CN102642810A - Combined process for preparing Fischer-Tropsch synthetic oil raw material gas by utilizing coke-oven gas - Google Patents
Combined process for preparing Fischer-Tropsch synthetic oil raw material gas by utilizing coke-oven gas Download PDFInfo
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Abstract
The invention relates to a combined process for preparing a Fischer-Tropsch synthetic oil raw material gas by utilizing a coke-oven gas. The combined process comprises the following steps of: with coarse coke-oven gas as a raw material, removing naphthalene, tar, hydrogen sulfide, hydrocyanic acid, ammonia, organic sulfur and other heavy-hydrocarbon impurities out of coarse coke-oven gas in a pretreatment unit;; then pressurizing the coarse coke-oven gas in a gas compression unit; then converting into CH4 through oxidation of non-catalysis part of the coke-oven gas; and finally carrying out precision desulfurization and deep desulfurization, thereby obtaining the high-quality Fischer-Tropsch synthetic oil raw material gas. According to the invention, through a step-by-step purification combined process, impurities and the sulfurous gas in the coke-oven gas are removed efficiently, so that coke-oven gas becomes the synthetic gas with high additional value and high economic benefit; the coking industrial chain is prolonged; the coke-oven gas is converted into fuel oil, greenhouse gas and toxic gas which are brought about by gas combustion are reduced; the combined process meets national requirements of energy conservation, emission reduction and industry policy and has the advantages of low sulfur, high degree of purification, obvious environment effect, high resource utilization ratio, relative low construction investment in devices, low operating cost and the like.
Description
Technical field
The present invention relates to a kind of preparation method of Fischer-Tropsch synthesis oil virgin gas, especially relate to the combination process that a kind of coke(oven)gas prepares the Fischer-Tropsch synthesis oil virgin gas.
Background technology
Coke-oven gas is the sub product that produces in the process of coking, and staple is hydrogen and methane, also has small amounts of olefins, carbon monoxide and carbonic acid gas, and carries impurity such as micro-tar, naphthalene, NH3, H2S secretly.1 ton of coke of every production will produce the coke-oven gas about 430 cubic metres, and wherein half is used to melt down combustion-supporting.For a long time, the coke-oven gas that coal chemical enterprise produces is all burnt with the mode of " a point day lamp " in vain, has not only wasted resource but also contaminate environment.For this reason, domestic coke-oven gas comprehensive utilization is extremely urgent.
Summary of the invention
The object of the invention be exactly provide in order to overcome the defective that above-mentioned prior art exists a kind of economic benefit obviously, high, the environment protecting of sulphur degree of purification obviously, the relatively low coke(oven)gas of construction investment of technical maturity, device prepares the combination process of Fischer-Tropsch synthesis oil virgin gas.
The object of the invention can be realized through following technical scheme:
A kind of coke(oven)gas prepares the combination process of Fischer-Tropsch synthesis oil virgin gas; It is characterized in that; This technology comprises thick coke(oven)gas pretreatment unit, gas compression unit, coke(oven)gas non-catalytic partial oxidation unit and precision desulfurization and deep desulfuration unit; Thick coke(oven)gas through pretreatment unit, is removed the naphthalene, tar, the NH that carry secretly in the thick coke-oven gas
3, H
2S and heavy hydrocarbons impurity are integrated gas to H through non-catalytic partial oxidation then
2: the mol ratio of CO is 2-3, again through precision and deep desulfuration, makes that total sulfur content gets final product less than 0.02ppm in the synthetic gas.
Described thick coke(oven)gas pretreatment unit is that thick coke-oven gas is got into the gas holder buffering; Pass through water cooler, oil removing tower respectively; Send into alternating temperature absorption (TSA) pretreatment process and transformation absorption (PSA) pretreatment process; Remove naphthalene, tar, hydrogen sulfide, prussic acid, ammonia, organosulfur and the heavy hydrocarbons impurity carried secretly in the thick coke-oven gas, make tar content in the coke(oven)gas less than 1mg/Nm
3, naphthalene content is less than 5mg/Nm
3, benzene content is less than 5mg/Nm
3, NH
3Content is less than 1mg/Nm
3, H
2S content is less than 2mg/Nm
3, organic sulfur content is less than 5mg/Nm
3
Described gas compression unit is that the gas after the cooling of coke(oven)gas pretreatment unit, the oil removing is got into one section supercharging of compressor; Be pressurized to 0.1-0.3MPa (G); Send into coke(oven)gas pretreatment unit TSA pretreatment process; Directly get into two sections superchargings of compressor through the gas behind the PSA pretreatment process again, be compressed to 3.5MPa (G) through three, four sections again.
