CN101649232B - Synthesis process of natural gas employing methanation of coke oven gas - Google Patents
Synthesis process of natural gas employing methanation of coke oven gas Download PDFInfo
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- CN101649232B CN101649232B CN200910018047XA CN200910018047A CN101649232B CN 101649232 B CN101649232 B CN 101649232B CN 200910018047X A CN200910018047X A CN 200910018047XA CN 200910018047 A CN200910018047 A CN 200910018047A CN 101649232 B CN101649232 B CN 101649232B
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 137
- 239000007789 gas Substances 0.000 title claims abstract description 106
- 238000000034 method Methods 0.000 title claims abstract description 54
- 239000003345 natural gas Substances 0.000 title claims abstract description 52
- 239000000571 coke Substances 0.000 title claims abstract description 37
- 230000008569 process Effects 0.000 title claims abstract description 25
- 230000015572 biosynthetic process Effects 0.000 title abstract description 6
- 238000003786 synthesis reaction Methods 0.000 title abstract description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 11
- 239000011593 sulfur Substances 0.000 claims abstract description 11
- 238000004140 cleaning Methods 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims description 48
- 235000009508 confectionery Nutrition 0.000 claims description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 229910052739 hydrogen Inorganic materials 0.000 claims description 19
- 238000006477 desulfuration reaction Methods 0.000 claims description 17
- 230000023556 desulfurization Effects 0.000 claims description 17
- 239000001257 hydrogen Substances 0.000 claims description 17
- 230000009466 transformation Effects 0.000 claims description 16
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 14
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 14
- 239000003054 catalyst Substances 0.000 claims description 14
- 238000010521 absorption reaction Methods 0.000 claims description 13
- 230000000977 initiatory effect Effects 0.000 claims description 10
- 238000000746 purification Methods 0.000 claims description 8
- 238000000926 separation method Methods 0.000 claims description 8
- 238000001179 sorption measurement Methods 0.000 claims description 8
- 229910021529 ammonia Inorganic materials 0.000 claims description 7
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 6
- 239000000428 dust Substances 0.000 claims description 6
- 238000005345 coagulation Methods 0.000 claims description 3
- 230000015271 coagulation Effects 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 239000012528 membrane Substances 0.000 claims description 3
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 claims description 2
- 230000002194 synthesizing effect Effects 0.000 abstract description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 21
- 238000005516 engineering process Methods 0.000 description 19
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 12
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 8
- 229910052799 carbon Inorganic materials 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 3
- 239000005864 Sulphur Substances 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 238000007906 compression Methods 0.000 description 3
- 230000006835 compression Effects 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000003610 charcoal Substances 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 239000000567 combustion gas Substances 0.000 description 2
- 230000003009 desulfurizing effect Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 239000002918 waste heat Substances 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- VCRLKNZXFXIDSC-UHFFFAOYSA-N aluminum oxygen(2-) zirconium(4+) Chemical compound [O--].[O--].[Al+3].[Zr+4] VCRLKNZXFXIDSC-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000009615 deamination Effects 0.000 description 1
- 238000006481 deamination reaction Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000002737 fuel gas Substances 0.000 description 1
- 239000008246 gaseous mixture Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 239000003949 liquefied natural gas Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical group O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 230000005070 ripening Effects 0.000 description 1
- 230000011218 segmentation Effects 0.000 description 1
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Abstract
The invention relates to a comprehensive utilization synthesis process of natural gas employing methanation of coke oven gas, belonging to the technical field of new energy utilization. The process comprises the following steps: compressing coke oven gas, preliminary cleaning, removing sulfur, performing first section methanation, performing second section methanation and separating natural gas to prepare natural gas which reaches the grade A technological requirements of natural gas national standard (GB17820-1999). The synthesis process of natural gas employing methanation of coke oven gas reaches the aim of high effective comprehensive utilization of natural gas and provides a new way of preparing and synthesizing natural gas.
Description
Technical field
The present invention relates to a kind of technology of gas employing methanation of coke oven synthetic natural gas comprehensive utilization, belong to the new energy use technology field.
