CN105132054B - A kind of method for producing synthesis gas - Google Patents
A kind of method for producing synthesis gas Download PDFInfo
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- CN105132054B CN105132054B CN201510388496.9A CN201510388496A CN105132054B CN 105132054 B CN105132054 B CN 105132054B CN 201510388496 A CN201510388496 A CN 201510388496A CN 105132054 B CN105132054 B CN 105132054B
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Abstract
A kind of method for producing synthesis gas is that coke-stove gas and coal gas are passed through into gas holder to be sufficiently mixed, and forms the coarse raw materials gas for meeting that downstream synthesis H:Cmoleratio general 1.0 5.0 requires；Coarse raw materials gas is purified after compression, removes H2S and CO2Deng impurity, the hydrogen sulfide of removing removes sulfur recovery, the CO of removing2Gas is vented.Coarse raw materials gas after purification carries out methane separation, isolates methane gas and is made liquefied natural gas product or compressed natural gas product, crude synthesis gas is purified and methane separation after be met the pure synthesis gas of synthesis downstream product hydrogen-carbon ratio requirement.The present invention has the advantages of comprehensive utilization of coal gas and coke-stove gas.
Description
Technical field
The invention belongs to a kind of method for producing synthesis gas.
Technical background
Synthesis gas is a kind of unstripped gas as industrial chemicals using carbon monoxide and hydrogen as key component.Synthesis gas is used
Way is to synthesize the most basic raw materials of product such as ammonia, natural gas, methanol, ethylene glycol, low-carbon alkene, artificial oil extensively.Synthesis gas
Raw material range is very wide, is produced by such as solid fuel gasification such as coal, charcoal of carbon containing mineral matter, also can be by lightweights such as natural gas and naphthas
Hydro carbons is produced, and can also be produced by heavy oil partial oxidation method.The technology of synthesis gas is prepared substantially by external major company such as shell
Company, Sa Suoer companies, BASF AG, XOM's monopolization.
The synthesis gas composition (volume %) of various method productions has very big difference:H2：32~67, CO：10~57, CO2：2~
28、CH4：0.1~14, N2：0.6~23.In addition, also micro H2S, the harmful components such as COS, HCN.It is made by these raw materials
The synthesis gas obtained, because its H/C mol ratio difference is huge, generally can not directly meet the needs of sintetics.Such as：As conjunction
The unstripped gas of ammonification, it is desirable to H/N2=3, produce the synthesis gas requirement H of methanol2/ CO ≈ 2 or (H2- CO2)/(CO+CO2) ≈ 2,
Production natural gas then requires synthesis gas H2/ CO ≈ 2 or (H2- CO2)/(CO+CO2)≈3.Therefore, after synthesis gas is made, still need
Its composition is adjusted, the main method of adjustment is to utilize water gas reaction (transformationreation), to reduce carbon monoxide, improves hydrogen
Content.
China is the first big coke production state in the world, production coke a large amount of coke-stove gas of by-product simultaneously.Coke-stove gas
Main component is (volume ratio)：50-60% hydrogen, 20-28% methane, 10-15% CO+CO2.It is in addition, also micro
H2S, the harmful components such as COS, HCN.These coke-stove gas part is used for methanol processed, synthesis ammonia and factory's combustion gas, and inclined
Remote area is then discharged in vain.Nearly 300 billion cubic meter more than needed is burnt every year in addition to production synthesis ammonia and methanol for coke-stove gas at present
Furnace gas, due to coke-stove gas form " the more carbon of hydrogen are few " the characteristics of, it is about 55% to cause the capacity usage ratio of coke-stove gas at this stage
Left and right, cause huge energy waste and environmental pollution.
The low-quality lignite on the ground such as rich coal resources in China, particularly Inner Mongol, Xinjiang enters through synthesis gas made from gasification furnace
The synthesis of row chemical products, by the few feature of the more hydrogen of the carbon of producing synthesis gas from coal, (gas forms percent by volume：CO：45-60%,
H2：22-28%, CO2：12-20, CH4：8-12%, H2S：0.21) understand, individually produced and synthesized by coke-stove gas or coal gas
The products such as ammonia, natural gas, methanol, ethylene glycol, low-carbon alkene, artificial oil, all exist component ratio it is unbalanced, using insufficient
Problem：The more carbon of coke-stove gas hydrogen are few, are individually used for sintetics and a large amount of hydrogen residues necessarily occur, or need supplement carbon in addition
Source；And the more hydrogen of coal gas carbon are few, exclusive use will occur that a large amount of carbon are remaining, or need a large amount of supplemental hydrogen sources in addition.