Described coke(oven)gas non-catalytic partial oxidation unit is with getting into the coke(oven)gas preheater from the Purge gas of compression section, with the gas converting heat that comes out from useless pot to 200-300 ℃, get into the nozzle at receiver top; Mix at receiver burner place with purity oxygen, purity oxygen is preheating to 200-300 ℃ through the oxygen preheat device, gets into the nozzle at receiver top; Conversion reaction is carried out in receiver; The receiver core temperature is more than 1200 ℃, and the reforming gas temperature that goes out receiver gets into a useless pot system and carries out waste heat recovery at 1300-1400 ℃; The while by-product high-pressure steam, steam removes the battery limit (BL) pipe network; Go out to give up the pot the reforming gas temperature at 300-370 ℃; Get into the coke(oven)gas preheater and be cooled to 200-270 ℃; Get into again that the cooling of feedwater preheater and de-salted water preheater is laggard goes into water wash column, wash the granule foreign that to take out of in the reforming gas off and cool to 40 ℃ (3.15MPa (G)).
The reforming gas that described non-catalytic partial oxidation unit obtains through water-gas blast furnace gas or coal gas of converter as the carbon source of the gas, H in the pilot-gas
2: the mol ratio of CO is 2-3.
Described H
2: the mol ratio of CO preferred 2.4.
Described precision desulfurization and deep desulfuration unit adopt PDS wet desulphurization, precision desulfurization and the deep desulfuration technology that combines, and total sulfur content in the synthetic gas is taken off to≤0.02ppm.
Compared with prior art, the present invention has the following advantages:
(1) economic benefit is obvious: the present invention is a raw material with coke-oven plant's by-product coke furnace gas; Through combination purification and conversion process; Prepare the synthetic gas of Fischer-Tropsch synthesis oil production usefulness with high added value; Turn waste into wealth, meet energy-saving and emission-reduction policy, the industry policy of country and the requirement of developing a circular economy;
(2) the sulphur degree of purification is high, environment protecting is obvious: in this process program, owing to adopted TSA temperature swing adsorption process, precision desulfurization and deep desulfuration respectively, can the total sulfur content of synthetic gas be reduced to 0.02ppm, sweetening effectiveness is obvious.And alternating temperature absorption and precision desulfurization and deep desulfuration technology are the Technologies that does not have pollution, clean environment firendly, do not have waste liquid, waste gas and useless solid the generation, and other technologies then can be brought many environmental issues, are difficult to dispose like waste liquid etc.Thereby environment protecting of the present invention is fairly obvious;
(3) construction investment of technical maturity, device is relatively low: the present invention is through combination purification and conversion process; Can effectively purify naphthalene, tar, hydrogen sulfide, prussic acid, ammonia, organosulfur and other heavy hydrocarbons impurity in the coal tar gas; Adopt non-catalytic oxidation technical transform CH4; The composition of control H2/CO in synthetic gas, all technology are mature and reliable all.The major equipment device all can be homemade, the expense of reducing investment outlay.
Embodiment
Below in conjunction with specific embodiment the present invention is elaborated.
Embodiment 1
The coke(oven)gas comprehensive administration project of domestic a certain industrial park, thick coke(oven)gas forms and content is seen table 1.