Background technology
Sweet natural gas is a kind of energy of clean and effective, and China's energy development Eleventh Five-Year Plan proposes, and the ratio that Sweet natural gas accounts for the primary energy source total quantity consumed will improve 2.5 percentage points in 5 years, reached 5.3% by 2010.
In recent years, though the increase of China's natural gas produced quantity is very fast, and has built a large amount of gas distributing systems and Infrastructure, the increase of Natural Gas Demand amount is faster, estimates that need in 2010 are from about 21,000,000,000 m of external import
3Along with Natural Gas Demand continues to increase, the technology of various synthesis of artificial Sweet natural gases is emerged in large numbers one after another, like coal preparing natural gas (SNG) etc., but considers that from aspects such as economy, suitabilities the coke-oven gas synthetic natural gas has the market competitiveness.
Coke-oven gas (COG) is the by product in the coal destructive distillation process of coking, for containing a small amount of CO, CO
2Rich H
2Gas, its composition is generally (referring to table 1):
Table 1
| Composition | H 2 | CH 4 | CO | CO 2 | CmHn | N 2 | O 2 |
| Form vol.% | 50～60 | 20～30 | 5～9 | 2～5 | 2～4 | 3～6 | 0.3～0.8 |
Simultaneously, also contain impurity such as a large amount of sulfide, tar, benzene, naphthalene, ammonia in the coke-oven gas.
China produces about 60,000,000,000 Nm of coke-oven gas per year
3(statistic data in 2008), a part are used to generating, and a part is used for making methyl alcohol, hydrogen manufacturing and life combustion gas, also has quite a few to be used as factory's combustion gas, and remote districts are then emitted in vain.The capacity usage ratio of coke-oven gas present stage is about about 55%; And according to its composition " the many carbon of hydrogen bes's few " characteristics; Utilize gas employing methanation of coke oven synthesis of artificial Sweet natural gas and by-product hydrogen will have very strong technology and economic competitiveness, can reach the purpose that improves the coke(oven)gas capacity usage ratio.
The technological core of coke-oven gas synthetic natural gas is a methanation technology, compares the ripening degree of coke oven gas purification and later separation technology, and the coke-oven gas methanation technology is still in industrialized developing.Do not see the industriallization report at present both at home and abroad as yet.
Patent CN1919985A discloses a kind of method of utilizing coke(oven)gas to prepare synthetic natural gas; After earlier coke(oven)gas being removed benzene, naphthalene, heavy hydrocarbon polymer, sulfide through purification, compression, heat exchange; Again under catalyst action; Carry out methanation reaction, make hydrogen and carbon monoxide and carbon dioxide reaction generation methane among the COG, obtaining with methane is main gas mixture; Then this gas mixture is got into pressure-swing absorption apparatus,, obtain the product gas of methane concentration more than 90%, i.e. synthetic natural gas through the transformation adsorption separation technology.
Patent CN101391935A discloses a kind of method of utilizing the coke(oven)gas synthesizing methane; Remove impurity, compression heat exchange and add key steps such as water vapour, one section methanation reaction, two sections methanation reactions, three sections methanation reactions, PSA separation of methane through purification, obtain the product gas of methane concentration more than 90%.Adopt the inventive method, utilize coke(oven)gas to be raw material, can obtain methane content height, foreign matter content is low, calorific value is high synthetic natural gas, and help protecting environment, save the energy, tap a new source of energy; In addition; In this method, through in raw coke oven gas, adding the suitable quantity of water steam before one section reaction, appropriate inhibition the degree of depth of methanation reaction; Thereby reduced the entire reaction course liberated heat; Help reacting the cooling of back gas, and prevent to analyse the charcoal reaction and cause catalyst deactivation, help normally moving continuously of whole synthesis technique.
More than two patents emphasis in technology mentioned methanation process and catalyzer, but these catalyzer do not pass through the test of industrial Demonstration Application, its technology is somewhat complicated also.
