Upgrading biogas Comparing different biogas upgrading techniques

Project group: Jos de Hullu, Jenny Maassen, Paul van Meel, Siamak Shazad and Jessica Vaessen Tutor: Laura Bini M.Sc. Coordinator: dr. ir. Jetse Reijenga http://students.chem.tue.nl/ifp24/ mdp1.st@tue.nl

Project
This poster presents the results of a multidisciplinary project executed at the Technical University of Eindhoven commissioned by Dirkse Milieutechniek BV (DMT) focused on the upgrading of biogas. Biogas is a result of anaerobic digestion of organic material, resulting in CH4 and CO2 gas and some pollutants. The CH4 can be used as a green energy source by upgrading biogas to natural gas quality and injecting it into the existing gas grid or to using it as a fuel. Upgrading of biogas signifies removal of the CO2 and pollutants such as H2S. Currently, several processes are available for the upgrading. Dirkse Milieutechniek is developing 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. Therefore, a literature study was conducted to create a clear overview of the present upgrading techniques allowing for an objective comparison. Several techniques were investigated and compared.

Atmosphere

Chemical absorption Upgrading Techniques H2S CO2

Water Treated Biogas Fe3+/EDTA

Scrubber

Biogas

Absorber

CO2 absorption using aqueousamino acid salt solutions:

Regenerator
Particle Separation
Air

Water

Fe2+/EDTA

Cooler

2 RN H2 + CO2 CO2 + OH + RN H3 H2 O

+ RN HCOO + RN H3 HCO3 RN H2 + H + H + + OH

(1) (2) (3) (4)

Main reaction:

Sulphur

Absorption and dissocation of H2S:

H2 S (g ) + H2 O H2 S (aq ) H2 S (aq ) H + + HS HS H + + S 2 S 2 + 2F e3+ S + 2F e2+ (2) (3) (4) (5)
Heat exchanger Gas stream in Absorption column Regeneration column

1 H2 S + O2 (g ) S + H2 O 2

(1)

Biogas out CO2

Introduction to Biogas
Upgrading biogas: Increasing calorific value removing H2S
Component Dutch natural gas Volume % 81,3 2,85 14,3 0,89 0,83 43,7 31,7 Canadian natural gas Volume % 94,9 2,50 1,60 0,70 0,75 49,5 37,8

Formation of S:

Regeneration of the iron-chelated solution:

1 1 O2 (g ) + H2 O(l) O2 (aq ) 2 2 1 O2 (aq ) + 2F e2+ 2F e3+ + 2OH 2 (6) (7)

The Wobbe index is a measurement for the combustion behaviour of a gas. If this value is too high or too low the combustion behaviour will be disturbed.
calorif ic value W obbe index = relative density (1)

CH4 C2H6 N2 CO2 Density kg/m3 Wobbe index MJ/m3 Calorific value MJ/kg

High pressure water scrubbing

Based on the physical absorption of dissolving gases in a liquid. The dissolubility of CO2 and H2S is much larger compared to the dissolubility of CH4. Also, the dissolubility of all components increases when pressure is higher. > 98%

H2S: biogas contains small amounts of H2S and some other pollutants. H2S is poisonous when inhaled. Furthermore, when water is present, H2S forms sulphuric acid (H2SO4), which is highly corrosive, rendering the biogas unusable.

Table 1: requirements for injection in a gas grid. To reach the calorific value of Dutch natural gas the methane purity should be > 88%. But if Canadian standards must be achieved the calorific value of biogas should be increased above the calorific value of methane therefore some higher alkanes must be added to the gas.

Adsorption vessel

Adsorption vessel

Adsorption vessel

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 con-

tribute to a far lesser extent to the greenhouse effect. Biogas is such a renewable fuel. It is a combustible gas mixture produced by the anaerobic fermentation of biomass by bacteria and takes a short time to form. The two main sources of biogas are domestic garbage landfills and fermentation of manure and raw sewage.