Thick coke(oven)gas component of table 1 and content
A kind of is raw material with the coke(oven)gas, the combination process of the required synthetic gas of preparation Fischer-Tropsch synthesis oil, and this technology may further comprise the steps:
(1) coke-oven gas pretreatment unit
Cause compressor to stop up easily owing to from the thick coke(oven)gas that the industrial park is come, contain benzene, naphthalene and tar etc., and impurity and hydrogen sulfide, prussic acid, ammonia, organosulfur etc. cause F-T synthetic catalyst poisoning and deactivation easily.So need carry out secondary-cleaned to coke-oven gas.At first get into the gas holder buffering from the thick coke-oven gas (pressure: 4KPa (G), temperature: 30 ℃) of industrial park, be pressurized to 30KPa (G), separate wherein through water cooler, oil removing tower that entrained oil drips, to alleviate the load of back workshop section through Root's blower.The gas that comes out gets into compressor and is pressurized to a 0.2MPa (G) for; One section coke(oven)gas that comes out of compressor gets into TSA alternating temperature absorption process; Wherein a pretreater is in the absorption de-oiling, takes off the naphthalene state, and another is in reproduced state, and two tower alternations realize the purification of coal gas.After the pre-treatment, the tar content in the coke(oven)gas is less than 1mg/Nm
3, naphthalene content is less than 5mg/Nm
3, benzene content is less than 5mg/Nm
3, NH
3Content is less than 1mg/Nm
3, H
2S content is less than 2mg/Nm
3, organic sulfur content is less than 5mg/Nm
3
(2) gas compression unit
Gas (～30KPa (G)) after the cooling of coke(oven)gas pretreatment unit, oil removing gets into one section inlet of compressor, is pressurized to 0.2MPa (G), behind interstage cooling, comes out to get into coke(oven)gas pretreatment unit TSA pretreatment process from the compressor one section outlet; Handle back gas through TSA and PSA and come out from the coke(oven)gas pretreatment unit, the impurity in the coke-oven gas removes basically, can directly get into two sections superchargings of compressor, again through three, four sections be compressed to 3.5MPa (G) after to coke(oven)gas non-catalytic partial oxidation operation.
(3) coke(oven)gas non-catalytic partial oxidation unit
Get into the coke(oven)gas preheater from the Purge gas of compression section, ℃ get into the nozzle at receiver top, mix at receiver burner place with oxygen from air separation facility with the gas converting heat to 257 that comes out from useless pot; Oxygen (3.5MPa (G), 30 ℃) from air separation facility is preheating to 239 ℃ through the oxygen preheat device, gets into the nozzle at receiver top; Conversion reaction is carried out in receiver, and the receiver core temperature is more than 1200 ℃, and the reforming gas temperature that goes out receiver gets into a useless pot system and carries out waste heat recovery at 1330 ℃, while by-product high-pressure steam (4.0MPa (G)), and steam removes the battery limit (BL) pipe network; Go out to give up the pot the reforming gas temperature about 350 ℃; Get into the coke(oven)gas preheater and be cooled to 240 ℃, get into feedwater preheater and de-salted water preheater again and be cooled to 133 ℃ and laggardly go into water wash column and wash the granule foreign that to take out of in the reforming gas off and cool to 40 ℃ (3.15MPa (G)).H2 in the reforming gas: CO=2.4, H
2The about 1mg/Nm3 of S content, the about 1mg/Nm of COS content
3At last, reforming gas removes precision desulfurization and deep desulfuration device.
(4) precision desulfurization and deep desulfuration unit
The reforming gas that rotation chemical industry section is come gets into smart thionizer after gas-liquid separator I is with IMPURITIES IN and wet goods removal; After the desulfurizing agent desulfurization, be warming up to 90 ℃ at this; Again behind depth hydrolysis's catalyzer, deep purifying desulfurizing agent deep desulfuration; Total sulfur is taken off to 0.02ppm, after after gas-liquid separator II removes moisture, obtain the required synthetic gas of qualified Fischer-Tropsch synthesis oil.