It is the method for raw material production natural gas liquids with the coke-oven gas that patent CN101280235A discloses a kind of; This method is that the method for raw material production natural gas liquids is at first through pre-treatment with coke-oven gas with the coke-oven gas; Make impurity such as its contained tar, naphthalene, benzene obtain deep purifying; After compression and desulfurization, carry out methanation reaction again, obtain containing CH through the low temperature separation process process again
4Liquefied natural gas product more than 85%, it is the hydrogen more than 99% that all the other noncondensable gases obtain purity through the PSA stripping technique, remaining stripping gas can be used as the manufactured gas, manufactured fuel gas.
Patent CN101100622A discloses a kind of method of utilizing the hydrogen resource production synthetic natural gas of coke(oven)gas, and its process step is following: a. coke(oven)gas is compressed to 0.5-5.0MPa after routine purifies detar, thick desulfurization, deamination, takes off benzene and take off naphthalene; B. again through fine desulfurizing technology, remove the impurity such as sulfide in the coke(oven)gas; C. the coke(oven)gas after smart desulfurization being handled is mended carbon, and mending the carbon amount is the 5-20% of coke(oven)gas volume; D. under catalyst action, carry out methanation reaction, obtaining with methane is main gaseous mixture.The invention still further relates to a kind of device of realizing utilizing coke(oven)gas production synthetic natural gas in addition.Characteristics in this patent are methods of proposing " benefit carbon " making full use of the excess hydrogen in the coke-oven gas, but the carbon source of seeking economic worth is the key of technology.
Above-mentioned technology all is based on the technical exploitation of multistage methanation (methanation more than three sections and three sections), because multistage methanation reaction equipment input amount is big, energy consumption is high, causes the cost of synthetic natural gas to increase.
Summary of the invention
The purpose of this invention is to provide the method that a kind of coke-oven gas prepares Sweet natural gas.Utilize this process method can coke-oven gas be processed the Sweet natural gas that meets the GB technical specification, and can recovery part concentration be 90%～100% hydrogen, the efficient recovery energy reaches the purpose that improves capacity usage ratio simultaneously.
The present invention realizes through following technical scheme:
A kind of method of gas employing methanation of coke oven synthetic natural gas comprises that preliminary cleaning, desulfurization, one section methanation reaction, two sections methanation reactions, Sweet natural gases separate, and step is following, is volume percent:
(1) preliminary cleaning:
Coke-oven gas is compressed to the reaction pressure of 0.3～0.8MPa, handles removing ammonia, prussiate, aromatic hydrocarbons, tar and the dust in the coke(oven)gas then through absorption method, absorption process or coagulation, slightly purify coke(oven)gas.
(2) desulfurization:
The thick purification coke(oven)gas that step (1) is made adopts medium temperature hydrolyzation or hydroconversion process to handle organosulfur in the coke-oven gas such as COS, CS
2Deng changing into inorganic sulfur H at a certain temperature
2S adopts wet desulphurization or dry desulfurization inorganic sulfur to be removed to≤10mg/Nm again
3, adopt fine desulfurization process by dry that the total sulfur in the coke-oven gas is removed to≤0.1mg/Nm at last
3, get pure coke-oven gas;
(3) one sections methanation reactions:
The pure coke-oven gas that step (2) is made mixes pure coke-oven gas and water vapour volume ratio 1: (0.1～0.4) through preheating after reaching 200～300 ℃ with water vapour; Getting into one section adiabatic reactor of methanation, is the katalysis reaction down of methanation catalyst at Ni, reaction pressure 0.3～0.8MPa, and 450～600 ℃ of reaction back temperature outs get the initial action coke-oven gas.This step can make 60～90% CO and 20～60% CO
2Change into CH
4
(4) two sections methanation reactions:
The initial action coke-oven gas that step (3) is made is cooled to 200～300 ℃, reclaims heat, gets into the methanation second stage reactor; At Ni reaction under the katalysis of methanation catalyst, reaction pressure 0.3～0.8MPa, 350～600 ℃ of reaction back temperature outs; Through overcooling, get rough Sweet natural gas.This step can make in one section methanation reaction, remaining CO and CO
2Change into CH
4, two sections methanator exit gass can obtain containing methane 50～70%, the mixed gas of hydrogen 20～40% after overcooling.
