover the required pressure. The pressure recovery can be enabled by several pressure valves. Now, some assumptions are made to be able to make a cost estimation. The type of adsorbent material used in the PSA is a carbon molecular sieve. The choice for this adsorbent material can be explained by the ability of removing N2 and O2 from the biogas. The lifetime of the adsorbent material is taken to be 3 to 4 years. Furthermore, there are four adsorber vessels needed in the plant. Figure 2.6 shows the overall scheme of the PSA-plant. The compressor, the four adsorber vessels, the vacuum pump and the H2 Sremoval step are included in the cost estimation. The several pressure valves which are required are included in the equations by the modular factor in it. The costs of the PSA-plant are divided in two parts: operational costs and capital costs. First, the operational costs will be calculated. The operational costs depend on the operating pressure, the flow rate, and the dimensions of the adsorber vessels. Therefore, first those parameters are determined. The operating pressure of the PSA-plant is 1 bar at the inlet and the product stream is at 5 bar. The bed length is set at 6 m with a diameter of 1,5 m assuming cyclic steady state. The inlet flow is assumed to be 250 N m3 /h.

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The following equation from [19] determines the operational costs: OC = Qin · W · EC Where: OC Qin W EC Operating costs [E/year] Average inlet flow [N m3 /year] Theoretical work [J/m3] Energy costs [E/J] (A.1)

The energy input amounts to 1,875 kW h. The energy price per kW h amounts to 0.10. The operational costs become 35,721-. The other part, the capital costs, can now be calculated. These are divided in three parts. The bed metal shell which includes the adsorber vessels, abbreviated with CShell ; the costs of the compressor, CComp ; and finally, the costs of the driver for the compressor, CDriver . The following equations are taken from [18]. CShell = P 0.584 · 4.93 · d · l + 3.74 · d2 + 739 Where: P d l Pressure [P a] Bed diameter [m] Bed length [m] 425.500,(A.3) (A.2)

The costs for the shell become

CComp = 14.020 · Q0.435 in Qin Volumetric flow rate at the inlet [f t3 /min] 79,423-.

The costs for the compressors become

CDriver = 11.68 · hp1.61 + 2.470 · hp0.32 Comp Comp hpComp Horse power of compressor [hp]; assumed to be 5 hp. 2,771-.

(A.4)

The costs for the driver of the compressor become

In order to calculate the cost of the PSA-plant, also the investment costs for the H2 S-removal part has to be taken into account, therefore, the costs used for H2 S-absorption is included which amount to 516.000,-. 42

The total capital costs are the cost of the bed metal shell summed up with the costs of the compressor, the costs of the driver of the compressor and the costs of the H2 S-removing part. The total capital costs become 1.023.694,The total running costs of the PSA can also be calculated by: CAnnual = CCap τpb tax Cop dr CCap + (1 − tax) · Cop + dr · tax · CCap τpb (A.5)

Capital cost [E] Pay back time [s] Tax rate [s] Operating cost [E] Depreciation rate [−]

The pay back time is set at 3 years, which is equal to 94.608.000 seconds. The tax rate is assumed to be 0,6 and the depreciation rate 0,125. The total running costs of the PSA-plant become 282.616,-. The final cost price per N m3 biogas become: 0,23.

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Appendix B Cryogenic equipment
Compressor 1 Manufacturer: Vilter (http : //www.vilter.com) Compressor type: oil flooded single screw compressor Motor power: 180Kw Price for complete package ready to work: 200,000

Compressor 2 Manufacturer: Vilter (http : //www.vilter.com) Compressor type: oil flooded single screw compressor Motor power: 200Kw Price for complete package ready to work: 250,000 Heat exchanger 1 Price is calculated by http : //www.matche.com/EquipCost/Exchanger.htm Heat exchanger type: Condenser, vertical tube Area: 70 f t2 Internal pressure: 150 psi Material: Carbon Steel Heat exchanger 2 Price is calculated by http : //www.matche.com/EquipCost/Exchanger.htm Heat exchanger type: Condenser, vertical tube Area: 150 f t2 Internal pressure: 300 psi Material: Carbon Steel

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Heat exchanger 3 Price is calculated by http : //www.matche.com/EquipCost/Exchanger.htm Heat exchanger type: Condenser, vertical tube Area: 100 f t2 Internal pressure: 150 psi Material: Carbon Steel

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Appendix C CO2 footprint
The carbon footprint is a method to measure the effect of a certain process on the environment in terms of the amount of green house gases produced during the entire process. The process encompasses the whole life cycle of a product, thus from the production of the raw material to disposal of the final product. This makes it a very extensive method. In order to produce such a carbon footprint, a certain path needs to be followed. This methodology will be explained in the following text. Because of the method being that extensive, the carbon footprint is not calculated for every biogas upgrading technique separately. Making a carbon footprint of a process will follow five major steps in order to calculate the green house gases produced during the supply chain. Table C.1 gives a schematic overview of the methodology. Step Step Step Step Step 1 2 3 4 5 Analyze internal product data Build supply chain process map Define boundary conditions and identify data requirements Collect primary and secondary data Calculate carbon emissions by supply chain process steps

Table C.1: The overview of the five major steps in order to calculate the carbon footprint

These steps always have to be followed one by one and boundaries have to be set. For instance, the carbon footprint can cover all the supply chain steps from raw material to disposal, but this can be adjusted. Step 3 in the methodology takes care of that.