At present in actual production, the characteristics of lacking to the more hydrogen of coal gas carbon, generally pass through water-gas shift, rational hydrogen carbon is made
Than；Few to the more carbon of coke-stove gas hydrogen, the characteristics of methane content is high, generally use methane carbon dioxide reformation solves, but no matter
It is water-gas shift, or methane reforming is all in the presence of investment is high, power consumption is big, operates the problems such as operation is complicated.
If coke-stove gas and synthesis gas mixed in proportion, it can reach and learn from other's strong points to offset one's weaknesses, be formed and meet to synthesize different chemical industry
The gas composition of product, " gas its use to the greatest extent " of coke-stove gas and coal gas is realized, turns waste into wealth, reduces water-gas shift or methane weight
Whole workshop section, it is low to reach technological process simple, small investment, operation, administration fee.This method not only produce obvious economic benefit and
Environmental benefit, it is also significant to Energy restructuring.
The content of the invention
It is an object of the invention to provide a kind of method of the production synthesis gas of the comprehensive utilization of coal gas and coke-stove gas.
The characteristics of present invention can make full use of the coal gas composition more hydrogen of carbon few, and the more carbon of coke-stove gas hydrogen are few, incite somebody to action both
Mix, learn from other's strong points to offset one's weaknesses by a certain percentage, meet the hydrogen-carbon ratio requirement of synthesis multiple product.Solve simultaneously and individually use coke-oven coal
Gas production chemical products need benefit carbon, and either methane reforming and person are individually needed to mend hydrogen or entered using coal gas inhibition and generation chemical product
The shortcomings that row water-gas shift, realize the comprehensive utilization of coal gas and coke-stove gas.
To achieve the above object, the present invention uses following scheme：
(1) coke-stove gas and coal gas are passed through into gas holder to be sufficiently mixed, formation meets that downstream synthesis H:Cmoleratio is general
The coarse raw materials gas of 1.0-5.0 requirements；
(2) coarse raw materials gas is purified after compression, removes H2S and CO2Deng impurity, the hydrogen sulfide of removing goes sulfur recovery, takes off
The CO removed2Gas is vented.Coarse raw materials gas after purification carries out methane separation, and isolating the obtained LNG product of methane gas, (liquefaction is natural
Gas) or CNG products (compressed natural gas), crude synthesis gas is purified and methane separation after be met synthesis downstream product hydrogen-carbon ratio
It is required that pure synthesis gas.
Synthesis gas as described above can be used for production natural gas, methanol, ethylene glycol, low-carbon alkene, dimethyl ether, artificial oil
Deng, but it is not limited to listed several prods.
The source of coke-stove gas as described above can be that tamping coke furnace, top dress coke oven, dichotomic type coke oven or twin are burnt
Stove.
The source of coal gas as described above can be crushed coal pressurized-gasification furnace, Lurgi gasifier, ash agglomerating stove, Texaco
The gasification furnaces such as coal slurry gasifier, multiinjector coal slurry gasifier or space flight stove, gas volume percentage composition are：CO：45-
60%, H2：22-28%, CO2：12-20, CH4：8-12%, H2S：0.15-0.35%
The mol ratio of coke-stove gas and coal gas as described above is 0.2-9.0：Between 1
Raw material gas purifying as described above can be tannin process, ADA methods, and thermokalite method, NHD methods, low-temp methanol wash method or network
Close the purifiers such as iron processes.
