GB2470197A - Hydrogen sulphide removal - Google Patents
Hydrogen sulphide removal Download PDFInfo
- Publication number
- GB2470197A GB2470197A GB0908143A GB0908143A GB2470197A GB 2470197 A GB2470197 A GB 2470197A GB 0908143 A GB0908143 A GB 0908143A GB 0908143 A GB0908143 A GB 0908143A GB 2470197 A GB2470197 A GB 2470197A
- Authority
- GB
- United Kingdom
- Prior art keywords
- biogas
- hydrogen sulphide
- filtering system
- granules
- system adapted
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 239000008187 granular material Substances 0.000 claims abstract description 12
- 238000001914 filtration Methods 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 9
- 239000000446 fuel Substances 0.000 claims abstract description 6
- 238000002485 combustion reaction Methods 0.000 claims abstract description 5
- 229940087654 iron carbonyl Drugs 0.000 claims abstract description 5
- -1 siloxanes Chemical class 0.000 claims abstract description 4
- CHRJZRDFSQHIFI-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;styrene Chemical compound C=CC1=CC=CC=C1.C=CC1=CC=CC=C1C=C CHRJZRDFSQHIFI-UHFFFAOYSA-N 0.000 claims abstract description 3
- 150000001412 amines Chemical class 0.000 claims abstract description 3
- 229920000642 polymer Polymers 0.000 claims abstract description 3
- 150000003856 quaternary ammonium compounds Chemical class 0.000 claims abstract description 3
- 239000002952 polymeric resin Substances 0.000 claims abstract 2
- 229920003002 synthetic resin Polymers 0.000 claims abstract 2
- 239000001257 hydrogen Substances 0.000 claims description 13
- 229910052739 hydrogen Inorganic materials 0.000 claims description 13
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 12
- 239000007789 gas Substances 0.000 abstract description 10
- 239000010865 sewage Substances 0.000 abstract description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 230000008929 regeneration Effects 0.000 description 5
- 238000011069 regeneration method Methods 0.000 description 5
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 239000000356 contaminant Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 239000002737 fuel gas Substances 0.000 description 2
- 239000002440 industrial waste Substances 0.000 description 2
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 2
- 238000011144 upstream manufacturing Methods 0.000 description 2
- 239000012855 volatile organic compound Substances 0.000 description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 229920001429 chelating resin Polymers 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 239000010791 domestic waste Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000010800 human waste Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 150000002506 iron compounds Chemical class 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
- F02B—INTERNAL-COMBUSTION PISTON ENGINES; COMBUSTION ENGINES IN GENERAL
- F02B43/00—Engines characterised by operating on gaseous fuels; Plants including such engines
- F02B43/10—Engines or plants characterised by use of other specific gases, e.g. acetylene, oxyhydrogen
- F02B43/12—Methods of operating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/48—Sulfur compounds
- B01D53/52—Hydrogen sulfide
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
- F02B—INTERNAL-COMBUSTION PISTON ENGINES; COMBUSTION ENGINES IN GENERAL
- F02B43/00—Engines characterised by operating on gaseous fuels; Plants including such engines
- F02B43/10—Engines or plants characterised by use of other specific gases, e.g. acetylene, oxyhydrogen
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
- F02B—INTERNAL-COMBUSTION PISTON ENGINES; COMBUSTION ENGINES IN GENERAL
- F02B77/00—Component parts, details or accessories, not otherwise provided for
- F02B77/04—Cleaning of, preventing corrosion or erosion in, or preventing unwanted deposits in, combustion engines
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
- F02M—SUPPLYING COMBUSTION ENGINES IN GENERAL WITH COMBUSTIBLE MIXTURES OR CONSTITUENTS THEREOF
- F02M21/00—Apparatus for supplying engines with non-liquid fuels, e.g. gaseous fuels stored in liquid form
- F02M21/02—Apparatus for supplying engines with non-liquid fuels, e.g. gaseous fuels stored in liquid form for gaseous fuels
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
- F02M—SUPPLYING COMBUSTION ENGINES IN GENERAL WITH COMBUSTIBLE MIXTURES OR CONSTITUENTS THEREOF
- F02M27/00—Apparatus for treating combustion-air, fuel, or fuel-air mixture, by catalysts, electric means, magnetism, rays, sound waves, or the like
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
- B01D2253/20—Organic adsorbents
- B01D2253/202—Polymeric adsorbents
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
- B01D2253/20—Organic adsorbents
- B01D2253/206—Ion exchange resins
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2256/00—Main component in the product gas stream after treatment
- B01D2256/24—Hydrocarbons
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/30—Sulfur compounds
- B01D2257/304—Hydrogen sulfide
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/05—Biogas
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/10—Internal combustion engine [ICE] based vehicles
- Y02T10/30—Use of alternative fuels, e.g. biofuels
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Engineering & Computer Science (AREA)
- Combustion & Propulsion (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Analytical Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Environmental & Geological Engineering (AREA)
- Gas Separation By Absorption (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
A method of operating a combustion engine using biogas as fuel where prior to the biogas reaching the engine it is passed through a filtering system adapted to remove hydrogen sulphide from the gas. Preferably the biogas is produced at landfill and sewage sites and is used to fuel engines to drive generators. The filtering system adapted to remove hydrogen sulphide may be located downstream of a filtering system adapted to remove siloxanes from the biogas. Preferably the system generally includes one or more beds of polymeric resin granules treated with quaternary ammonium compound or an amine or may be a styrene-divinyl benzene polymer treated with iron carbonyl which capture the hydrogen sulphide molecules and keep them bound to the granules until the filter is regenerated.