Embodiment 2
A kind of coke(oven)gas prepares the combination process of Fischer-Tropsch synthesis oil virgin gas; This technology comprises thick coke(oven)gas pretreatment unit, gas compression unit, coke(oven)gas non-catalytic partial oxidation unit and precision desulfurization and deep desulfuration unit; Thick coke(oven)gas pretreatment unit is that thick coke-oven gas is got into the gas holder buffering; Pass through water cooler, oil removing tower respectively; Send into TSA alternating temperature absorption pretreatment process and PSA pretreatment process, remove naphthalene, tar, hydrogen sulfide, prussic acid, ammonia, organosulfur and the heavy hydrocarbons impurity carried secretly in the thick coke-oven gas, make tar content in the coke(oven)gas less than 1mg/Nm
3, naphthalene content is less than 5mg/Nm
3, benzene content is less than 5mg/Nm
3, NH
3Content is less than 1mg/Nm
3, H
2S content is less than 2mg/Nm
3, organic sulfur content is less than 5mg/Nm
3, gas compression unit afterwards is that the gas after the cooling of coke(oven)gas pretreatment unit, the oil removing is got into one section supercharging of compressor, is pressurized to 0.1MPa (G); Send into coke(oven)gas pretreatment unit TSA) pretreatment process, directly get into two sections superchargings of compressor through the gas after the processing of PSA pretreatment process, be compressed to 3.5MPa (G) through three, four sections again; Carry out coke(oven)gas non-catalytic partial oxidation unit then, will get into the coke(oven)gas preheater, with the gas converting heat to 200 that comes out from useless pot ℃ from the Purge gas of compression section; Get into the nozzle at receiver top, mix at receiver burner place with purity oxygen, purity oxygen is preheating to 200 ℃ through the oxygen preheat device; Get into the nozzle at receiver top, conversion reaction is carried out in receiver, and the receiver core temperature is more than 1200 ℃; The reforming gas temperature that goes out receiver is at 1300 ℃; Get into a useless pot system and carry out waste heat recovery, the while by-product high-pressure steam, steam removes the battery limit (BL) pipe network; Go out to give up the pot the reforming gas temperature at 300 ℃; Get into the coke(oven)gas preheater and be cooled to 200 ℃; Get into again that the cooling of feedwater preheater and de-salted water preheater is laggard goes into water wash column; Wash the granule foreign that possibly take out of in the reforming gas off and cool to 40 ℃ (3.15MPa (G)), the reforming gas that the non-catalytic partial oxidation unit obtains through water-gas blast furnace gas or coal gas of converter as the carbon source of the gas, H in the gas
2: the mol ratio of CO is 2, and precision desulfurization and deep desulfuration unit adopt PDS wet desulphurization, precision desulfurization and the deep desulfuration technology that combines, and total sulfur content in the synthetic gas is taken off to≤0.02ppm.
Embodiment 3
A kind of coke(oven)gas prepares the combination process of Fischer-Tropsch synthesis oil virgin gas; This technology comprises thick coke(oven)gas pretreatment unit, gas compression unit, coke(oven)gas non-catalytic partial oxidation unit and precision desulfurization and deep desulfuration unit; Thick coke(oven)gas pretreatment unit is that thick coke-oven gas is got into the gas holder buffering; Pass through water cooler, oil removing tower respectively; Send into TSA pretreatment process and PSA pretreatment process, remove naphthalene, tar, hydrogen sulfide, prussic acid, ammonia, organosulfur and the heavy hydrocarbons impurity carried secretly in the thick coke-oven gas, make tar content in the coke(oven)gas less than 1mg/Nm
3, naphthalene content is less than 5mg/Nm
3, benzene content is less than 5mg/Nm
3, NH
3Content is less than 1mg/Nm
3, H
2S content is less than 2mg/Nm
3, organic sulfur content is less than 5mg/Nm
3The gas compression unit is that the gas after the cooling of coke(oven)gas pretreatment unit, the oil removing is got into one section supercharging of compressor; Be pressurized to 0.3MPa (G); Send into coke(oven)gas pretreatment unit TSA pretreatment process; Gas through after the processing of PSA pretreatment process directly gets into two sections superchargings of compressor, is compressed to 3.5MPa (G) through three, four sections again.Coke(oven)gas non-catalytic partial oxidation unit is with getting into the coke(oven)gas preheater from the Purge gas of compression section, with the gas converting heat to 300 that comes out from useless pot ℃, gets into the nozzle at receiver top; Mix at receiver burner place with purity oxygen, purity oxygen is preheating to 300 ℃ through the oxygen preheat device, gets into the nozzle at receiver top; Conversion reaction is carried out in receiver; The receiver core temperature is more than 1200 ℃, and the reforming gas temperature that goes out receiver gets into a useless pot system and carries out waste heat recovery at 1400 ℃; The while by-product high-pressure steam, steam removes the battery limit (BL) pipe network; Go out to give up the pot the reforming gas temperature at 370 ℃; Get into the coke(oven)gas preheater and be cooled to 270 ℃; Get into again that the cooling of feedwater preheater and de-salted water preheater is laggard goes into water wash column; Wash the granule foreign that possibly take out of in the reforming gas off and cool to 40 ℃ (3.15MPa (G)), the reforming gas that the non-catalytic partial oxidation unit obtains through water-gas blast furnace gas or coal gas of converter as the carbon source of the gas, H in the gas
2: the mol ratio of CO is 3.Precision desulfurization and deep desulfuration unit adopt PDS wet desulphurization, precision desulfurization and the deep desulfuration technology that combines, and total sulfur content in the synthetic gas is taken off to≤0.02ppm.