(5) Sweet natural gas separates
The rough Sweet natural gas that step (4) is made adsorbs or membrane sepn through transformation, obtains rich water Sweet natural gas and hydrogen-rich gas respectively, and rich water Sweet natural gas through transformation absorption or alternating temperature adsorption dewatering, is promptly got Sweet natural gas.Rich water Sweet natural gas contains CH
4More than 90%, hydrogen-rich gas contains H
2More than 90%.
Said reaction pressure is 0.3～0.6MPa.
Water vapour in the said step (3) reclaims the water vapour that heat recirculated water produces when utilizing the cooling of step (4) initial action coke-oven gas for coming from.
Ni described in step (3) and the step (4) is that methanation catalyst is a prior art, and this catalyzer is host with Ni, and carrier is aluminum oxide or aluminium oxide-zirconium oxide.As can adopt the M-849 methanation catalyst of Dalian Pratt Chemical Technology Co., Ltd's production and sales.
The ammonia content of above-mentioned thick purification coke(oven)gas is less than or equal to 200mg/Nm
3, aromaticity content is less than or equal to 30mg/Nm
3, tar content is less than or equal to 0.5mg/Nm
3, dust content is less than or equal to 0.5mg/Nm
3
Above-mentioned pure coke-oven gas sulphur content is less than or equal to 0.1mg/Nm
3Coke-oven gas after the preliminary cleaning is adopted medium temperature hydrolyzation or hydrocracking earlier, with organosulfur in the coke-oven gas such as COS, CS
2Deng changing into H at a certain temperature
2S, its Transformation efficiency is up to 90～98%.And then adopt wet method or dry desulfurizing process, inorganic sulfur is removed to≤10mg/Nm
3Adopt fine desulfurization process by dry that the total sulfur in the coke-oven gas is removed to≤0.1mg/Nm at last
3
Absorption method in the above-mentioned preliminary cleaning, absorption process or coagulation, the medium temperature hydrolyzation method in the desulfurization, hydroconversion process, wet desulphurization, dry desulfurization and fine desulfurization process by dry are handled and are this area common technology.Transformation absorption during Sweet natural gas separates, alternating temperature absorption or membrane separation process also all are prior aries.
Add self-produced water vapor in the methanation reaction process in the raw coke oven gas, help controlling CO, CO
2The methanation reaction transformation efficiency, thus reach control reaction temperature and heat exhaust, effectively suppress the generation of knot charcoal reaction and the purpose of protection methanation catalyst.
Advantage of the present invention:
1. coke-oven gas combination purification technique, methanation, CH among the present invention
4Separating technology all carries out under lower pressure, and technological design is reasonable, and energy consumption is low;
2. methanation process adopts two sections adiabatic reactors among the present invention, and is low voltage operated, need not to adopt gas segmentation circulation technology, and technical process is simple and reliable, the easy to operate stable control that is prone to, and energy consumption is low;
3. the present invention meets GB by coke-oven gas synthetic Sweet natural gas, can directly be incorporated into the power networks or produces compressed natural gas, natural gas liquids; The hydrogen of by-product, high-quality steam and refrigerating duty can directly supply chemical enterprise to use, thereby the capacity usage ratio of coke(oven)gas is brought up to high levels.
Description of drawings
Fig. 1 is a process flow sheet of the present invention.
Embodiment
Below in conjunction with embodiment the present invention is made further detailed description.But should this be interpreted as that the scope of the above-mentioned theme of the present invention only limits to following embodiment.
Technology among the embodiment and condition all can adopt this area routine techniques if no special instructions, and the reagent of mentioning in the reaction all can adopt common agents if no special instructions, and per-cent is volume percent.