Raw material gas purifying device as described above is preferably to use low temperature washing device for methanol, and operation temperature is -35~-55
DEG C, operating pressure 2.0-6.5MPa, H in the unstripped gas after low-temp methanol is washed2S<0.1ppm,CO2<20ppm。
The coarse raw materials gas complicated component formed due to synthesis gas and coke-stove gas.Its gas component includes CO, H2、CO2、CH4
The H of denier2S, organic sulfur, tar, aliphatic acid, naphtha etc..CO, H are removed in these components2Active principle, remaining all groups
Dividing includes CO2All it is the objectionable impurities for needing to remove with sulfide, it is seen that it purifies the arduousness of task.Make a general survey of current various gases
Purification technique, can take on this person with heavy responsibilities's non-cryogenic methanol and wash and do not belong to.Because only low temperature methanol cleaningization just can be same
All various harmful components, such as CO are neatly removed in one device2、H2S、COS、C4H4S、HCN、NH3、H2O、C2Above hydro carbons
(including light oil, aromatic hydrocarbon, naphtha, alkene and colloid etc.) and other carbonyls etc., and other any purification works
Skill can not all accomplish.In addition, low-temp methanol washing process also has following various significant excellent compared with other purification techniques
Point：
1. absorbability is strong, solution internal circulating load is small
2. methanol solvate is cheap and easy to get, regeneration energy consumption is low
3. gas purification degree is high
4. solvent heat endurance and chemical stability are good, solvent is non-degradable, non-foaming, and equipment is not corroded
5. first alcohol and water can be dissolved each other with arbitrary proportion, its dry feedstock gas can be used using this characteristic
Low-temp methanol washes the removing for realizing plurality of impurities in the same apparatus, relative to a variety of net of other purification methods
For changing process combination, process is relatively single, reasonable, management easy to operation.
Methane separation as described above can use pressure swing adsorption or the U.S. safe this and the neat company of Bock Lightware
Cold separation technology, separation temperature is -150 DEG C to -170 DEG C, preferably -155 DEG C Dao -165 DEG C, separating pressure 3-8Mpa, excellent
Select 4.0-5.5Mpa.
The present invention compared with prior art, has a clear superiority, specific manifestation is as follows：
1st, the characteristics of present invention is few according to the more carbon of coke-stove gas hydrogen, and the more hydrogen of coal gas composition carbon are few, by both by certain
Ratio mixes, and learns from other's strong points to offset one's weaknesses, and coal gas is purified, methane separation, pure synthesis gas is made, while isolate gas product
Raw material as higher value uses.
2nd, synthesis gas hydrogen-carbon ratio is controllable, meets that multiple product synthesis requires.The present invention is by coke-stove gas and coal gas by not
The synthesis gas being mixed to prepare in proportion can meet synthesize multiple product hydrogen-carbon ratio requirement, such as production synthesis ammonia, natural gas,
The hydrogen-carbon ratio of the product requirements such as methanol, low-carbon alcohols, dimethyl ether, ethylene glycol, low-carbon alkene, artificial oil from 1.0 to 5.0, and
It is difficult individually to meet hydrogen-carbon ratio requirement by coke-stove gas or coal gas.
3rd, the present invention solves simultaneously individually needs to mend carbon or individually uses coal using coke-stove gas production chemical products
Gas inhibition and generation chemical product processed needs to mend hydrogen, and the technological process length that above two gas is recycled, complex operation are costly
Shortcoming.The present invention organically combines the shortcomings that two kinds of gas resources, the advantages of becoming to have complementary advantages, and can be burnt by controlling
The mixing ratio of producer gas and coal gas realizes the requirement for synthesizing different downstream product to hydrogen-carbon ratio, realizes coal gas and coke-stove gas
Turn waste into wealth, comprehensively utilize.
Brief description of the drawings
Fig. 1 is the process chart of the present invention.
Embodiment
With reference to specific embodiment, the present invention is described in detail, and these embodiments are only used in more detail specifically
The bright present invention, and the scope that should not be construed as the above-mentioned theme of the present invention is only limitted to the limitation of following embodiments.
Embodiment 1：By coke-stove gas caused by tamping coke furnace, (percent by volume composition is H2：53%, CH4：26%, CO+
CO2:15%, N2：6%) (percent by volume composition is CO to the coal gas produced with crushed coal pressure gasifying：52%, H2：23%,
CO2：14%, CH4：11%, H2S：0.2%) mole flow-rate ratio 5.0 is pressed：1 is sent into gas holder, and it is H to form gas volume composition2：
48.0%, CO：14.5%, CO2:9.0%, CH4：23.5%, N2：4.8%, H2S：0.033% unstripped gas.Unstripped gas is through pressure
Enter low temperature methanol cleaning after contracting, H is removed under the conditions of -42 DEG C of temperature, pressure 4.0MPa2S and CO2Deng impurity, H is obtained2S
Content is less than 0.1ppm, CO2Content is less than 20ppm unstripped gas, the rear H of removing2S removes sulfur recovery, the CO of removing2Gas is vented.Only
Unstripped gas after change enters cryogenic separation methane separation, and LNG is made in separation of methane under the conditions of pressure 4.0MPa, -153 DEG C of temperature
(liquefied natural gas) product, it is 3.31 to obtain H:Cmoleratio, can meet that the pure synthesis gas of natural gas motorcar is produced in methanation.