Biogas Methane

CH4 Volume % 60 100

Calorific value MJ/kg 21.5 38.0

Table 2: Biogas mainly consists of combustible CH4 and non-combustible CO2. 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 its calorific value.

Pressure swing adsorption

Four adsorber vessels operate in an alternating cycle to allow for continuous operation: 1. adsorption 2. regeneration 3. pressure build-up
H2S Removal
Compressor
Biogas
Gas molecules CH4 N2/O2 H2O/H2S CO2

> 97 % CH4-rich gas

Purge Gas

Comparison
This table shows the most important facts for each technique to allow for an easy and objective comparison.
Technique Investment cost 353,000 Running cost 134,500 Cost price upgraded biogas /N m3 biogas 0.17 Maximum achievable yield % 90 Maximum achievable purity % 98 Advantages Disadvantages

Carbon molecular sieve

CH4 Production

Chemical sorption

ab-

Almost complete H2 S re- Only removal of one compomoval nent in column Expensive catalyst Removes gases and particulate matter High purity, good yield Simple technique, no special chemicals or equipment required Neutralization of corrosive gases Limitation of H2 S absorption due to changing pH H2 S damages equipment Requires a lot of water, even with the regenerative process

Gas Conditioning

High pressure water scrubbing

265,000

110,000

0.13

94

98

Condensate

Waste Gas Vacuum pump for regeneration

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 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

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

This picture shows the results of a model made in the Aspen Plus software package.
Recirculation of product stream as cooling agent

Cryogenic separation

908,500

397,500

0.44

98

91

Membrane separation

233,000

81,750

0.12

78

89.5

-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

This list compares the (dis)advantages of the techniques in the current opinion of DMT to the findings of the project group. Chemical Absorption + Removal of H2S, H2O and CO2 in one step H2 and CO2 are separated using different absorption columns - Active carbon required for CO2 recycling Other absorbents also possible High Pressure Water Scrubbing + Removal of H2S, H2O, CO2 in one step This has to be done in two steps or the H2 has to be removed from the water afterwards + Dry gas at pressure. With use of silicates it will dry So, like chemical absorption a drying step is still required - Large Water scrubbing can be implemented quite compactly. For large flows however, the scrubbing column becomes increasingly larger. Pressure swing adsorption + Removal of H2S, H2O, CO2 in one step For H2S removal an extra step is required because it poisons the adsorbent material Cryogenic separation - Relative high investment costs Investment costs are exceptionally high compared to the other techniques Membrane separation - Not a proven technique Cirmac already built a plant using membrane separation proving this technology - Chemicals required The membranes investigated do not require additional chemicals - Regeneration is energy expensive No regeneration is necessary. Membranes have a long lifetime - Relative high investment costs The costs of investment are lowest of the five techniques investigated

Compressor

Cooler

Compressor

Cooler Distillation Column

Product 91 % CH4 8 % N2 1% other

Waste 0.6 % CH4 98 % CO2

Membrane separation
H2S removal: with separate removel step also posible with certain membranes CH4 purity and yield highly dependent on choise of membrane Internally staged membrane increases purity Biogas

CO2 (+ H2S) + 10 ~15 % CH4

Conclusions
High pressure water scrubbing is the cheapest option. PSA and membrane separation waste streams are easily dealt with. The other techniques have waste streams which need more advanced waste treatment. Membrane separation and high pressure water scrubbing are the easiest processes to operate. No catalysts or chemicals are needed. Cryogenic separation works at very low temperatures and high pressures which requeirs an operator and safety restrictions have to be set making it and expensive technique. Overall, high pressure water scrubbing performs the best for DMT: low cost price, high purity and yield, only one waste stream needs treatment and it is a continuous process.

Compressor

Membrane separator
CO2 (+ H2S) > 90 % CH4

Internally staged

H2S Removal

> 78 % CH4