Embodiment 1
The method of gas employing methanation of coke oven synthetic natural gas as shown in Figure 1, coke-oven gas 50000Nm
3/ h is compressed to the reaction pressure of 0.3～0.49MPa through spiral-lobe compressor, handles removing ammonia then through absorption process, and aromatic hydrocarbons, tar and dust get into medium temperature hydrolyzation again, are H with tempreture organic sulphur hydrolysis
2S adopts wet desulphurization then, removes micro-H with fine desulfurization process by dry process at last
2S gets pure coke-oven gas.This moment, pure coke-oven gas consisted of H
2: 54.4%, CH
4: 28.2%, CO:6.3%, CO
2: 4.0%, N
2: 3.1%, C
mH
n: 2.1%, total sulfur≤0.1mg/Nm
3, tar≤0.5mg/Nm
3, aromatic hydrocarbons≤30mg/Nm
3
Pure coke-oven gas is after being preheating to 300 ℃; Add water vapor, the water vapor add-on is 20% of a pure coke-oven gas, mixes the back and gets into one section methanator; Reaction pressure 0.3～0.49MPa; Under the methanation catalyst effect that Dalian Pratt Chemical Technology Co., Ltd produces, the transformation efficiency of CO methanation is 80%, CO
2The transformation efficiency of methanation is 30%, and 550 ℃ of temperature outs get the initial action coke-oven gas.
The initial action coke-oven gas, waste heat boiler is got into two sections methanators after reclaiming heat, reaction pressure 0.3～0.49MPa, and under the methanation catalyst effect that Dalian Pratt Chemical Technology Co., Ltd produces, the transformation efficiency of CO methanation is 100%, CO
2The transformation efficiency of methanation is 90%, 400 ℃ of temperature outs, be cooled to normal temperature after, rough Sweet natural gas.Rough Sweet natural gas is formed H
2: 18.8%, CH
4: 44.3%, CO:0%, CO
2: 0.18%, N
2: 3.2%, H
2O:33.4%.
Rough Sweet natural gas is dewatered, adopt pressure swing adsorption/separation of methane and hydrogen then, obtain 23000Nm
3Sweet natural gas (the CH of/h
4>=90%) and 10000Nm
3Rich hydrogen (the H of/h
2>=90%) gas.
Behind above-mentioned Sweet natural gas employing transformation adsorption dewatering, water dew point is lower 5 ℃ than envrionment temperature in the Sweet natural gas, satisfies the technical specification (a type) of Sweet natural gas GB (GB17820-1999).
Embodiment 2
The method of gas employing methanation of coke oven synthetic natural gas as shown in Figure 1, coke-oven gas 20000Nm
3/ h is compressed to the reaction pressure of 0.5～0.8MPa through reciprocating compressor, handles removing ammonia then through absorption method, and aromatic hydrocarbons, tar and dust get into medium temperature hydrolyzation again, are H with tempreture organic sulphur hydrolysis
2S adopts wet desulphurization then, removes micro-H with fine desulfurization process by dry process at last
2S gets pure coke-oven gas.This moment, pure coke-oven gas consisted of H
2: 56.5%, CH
4: 25.0%, CO:5.9%, CO
2: 2.8%, N
2: 5.0%, C
mH
n: 3.0%, total sulfur≤0.1mg/Nm
3, tar≤0.5mg/Nm
3, aromatic hydrocarbons≤30mg/Nm
3
Pure coke-oven gas is after being preheating to 250 ℃; Add water vapor, the water vapor add-on is 30% of a pure coke-oven gas, gets into one section methanator; Reaction pressure 0.5～0.8MPa; Under the methanation catalyst effect that Dalian Pratt Chemical Technology Co., Ltd produces, the transformation efficiency of CO methanation is 65%, CO
2The transformation efficiency of methanation is 21%, and 490 ℃ of temperature outs get the initial action coke-oven gas.
The initial action coke-oven gas gets into two sections methanators after waste heat boiler reclaims heat, reaction pressure 0.5～0.8MPa, and under the methanation catalyst effect that Dalian Pratt Chemical Technology Co., Ltd produces, the transformation efficiency of CO methanation is 100%, CO
2The transformation efficiency of methanation is 90%, 480 ℃ of temperature outs, be cooled to normal temperature after, rough Sweet natural gas.Rough Sweet natural gas is formed H
2: 15.7%, CH
4: 40.2%, CO:0%, CO
2: 0.11%, N
2: 4.1%, H
2O:39.9%.
Rough Sweet natural gas is dewatered, adopt pressure swing adsorption/separation of methane and hydrogen then, obtain 6500Nm
3Sweet natural gas (the CH of/h
4>=90%) and 5000Nm
3Hydrogen-rich gas (the H of/h
2>=90%).