Description
REMOVING HYDROGEN SULPHIDE FROM AIR AND GAS STREAMS
This invention relates to removing hydrogen sulphide from air and gas streams.
In recent years there has been increasing use of biogas produced at landfill and sewage sites to fuel engines that drive generators that produce electricity. The biogas, which is derived from the decomposition of waste, generally contains between 30% and 65% methane; unfortunately, the gas also contains contaminants that can damage the engines using the gas as fuel. Critically the presence of hydrogen sulphide is detrimental because of the acidic nature of hydrogen suiphide, both in its gaseous form and because of its ability to form sulphuric acid when in contact with moisture. The presence of acidic compounds within the engine promotes corrosion of internal parts leading to expensive maintenance and repairs.
In addition the presence of hydrogen suiphide will corrode and damage other parts of the gas system including the pipe work carrying the gas, filters to remove particles, and valves and instruments fitted to the system.
According to the present invention, there is provided a method of operating a combustion engine using biogas as fuel where, prior to the biogas reaching the engine, it is passed through a filtering system adapted to remove hydrogen suiphide from the biogas.
The preferred way of carrying out this filtering is to pass the biogas through a filter including one or more beds of activated granules which capture the hydrogen sulphide molecules and keep them bound to the granules until the filter is regenerated.
Preferably the filtering is carried out as far upstream as practical, so as to protect other plant and equipment as well as the engine itself. However, in many cases, the existing plant will include a siloxane filter to remove siloxanes and other volatile organic compounds from the feed of biogas, as these have long been known to give rise to problems with engine running, particularly the build-up of hard deposits within the engine itself. In such cases, it is preferable to install the hydrogen suiphide filtering system after the siloxane filter, because if the hydrogen suiphide filter was upstream of the siloxane filter, it could trap some siloxanes and other volatile organic compounds, leading to reduced performance or even blocking. Downstream of the siloxane filter, the gas stream is mostly clear of other contaminants, so allowing the hydrogen suiphide filter to operate effectively to remove the hydrogen sulphide.
As noted above, the preferred filtering system is a bed of granules which absorb the hydrogen suiphide from the flow of biogas. In such a case, the concentration of hydrogen sulphide builds up in the material of the bed, reducing its efficiency. This may be restored by regeneration in standard fashion, usually at intervals of from 3 to 6 hours, the optimum interval depending on the absorption capacity of the material of the bed, the concentration of hydrogen suiphide and the amount of biogas flowing through the system.
The regeneration process is preferably carried out simply by passing hot air across the filter bed(s) thus releasing the hydrogen sulphide molecules into the hot air stream. The air temperature is preferably from 80 to 150°C.
Because it is usually undesirable simply to release the hydrogen sulphide expelled from the bed(s) during regeneration, the hot hydrogen sulphide-containing exhaust stream is preferably treated with ozone, conveniently injected directly into the air stream. This reacts with the hydiogen sulphide particularly if the stream of exhaust gas is subjected to UV radiation, to produce sulphur and water vapour, and the latter may then simply be released to atmosphere. The sulphur may be collected and disposed of.
Alternatively the warm air stream containing hydrogen suiphide released during regeneration can be treated with an electron beam or plasma torch system to decompose the molecules of hydrogen sulphide into its constituent elements.
We have found that a wide variety of granules may be used as the filter medium, particularly commercially available polymeric adsorbent materials, such as ion exchange resins or other adsorbent polymer materials, for example Dow Chemicals Dowex M 43, and Rohm & Haas Amberlite XAD 7 HP. These are preferably doped with a quaternary ammonium compound or a suitable amine to attract and adsorb the hydrogen sulphide molecules, while enabling their easy release during the desorption process.
Alternative materials which have been found to work well are styrene divinyl benzene polymer granules, for example Purolite MN200, Dow Optipore 503 and Rohm & Haas XAD4, coated with a iron compound such as Fe2(CO)g (iron carbonyl). The iron carbonyl will attract the H2S molecules and absorb them until released by heating during regeneration.
The following examples illustrate how the invention can be put into practice:
Example 1
A landfill site was identified on which was located a 3516 Caterpillar reciprocating engine, the engine running on methane biogas produced by the decomposing of industrial and household waste at the site, and driving a generator.
