CN105001928A - Method for preparing synthetic oil from synthesis gas through methanol preparation - Google Patents
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Abstract
According to a method for preparing synthetic oil from synthesis gas through methanol preparation, coke oven gas and coal-based synthesis gas are fully mixed to form a gas mixture; a part of the gas mixture undergoes the sulfur-tolerant shift process; the gas mixture which has undergone the sulfur-tolerant shift process and the rest of the gas mixture are compressed and then the compressed gas mixture is purified to remove impurities such as H2S, etc.; the removed hydrogen sulfide is desulfurized to be recovered; the purified crude feed gas undergoes methane separation to prepare purified feed gas; a liquefied natural gas product is prepared from the separated methane; the purified feed gas undergoes methanol synthesis to prepare methanol; after methanol is separated, synthesis of synthetic oil is carried out; purge gas obtained after methanol separation undergoes pressure swing adsorption for separation; the separated CO and H2 return to the purification process; and the separated CO2 and liquefied ammonia undergo urea synthesis to prepare urea. The method provided by the invention has advantages as follows: products are diversified; excess production capacity is adjusted; energy conservation and emission reduction are promoted; energy structure is adjusted; utilization rate of feed gas is raised; and production cost of synthetic oil is reduced.
Description
Technical field
The invention belongs to a kind of method of synthesis gas through methanol synthetic oil.
Technical background
The feature of China's energy structure is " rich coal, oil-poor, weak breath ", coal will occupy the principal status of public economy of China's energy structure for a long time, and the dependence on foreign countries for oil of China is more than 60%, particularly processed oil increase in demand, be badly in need of development substitute energy source for petroleum, therefore, the important selection that synthesis gas through methanol synthetic oil has become national energy strategy is undoubtedly developed.
Coal liquifaction technique mainly contains coal direct liquefaction technique and indirect liquefaction technique.Coal direct liquefaction technique mainly contains German IGOR company, the Direct liquefaction technology that the two-stage catalytic liquefaction process of hydrocarbon polymer research (HTI) company of the U.S. and the coalification of China Coal Research Institute Beijing are developed, but coal direct liquefaction severe reaction conditions, temperature of reaction more than 450 DEG C, reaction pressure is at about 70MP, and yield is low, product is complicated, separation difficulty.Indirect coal liquefaction technique.The indirect liquefaction technology of coal first coal is all gasificated into synthetic gas, then with coal based synthetic gas (carbon monoxide and hydrogen) for raw material, under certain temperature and pressure, catalyzed and synthesized the technique for hydrocarbon fuel oil and industrial chemicals and product, this can synthetic gasoline, alkene, aromatic hydrocarbons etc. by synthesis gas through methanol synthetic oil, and obtained synthetic oil shock resistance is good, impurity component is few, has good prospects for commercial application.China carries out iron-based, the large class catalyzer Fisher-Tropsch synthesis fuels indirect coal liquefaction technology research of cobalt-based two and engineering development from the eighties in 20th century, completes the coal-based synthetic oil industrial experiment of 2000 tons/year of scales, obtains good experiment effect.
China's synthetic gas aboundresources can be the coke-oven gas of coking industry by-product, can also be coal, particularly the synthetic gas that obtains of low grade coal upgrading vaporizing system, and all containing abundant hydrocarbon resource, is the desirable feedstock of synthetic oil processed.But, due to the feature of coke-oven gas composition " the many carbon of hydrogen is few ", be used alone coke-oven gas inhibition and generation chemical product and must occur that a large amount of hydrogen remains, or need other supplementary carbon source, the capacity usage ratio of coke-oven gas present stage is caused to be about about 55%, cause huge energy dissipation and environmental pollution, and coal based synthetic gas exists the few feature of the many hydrogen of carbon, carrying out Chemicals synthesis needs supplementary a large amount of hydrogen.Visible, produce synthetic oil separately by coke-oven gas or coal based synthetic gas, all there is component and utilize insufficient problem.If coke-oven gas and coal based synthetic gas are mixed in proportion, can reached and learn from other's strong points to offset one's weaknesses, (H:Cmoleratio is H to form the hydrogen-carbon ratio condition meeting synthesis gas through methanol synthetic oil
2/ CO=0.8-3.0,), coke-oven gas and synthetic gas " it uses gas to the greatest extent " will be realized, also the methane separation be rich in can be made LNG (natural gas liquids) or CNG (compressed natural gas), the carbonic acid gas of affluence and liquefied ammonia are reacted obtained urea, turn waste into wealth, also will reduce greenhouse gas emission, produce obvious economic benefit and environmental benefit, also significant to Energy restructuring.