Behind above-mentioned dirt gas employing alternating temperature adsorption dewatering, water dew point is lower 5 ℃ than envrionment temperature in the Sweet natural gas, satisfies the technical specification (a type) of Sweet natural gas GB (GB17820-1999).
Claims (4)
1. the method for a gas employing methanation of coke oven synthetic natural gas comprises that preliminary cleaning, desulfurization, one section methanation reaction, two sections methanation reactions, Sweet natural gases separate, and step is following, is volume percent:
(1) preliminary cleaning:
Coke-oven gas is compressed to the reaction pressure of 0.3～0.8MPa, handles removing ammonia, prussiate, aromatic hydrocarbons, tar and the dust in the coke(oven)gas then through absorption method, absorption process or coagulation, slightly purify coke(oven)gas;
(2) desulfurization:
The thick purification coke(oven)gas that step (1) is made adopts medium temperature hydrolyzation or hydroconversion process to handle the organosulfur COS in the coke-oven gas, CS
2Change into inorganic sulfur H at a certain temperature
2S adopts wet desulphurization or dry desulfurization inorganic sulfur to be removed to≤10mg/Nm again
3, adopt fine desulfurization process by dry that the total sulfur in the coke-oven gas is removed to≤0.1mg/Nm at last
3, get pure coke-oven gas;
(3) one sections methanation reactions:
The pure coke-oven gas that step (2) is made mixes pure coke-oven gas and water vapour volume ratio 1: (0.1～0.4) through preheating after reaching 200～300 ℃ with water vapour; Getting into one section adiabatic reactor of methanation, is the katalysis reaction down of methanation catalyst at Ni, reaction pressure 0.3～0.8MPa, and 450～600 ℃ of reaction back temperature outs get the initial action coke-oven gas;
(4) two sections methanation reactions:
The initial action coke-oven gas that step (3) is made is cooled to 200～300 ℃, reclaims heat, gets into the methanation second stage reactor; At Ni reaction under the katalysis of methanation catalyst, reaction pressure 0.3～0.8MPa, 350～600 ℃ of reaction back temperature outs; Through overcooling, get rough Sweet natural gas;
(5) Sweet natural gas separates:
The rough Sweet natural gas that step (4) makes is handled with pressure swing adsorption technique or membrane separation process, got rich water Sweet natural gas and hydrogen-rich gas, rich water Sweet natural gas through transformation absorption or alternating temperature adsorption dewatering, is promptly got Sweet natural gas.
2. the method for gas employing methanation of coke oven synthetic natural gas as claimed in claim 1 is characterized in that, said reaction pressure is 0.3～0.6MPa.
3. the method for gas employing methanation of coke oven synthetic natural gas as claimed in claim 1 is characterized in that, the water vapour in the said step (3) reclaims the water vapour that heat recirculated water produces when utilizing the cooling of step (4) initial action coke-oven gas for coming from.
4. the method for gas employing methanation of coke oven synthetic natural gas as claimed in claim 1 is characterized in that, the ammonia content of the thick purification coke(oven)gas that step (1) makes is less than or equal to 200mg/Nm
3, aromaticity content is less than or equal to 30mg/Nm
3, tar content is less than or equal to 0.5mg/Nm
3, dust content is less than or equal to 0.5mg/Nm
3
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| CN108011119B (en) * | 2017-12-18 | 2020-12-01 | 陕西省石油化工研究设计院 | Method and system for clean power generation and resource utilization of hydrogen-containing waste gas coupled fuel cell |
| CN113845089B (en) * | 2021-08-13 | 2024-03-12 | 中国石油大学(北京) | Method for producing synthesis gas for reduced iron by using coke oven gas |
| CN114060899A (en) * | 2021-11-29 | 2022-02-18 | 北京华能长江环保科技研究院有限公司 | Distributed energy utilization system for heating and power generation |
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| CN101508922A (en) * | 2009-03-16 | 2009-08-19 | 西南化工研究设计院 | Methanation reaction process using oven gas to prepare substitute natural gas |
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