Analysis of the infeed gas showed it to contain 2500ppm of hydrogen s ul ph ide.
A filter was then inserted into the feed line to the engine, following a strip down and cleaning of its combustion surfaces. The filter consisted of a cylindrical housing of diameter 800mm and length 400 mm, which was filled with 45 kg of Ferrocal (an iron carbonyl coated polystyrene granule material, ex Pptek Limited). Analysis of the hydrogen suiphide level in the output stream of fuel gas which constituted the infeed to the engine and which had a volumetric flow rate of around l2000m3fhour showed it to contain 3ppm of hydrogen sulphide.
Example 2
A sewage treatment site was identified on which was situated a Jenbacher 420 reciprocating engine, fuelled by methane biogas produced by the decomposition of products from both human and industrial waste, and driving a generator. Analysis of the infeed gas showed it to contain 4500ppm hydrogen sulphide.
A filter was then inserted into the feed line to the engine, following a strip down and cleaning of its combustion surfaces. The filter consisted of a cylindrical housing of diameter 800mm and length 400 mm, which was filled with 45 kg of Dowex M43. Analysis of the hydrogen sulphide level in the output stream of fuel gas which constituted the infeed to the engine and which had a volumetric flow rate of around 1200m3/hour showed it to contain no detectable level of hydrogen sulphide.
Claims (5)
- CLAIMS1. A method of operating a combustion engine using biogas as fuel where, prior to the biogas reaching the engine, it is passed through a filtering system adapted to remove hydrogen suiphide from the biogas.
- 2. A method according to Claim 1 wherein the biogas is passed through a filter including one or more beds of activated granules which capture the hydrogen suiphide molecules and keep them bound to the granules until the filter is regenerated.
- 3. A method according to Claim 1 or 2 wherein the filtering system adapted to remove hydrogen sulphide is located downstream of a filtering system adapted to remove siloxanes from the biogas stream.
- 4. A method according to any one of Claims 1 to 3 wherein the granules are of a polymeric resin treated with a quaternary ammonium compound or an amine.
- 5. A method according to any one of Claims 1 to 3 wherein the granules are of a styrene-divinyl benzene polymer and are treated with iron carbonyl.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB0908143A GB2470197A (en) | 2009-05-12 | 2009-05-12 | Hydrogen sulphide removal |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB0908143A GB2470197A (en) | 2009-05-12 | 2009-05-12 | Hydrogen sulphide removal |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| GB0908143D0 GB0908143D0 (en) | 2009-06-24 |
| GB2470197A true GB2470197A (en) | 2010-11-17 |
Family
ID=40833868
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB0908143A Withdrawn GB2470197A (en) | 2009-05-12 | 2009-05-12 | Hydrogen sulphide removal |
Country Status (1)
| Country | Link |
|---|---|
| GB (1) | GB2470197A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102278203A (en) * | 2011-06-25 | 2011-12-14 | 汕头市信一塑机制造有限公司 | Oxyhydrogen carbon removing method for automobile engine |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2305970A (en) * | 1995-10-02 | 1997-04-23 | Kohler Co | Biogas-fuelled i.c. engine, eg for driving a generator, with injection of corrosion-inhibiting oil on shutdown |
| GB2440123A (en) * | 2006-07-19 | 2008-01-23 | Pptek Ltd | Cleaning a gas feed to an internal combustion engine |
| WO2008089147A2 (en) * | 2007-01-15 | 2008-07-24 | Cha Corporation | Microwave induced destruction of siloxanes and hydrogen sulfide in biogas |
-
2009
- 2009-05-12 GB GB0908143A patent/GB2470197A/en not_active Withdrawn
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2305970A (en) * | 1995-10-02 | 1997-04-23 | Kohler Co | Biogas-fuelled i.c. engine, eg for driving a generator, with injection of corrosion-inhibiting oil on shutdown |
| GB2440123A (en) * | 2006-07-19 | 2008-01-23 | Pptek Ltd | Cleaning a gas feed to an internal combustion engine |
| WO2008089147A2 (en) * | 2007-01-15 | 2008-07-24 | Cha Corporation | Microwave induced destruction of siloxanes and hydrogen sulfide in biogas |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102278203A (en) * | 2011-06-25 | 2011-12-14 | 汕头市信一塑机制造有限公司 | Oxyhydrogen carbon removing method for automobile engine |
| CN102278203B (en) * | 2011-06-25 | 2013-04-24 | 汕头市信一塑机制造有限公司 | Oxyhydrogen carbon removing method for automobile engine |
Also Published As
| Publication number | Publication date |
|---|---|
| GB0908143D0 (en) | 2009-06-24 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| 732E | Amendments to the register in respect of changes of name or changes affecting rights (sect. 32/1977) |
Free format text: REGISTERED BETWEEN 20120202 AND 20120208 |
|
| WAP | Application withdrawn, taken to be withdrawn or refused ** after publication under section 16(1) |