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Figure C.1: The steps used in order to produce the whole supply chain process map, picture taken from [28]

Step 1: Analyze internal product data The main goal of this first step is to develop a deeper understanding of the product. This implies determining what raw materials the product is made of and which actions or process are needed to convert the raw material into the desired final product. Next to that, the waste streams and the produced co-products have to be known. It is necessary carefully evaluate each step in the entire process. Step 2: Build supply chain process map The objective of the second step is to produce the whole supply chain process map, which can be visualized using figure C.1. Step 3: Define boundary conditions and identify data requirements The third step has two sub-objectives. First, the boundaries need to be set which have to be followed for the product. After that, the required data is needed in order to set up the mass balances and the carbon footprint. Step 4: Collect primary and secondary data From the data collected in the third step of the methodology, the required data is found. This data can be used in order to develop the mass balance 47

and also to calculate the GreenHouse Gas emissions (GHG emissions) for each step in the process. Step 5: Calculate GHG emissions by supply chain process steps Now all the required data is collected, a model can be designed to actually calculate the mass balance and the GHG emissions of each step in the process. After the five steps, the carbon footprint is ready. It gives insight in the GHG emissions produced in the process. Then it is necessary to take a critical look at the environmental performance of your process. When the emissions are too large or harmful, the carbon footprint can help to design a solution in order to reduce and control the produced greenhouse gas emissions.

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Appendix D Visit to SMB Stortgas BV in Tilburg
Since 1987, DMT has grown to be a multidisciplinary international and leading company with important reference projects within the environmental sector. DMT is expert in: air treatment and odor abatement systems, desulphurization unit (both biological and chemical), ground water purification and soil remediation plants, water treatment plants and aeration systems and water management. At this moment DMT is developing its biogas upgrading technology. For SMB stortgas BV in Tilburg, a high pressure water scrubbing plant is installed. In Tilburg, a municipal association initiated a complex, including a landfill gas installation, a biogas plant, and an upgrading plant which has been running since 1994. The upgraded gas, which has natural gas quality, is injected into the natural gas network. An association has been created involving 9 municipalities, of which Tilburg is the largest. The name is SMB (Samenwerkingsverband Midden Brabant) and the objective is to solve the waste problem in the cities. In total, the 9 municipalities have 480,000 inhabitants, who yearly produce 40,000 tons of organic waste. As a landfill biogas treatment plant was already present in Tilburg, SMB chose anaerobic digestion of the organic waste, which means Vegetable, Fruit and Garden waste, (VFG) [30]. In order to obtain more detailed information about the upgrading processes of biogas and also to get answers to our questions regarding this upgrading technique, we visited the SMB high pressure water scrubbing plant in Tilburg. Our visit took place on the 9th of April 2008. We arranged a meeting with René van den Kieboom. The visit started with a general presentation about the upgrading plant in Tilburg, which was followed with a detailed explanation about each separation unit. After this presentation there was the opportunity for asking our questions. Since this excursion was 49

Figure D.1: The HPWS plant in Tilburg

planned in the middle of our project we had many questions, both about the technique of biogas upgrading as well as the treating method of the waste streams and a cost estimation according to this technique. The questions were extensively answered. Finally we went to the site to have a closer look at different units of the plant, where the given presentation was coupled to more detailed information about each separation unit of the plant. We talked further about the different theoretical features of the process and how they turn out to behave during operation. The picture shows the plant we visited. Address Vloeiveldweg 10 5048 TD Tilburg Telephone: 013-4556163

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Appendix E Visit to Carbiogas BV in Nuenen
Cirmac International BV is a world-wide operating company, specialized in gas treatment systems for the petrochemical and chemical industry, refineries and other industries. Cirmac is part of the Rosscor Group of companies. In order to obtain more detailed information about the upgrading processes of biogas, we visited an installation build by Cirmac on the 20th of May 2008 in Tilburg at a site of Carbiogas BV. We arranged a meeting with Ing. Olivier Kuijer and Ing. Maarten van den Heuvel in Nuenen.

Figure E.1: The VPSA plant in Nuenen

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The visit started with a presentation about the plant in Nuenen, in which we got insight in the processes of pressure swing adsorption and membrane separation. At that moment we still missed some information about the cost estimation of a few upgrading processes. Our questions were answered extensively, which gave us the opportunity to fill the gaps in our theories. After the presentation, we went outside to take a look at the upgrading installation. The installation we viewed can be seen in the picture, it is a vacuum pressure swing adsorption (VPSA) installation. We discussed the different theoretical features of the process and how these turn out to behave during operation. Furthermore, we spoke about the waste streams, how they are kept as low as possible and how they are disposed. Finally, we walked to the top of a landfill, to have a look at the biogas wells and to see how a landfill is operated to obtain a large amount biogas with the right conditions.

Address Gulberg 7 5674 TE Nuenen Telephone: 040-839683

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