Patent CN201410079811.5 discloses a kind of technique of synthetic gas gasoline, and this technique first synthetic gas is made dme in paste state bed reactor, and then synthetic gasoline in fixed bed,
Patent CN200710061506.3 discloses a kind of technique of synthetic gas synthetic gasoline coproduction aromatic hydrocarbons, and this invention loads in paste state bed reactor by methanol-fueled CLC and methanol dehydration catalyst mixing, and synthetic oil ZSM-5 catalyzer loads fixed-bed reactor
Summary of the invention
The object of this invention is to provide a kind of product diversification, regulate superfluous production capacity, promote energy-saving and emission-reduction, readjust the energy structure, improve the utilization ratio of unstripped gas, reduce synthetic oil production cost by coke-oven gas and the coal based synthetic gas method through Methanol synthetic oil.
It is few that the present invention makes full use of the many carbon of coke-oven gas composition hydrogen, and the few feature of the many hydrogen of coal based synthetic gas carbon, both are had complementary advantages, mixing by a certain percentage reaches the hydrogen-carbon ratio meeting synthetic oil processed, coke-oven gas production synthetic oil is adopted separately to need to mend carbon or adopt separately coal based synthetic gas synthetic oil to need to mend the shortcoming of hydrogen to overcome, energy by-product LNG (natural gas liquids) or CNG (compressed natural gas) simultaneously, the carbon dioxide of affluence and liquefied ammonia can also be reacted obtained urea synthesis, to improve unstripped gas utilization ratio.
Adopt synthetic oil production method of the present invention, useful component in unstripped gas can be made full use of, for the Appropriate application of coke-oven gas and coal based synthetic gas provides a kind of effective way, be conducive to product diversification, regulate superfluous production capacity, promote energy-saving and emission-reduction, readjust the energy structure, improve the utilization ratio of unstripped gas, reduce synthetic oil production cost, significantly improve Business Economic Benefit and social environment benefit.
For achieving the above object, the present invention adopts following scheme:
(1) coke-oven gas and coal based synthetic gas are passed into gas holder and be thoroughly mixed to form gas mixture, a part gas mixture compress together with remaining gas mixture through sulfur-resisting transformation, formed meet through Methanol synthetic oil hydrogen-carbon ratio be 0.8-3.0 require coarse raw materials gas;
(2) coarse raw materials gas enters purification after compression, removes H
2the impurity such as S, the hydrogen sulfide desulfuration removed reclaims, coarse raw materials gas after purification enters methane separation and obtains clean unstripped gas, isolated methane makes liquefied natural gas product, clean unstripped gas carries out methanol-fueled CLC and obtains methyl alcohol, methyl alcohol carries out synthetic oil synthesis after being separated, and the periodic off-gases that separating methanol obtains is separated through PSA (pressure-variable adsorption), isolated CO, H
2turn back to purification, isolated CO
2carry out urea synthesis with liquefied ammonia and obtain urea.
The mol ratio of coke-oven gas as above and coal based synthetic gas is between 0.05-5.0:1.
The volume percent that gas mixture as above carries out sulfur-resisting transformation accounts for the 5-95% of total gas mixture.
The catalyzer of resistant to sulfur water-gas shift as above adopts Qingdao connection letter QDB series catalysts, B302Q, B303Q model catalyzer that Hubei chemistry institute is produced, the one of the K8-11 model catalyzer that ICI company of Britain produces or QCS-01, QCS-02, QCS-04 catalyzer that Qilu Petrochemical research institute produces, operational condition is pressure 1.0-8.0MPa, temperature 200-700 DEG C, air speed is 2000-7000h
-1.
The source of coke-oven gas as above can be tamping coke furnace, top dress coke oven, dichotomic type coke oven or twin coke oven.