Claims (7)
1. a coke(oven)gas prepares the combination process of Fischer-Tropsch synthesis oil virgin gas; It is characterized in that; This technology comprises thick coke(oven)gas pretreatment unit, gas compression unit, coke(oven)gas non-catalytic partial oxidation unit and precision desulfurization and deep desulfuration unit; Thick coke(oven)gas through pretreatment unit, is removed the naphthalene, tar, the NH that carry secretly in the thick coke-oven gas
3, H
2S and heavy hydrocarbons impurity are integrated gas to H through non-catalytic partial oxidation then
2: the mol ratio of CO is 2-3, again through precision and deep desulfuration, makes that total sulfur content gets final product less than 0.02ppm in the synthetic gas.
2. a kind of coke(oven)gas according to claim 1 prepares the combination process of Fischer-Tropsch synthesis oil virgin gas; It is characterized in that; Described thick coke(oven)gas pretreatment unit is that thick coke-oven gas is got into the gas holder buffering; Pass through water cooler, oil removing tower respectively, send into alternating temperature absorption pretreatment process and adsorb de-oiling, take off naphthalene, get into transformation absorption pretreatment process again; Remove remaining naphthalene, tar, hydrogen sulfide, prussic acid, ammonia, organosulfur and heavy hydrocarbons impurity, make tar content in the coke(oven)gas less than 1mg/Nm
3, naphthalene content is less than 5mg/Nm
3, benzene content is less than 5mg/Nm
3, NH
3Content is less than 1mg/Nm
3, H
2S content is less than 2mg/Nm
3, organic sulfur content is less than 5mg/Nm
3
3. a kind of coke(oven)gas according to claim 1 prepares the combination process of Fischer-Tropsch synthesis oil virgin gas; It is characterized in that; Described gas compression unit is that the gas after the cooling of coke(oven)gas pretreatment unit, the oil removing is got into one section supercharging of compressor, is pressurized to 0.1-0.3MPa (G), sends into coke(oven)gas pretreatment unit alternating temperature absorption pretreatment process; Directly get into two sections superchargings of compressor through the gas behind the transformation absorption pretreatment process again, be compressed to 3.5MPa (G) through three, four sections again.
4. a kind of coke(oven)gas according to claim 1 prepares the combination process of Fischer-Tropsch synthesis oil virgin gas, it is characterized in that, described coke(oven)gas non-catalytic partial oxidation unit is that the Purge gas from compression section is got into the coke(oven)gas preheater; With the gas converting heat that comes out from useless pot to 200-300 ℃, get into the nozzle at receiver top, mix at receiver burner place with purity oxygen; Purity oxygen is preheating to 200-300 ℃ through the oxygen preheat device; Get into the nozzle at receiver top, conversion reaction is carried out in receiver, and the receiver core temperature is more than 1200 ℃; The reforming gas temperature that goes out receiver is at 1300-1400 ℃; Get into a useless pot system and carry out waste heat recovery, the while by-product high-pressure steam, steam removes the battery limit (BL) pipe network; Go out to give up the pot the reforming gas temperature at 300-370 ℃; Get into the coke(oven)gas preheater and be cooled to 200-270 ℃; Get into again that the cooling of feedwater preheater and de-salted water preheater is laggard goes into water wash column, wash the granule foreign that to take out of in the reforming gas off and cool to 40 ℃ (3.15MPa (G)).
5. a kind of coke(oven)gas according to claim 4 prepares the combination process of Fischer-Tropsch synthesis oil virgin gas, it is characterized in that, the reforming gas that described non-catalytic partial oxidation unit obtains through water-gas blast furnace gas or coal gas of converter as the carbon source of the gas, H in the pilot-gas
2: the mol ratio of CO is 2-3.