Embodiment 2
By (percent by volume composition is H to coke-stove gas caused by the dress coke oven of top2：62%, CH4：23%, CO+CO2:10%,
N2：5%) (percent by volume composition is CO to the coal gas produced with crushed coal pressure gasifying：59%, H2：20%, CO2：12%,
CH4：9%, H2S：0.25%) mole flow-rate ratio 2.5 is pressed：1 is sent into gas holder, and it is H to form gas volume composition2：50.0%, CO：
20.4%, CO2:7.0%, CH4：19.0%, N2：3.6%, H2S：0.013% unstripped gas, unstripped gas enter heat after compression
Alkali purification, H is removed under the conditions of pressure 2.0MPa, 98 DEG C of temperature2S and CO2Deng impurity, H is obtained2S contents are less than 0.1ppm,
CO2Content is less than 20ppm unstripped gas, the rear H of removing2S removes sulfur recovery, the CO of removing2Gas is vented.Coarse raw materials gas after purification
Into cryogenic separation methane separation, LNG (liquefied natural gas) is made in separation of methane under the conditions of pressure 4.6MPa, -163 DEG C of temperature
Product, it is 2.45 to obtain H:Cmoleratio, can meet the pure synthesis gas that synthesising gas systeming carbinol uses.
Embodiment 3
By coke-stove gas caused by tamping coke furnace, (percent by volume composition is H2：58%, CH4：27%, CO+CO2:11%,
N2：3%) (percent by volume composition is CO to the coal gas produced with Lurgi gasifier：51%, H2：25%, CO2：9%, CH4：
15%, H2S：0.21%) mole flow-rate ratio 2.0 is pressed：1 is sent into gas holder, and it is H to form gas volume composition2：47.0%, CO：
22.9%, CO2:5.1%, CH4：23.0%, N2：2.0%, H2S：0.06% unstripped gas, unstripped gas enter low temperature after compression
Methanol cleaning, H is removed under the conditions of -50 DEG C of temperature, pressure 5.1MPa2S and CO2Deng impurity, H is obtained2S contents are less than
0.1ppm,CO2Content is less than 20ppm unstripped gas, the rear H of removing2S removes sulfur recovery, the CO of removing2Gas is vented.It is thick after purification
Unstripped gas enters cryogenic separation methane separation, and LNG (liquefaction is made in separation of methane under the conditions of pressure 5.2MPa, -163 DEG C of temperature
Natural gas) product, it is 2.05 to obtain H:Cmoleratio, can meet the pure synthesis gas that synthesis gas artificial oil uses.
Embodiment 4
By coke-stove gas caused by twin coke oven, (percent by volume composition is H2：55%, CH4：25%, CO+CO2:
7%, N2：4%) (percent by volume composition is CO to the coal gas produced with crushed coal pressure gasifying：59%, H2：19%, CO2：
14%, CH4：8%, H2S：0.25%) mole flow-rate ratio 1.3 is pressed：1 is sent into gas holder, and it is H to form gas volume composition2：39.3%,
CO：29.0%, CO2:11.7%, CH4：17.6%, N2：2.3%, H2S：0.012% unstripped gas, unstripped gas are compressed laggard
Enter the purification of NHD methods, H is removed under the conditions of operating pressure 3.0MPa, -5 DEG C of temperature2S and CO2Deng impurity, H is obtained2S contents are less than
0.1ppm,CO2Content is less than 20ppm unstripped gas, the rear H of removing2S removes sulfur recovery, the CO of removing2Gas is vented.It is thick after purification
Unstripped gas carries out pressure-variable adsorption methane separation, and at 20-40 DEG C, pressure 5.0MPa absorption, pressure 0.05MPa is desorbed separation of methane
Afterwards, it is compressed to 30.0MPa and CNG (compressed natural gas) product is made, it is 1.35 that H:Cmoleratio is obtained after separation of methane, can be met
The pure synthesis gas that synthesis gas preparing dimethy ether uses.
Embodiment 5
By (percent by volume composition is H to coke-stove gas caused by the dress coke oven of top2：56%, CH4：27%, CO+CO2:14%,
N2：3%) (percent by volume composition is CO to the coal gas produced with texaco coal-water slurry gasification stove：51%, H2：25%, CO2：
9%, CH4：15%, H2S：0.25%) mole flow-rate ratio 7.0 is pressed：1 is sent into gas holder, and it is H to form gas volume composition2：51.6%,
CO：16.7%, CO2:3.9%, CH4：25.3%, N2：2.6%, H2S：0.02% unstripped gas, unstripped gas enter after compression
Low temperature methanol cleaning, H is removed under the conditions of -48 DEG C of temperature, pressure 6.0MPa2S and CO2Deng impurity, H is obtained2S contents are less than
0.1ppm,CO2Content is less than 20ppm unstripped gas, the rear H of removing2S removes sulfur recovery, the CO of removing2Gas is vented.It is thick after purification
Unstripped gas enters cryogenic separation methane separation, and LNG (liquefaction is made in separation of methane under the conditions of pressure 6.0MPa, -166 DEG C of temperature
Natural gas) product, H:Cmoleratio is obtained after separation of methane as 3.08, the pure synthesis that synthesis gas preparing natural gas uses can be met
Gas.
Claims (3)
- A kind of 1. method for producing synthesis gas, it is characterised in that comprise the following steps：(1) coke-stove gas and coal gas are passed through into gas holder to be sufficiently mixed, formation meets that downstream synthesis H:Cmoleratio is 1.0-5.0 It is required that coarse raw materials gas；(2) coarse raw materials gas is purified after compression, removes H2S and CO2Impurity, the H of removing2S removes sulfur recovery, the CO of removing2Gas Emptying；Coarse raw materials gas after purification carries out methane separation, isolates methane gas and liquefied natural gas product or compression is made naturally Gas product, crude synthesis gas is purified and methane separation after be met the pure synthesis gas of synthesis downstream product hydrogen-carbon ratio requirement；The source of described coke-stove gas is tamping coke furnace, top dress coke oven, dichotomic type coke oven or twin coke oven；The source of described coal gas is crushed coal pressurized-gasification furnace, Lurgi gasifier, ash agglomerating stove, texaco coal-water slurry gasification Stove, multiinjector coal slurry gasifier or space flight stove；Described coke-stove gas and the mol ratio of coal gas are 0.2-9.0：Between 1；Described raw material gas purifying uses low temperature washing device for methanol, and operation temperature is -35~-55 DEG C, operating pressure 2.0- 6.5MPa, H in the coarse raw materials gas after low-temp methanol is washed2S<0.1ppm,CO2<20ppm；Described methane separation using pressure swing adsorption or the U.S. safe this and the neat company of Bock Lightware cold separation technology, Separation temperature is -150 DEG C to -170 DEG C, separating pressure 3-8MPa.
- A kind of 2. method for producing synthesis gas as claimed in claim 1, it is characterised in that the separation temperature be -155 DEG C to - 165 DEG C, separating pressure 4.0-5.5MPa.
- 3. a kind of method for producing synthesis gas as described in claim any one of 1-2, it is characterised in that described synthesis gas is used In production natural gas, methanol, ethylene glycol, low-carbon alkene, dimethyl ether or artificial oil.
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| CN102181315A (en) * | 2011-03-29 | 2011-09-14 | 太原理工大学 | Process for producing natural gas by coal coking and pyrolysis coal gas thereof |
| CN102942972A (en) * | 2012-11-14 | 2013-02-27 | 中国电子工程设计院 | Method for producing liquefied natural gas by coke oven gas |
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2015
- 2015-07-03 CN CN201510388496.9A patent/CN105132054B/en active Active
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1080129A (en) * | 1965-07-24 | 1967-08-23 | Koppers Gmbh Heinrich | Process for the production of a natural gas substitute from coke-oven gas |
| CN102181315A (en) * | 2011-03-29 | 2011-09-14 | 太原理工大学 | Process for producing natural gas by coal coking and pyrolysis coal gas thereof |
| CN102942972A (en) * | 2012-11-14 | 2013-02-27 | 中国电子工程设计院 | Method for producing liquefied natural gas by coke oven gas |
Non-Patent Citations (1)
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| 水煤气、焦炉煤气联产甲醇工艺的探索与实践;李毓良等;《山东化工》;20110430;第40卷(第4期);第1.1节和第1.3节 * |
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