6. a kind of coke(oven)gas according to claim 5 prepares the combination process of Fischer-Tropsch synthesis oil virgin gas, it is characterized in that, described H
2: the mol ratio of CO preferred 2.4.
7. a kind of coke(oven)gas according to claim 1 prepares the combination process of Fischer-Tropsch synthesis oil virgin gas; It is characterized in that; Described precision desulfurization and deep desulfuration unit adopt PDS wet desulphurization, precision desulfurization and the deep desulfuration technology that combines, and total sulfur content in the synthetic gas is taken off to≤0.02ppm.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI486203B (en) * | 2013-12-19 | 2015-06-01 | China Steel Corp | Method for extending the operating cycle of hydrogen sulfide scrubber in coke oven |
| CN106241736A (en) * | 2016-08-03 | 2016-12-21 | 西南化工研究设计院有限公司 | A kind of technique utilizing coke-stove gas extraction metallurgy reducing gases |
| CN106520177A (en) * | 2015-09-14 | 2017-03-22 | 上海华西化工科技有限公司 | Method of directly preparing fuel oil from coke oven gas |
| CN106520179A (en) * | 2015-09-14 | 2017-03-22 | 上海华西化工科技有限公司 | Method for combined production of fuel oil with coke oven gas and carbon dioxide-enriched gas |
| CN106520178A (en) * | 2015-09-14 | 2017-03-22 | 上海华西化工科技有限公司 | Method for combined production of fuel oil with coke oven gas and small-size coke prepared gas |
| CN106902614A (en) * | 2017-03-27 | 2017-06-30 | 山东钢铁集团日照有限公司 | A kind of method of organic sulfur in removing coke-stove gas |
| CN109264667A (en) * | 2018-11-23 | 2019-01-25 | 成都聚环球能源科技有限公司 | It is a kind of using coke-stove gas as the method and apparatus of waste synthesis gas |
| CN110669542A (en) * | 2019-08-06 | 2020-01-10 | 山西新石清洁能源科技有限公司 | Method and device for preparing Fischer-Tropsch wax by using coke oven gas |
| CN110683510A (en) * | 2019-09-30 | 2020-01-14 | 盛卫东 | Device for preparing hydrogen meeting vehicle hydrogen standard from biomass gas |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI486203B (en) * | 2013-12-19 | 2015-06-01 | China Steel Corp | Method for extending the operating cycle of hydrogen sulfide scrubber in coke oven |
| CN106520177A (en) * | 2015-09-14 | 2017-03-22 | 上海华西化工科技有限公司 | Method of directly preparing fuel oil from coke oven gas |
| CN106520179A (en) * | 2015-09-14 | 2017-03-22 | 上海华西化工科技有限公司 | Method for combined production of fuel oil with coke oven gas and carbon dioxide-enriched gas |
| CN106520178A (en) * | 2015-09-14 | 2017-03-22 | 上海华西化工科技有限公司 | Method for combined production of fuel oil with coke oven gas and small-size coke prepared gas |
| CN106241736A (en) * | 2016-08-03 | 2016-12-21 | 西南化工研究设计院有限公司 | A kind of technique utilizing coke-stove gas extraction metallurgy reducing gases |
| CN106902614A (en) * | 2017-03-27 | 2017-06-30 | 山东钢铁集团日照有限公司 | A kind of method of organic sulfur in removing coke-stove gas |
| CN106902614B (en) * | 2017-03-27 | 2019-10-18 | 山东钢铁集团日照有限公司 | A kind of method of organic sulfur in removing coke-stove gas |
| CN109264667A (en) * | 2018-11-23 | 2019-01-25 | 成都聚环球能源科技有限公司 | It is a kind of using coke-stove gas as the method and apparatus of waste synthesis gas |
| CN110669542A (en) * | 2019-08-06 | 2020-01-10 | 山西新石清洁能源科技有限公司 | Method and device for preparing Fischer-Tropsch wax by using coke oven gas |
| CN110683510A (en) * | 2019-09-30 | 2020-01-14 | 盛卫东 | Device for preparing hydrogen meeting vehicle hydrogen standard from biomass gas |
| CN110683510B (en) * | 2019-09-30 | 2023-04-18 | 盛卫东 | Device for preparing hydrogen meeting vehicle hydrogen standard from biomass gas |
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