The source of coal based synthetic gas as above can be the vapourizing furnaces such as crushed coal pressurized-gasification furnace, Lurgi gasifier, ash agglomerating stove, texaco coal-water slurry gasification stove, multi-nozzle coal slurry gasifier or space flight stove.
Raw material gas purifying as above can be tannin process, ADA method, thermokalite method, NHD method, low-temperature rectisol method or complex iron etc.
Raw material gas purifying as above preferentially adopts low-temperature rectisol technology, and service temperature is-35 ~-55 DEG C, and working pressure is 2.0-6MPa, H in the coarse raw materials gas after low-temperature rectisol
2s<0.1ppm.
Due to the coarse raw materials gas complicated component that synthetic gas and coke-oven gas form.Its gaseous fraction comprises CO, H
2, CO
2, CH
4the H of denier
2s, organosulfur, tar, lipid acid, petroleum naphtha etc.Except CO, H in these components
2active principle, all the other all components comprise CO
2all need the detrimental impurity that removes with sulfide, the arduousness of its purification task as seen.Make a general survey of current various gas purifying technique, this person with heavy responsibilities's non-cryogenic methanol wash column can be taken on and do not belong to.This is because only have low-temperature rectisol to purify just all can remove various objectionable constituent neatly, such as CO in same device
2, H
2s, COS, C
4h
4s, HCN, NH
3, H
2o, C
2above hydro carbons (comprising light oil, aromatic hydrocarbon, petroleum naphtha, alkene and colloid etc.) and other carbonyl compound etc., and other any purification process all cannot be accomplished.In addition, low-temp methanol washing process also has following various significant advantage compared with other purification process:
1. receptivity is strong, and solution circulated amount is little
2. methanol solvate is cheap and easy to get, and regeneration energy consumption is low
3. gas purification degree is high
4. solvent thermal stability and chemical stability good, solvent is not degraded, non-foaming, does not corrode equipment
5. first alcohol and water can dissolve each other by arbitrary proportion, utilizes this characteristic can with its dried feed gas
Low-temperature rectisol achieves removing of plurality of impurities in the same apparatus, and for the multiple purification process combination of other purifying methods, operation is relatively single, reasonable, and convenient operation manages.
Methane separation as above can adopt supercritical gas extraction isolation technique or adopt the cold separation technology of the U.S. safe this and the neat company of Bock Lightware, separation temperature-150 DEG C to-170 DEG C, preferably-155 DEG C to-165 DEG C, separating pressure 3-8Mpa, preferred 4.0-5.5Mpa.
Methanol-fueled CLC as above can adopt fixed bed, slurry bed system, trickle bed or fluidized-bed reactor.
Methanol synthesis catalyst as above can adopt C301 type, C207-1 type, the NC501 type high-pressure synthesis catalyst for methanol of Research Institute of Nanjing Chemical Industry Group, or adopt C301-1 type, NC501-1 type, the C307 type of Research Institute of Nanjing Chemical Industry Group, or adopt the one in the XNC-98 type mesolow catalst for synthesis of methanol of sky, Sichuan one scientific & technical corporation, high-pressure type catalyst reaction pressure 15.0-30.0MPa, mesolow type catalyst reaction pressure is 2.5 ~ 15.0MPa, temperature of reaction is all 180 ~ 360 DEG C, and reaction velocity is all 4000 ~ 30000h
-1.
The sorbent material of pressure-variable adsorption as above is the one in X/Y molecular sieve, gac, Kiselgel A, activated alumina, and adsorptive pressure is 1.5-5.0MPa, and desorption pressures is 0.1-0.8MPa, and service temperature is less than 40 DEG C.
Synthetic oil as above adopts fixed-bed reactor, the ZSM-5 molecular sieve catalyzer that catalyzer is Shanxi coalification, or the ZSM-5 molecular sieve catalyzer that Exxon-Mobil Corp. produces, operational condition is: reaction pressure is 1.0-4.0MPa, temperature of reaction is 260-490 DEG C, methanol weight air speed 0.8-2.0h
-1.
Urea synthesis reaction temperature as above 160 ~ 175 DEG C, reaction pressure 14.0 ~ 24.0MPa, air speed is 3000-35000h
-1, N/C mol ratio is 2.6 ~ 3.3.
Advantage of the present invention: it is few that the present invention makes full use of the many carbon of coke-oven gas composition hydrogen, and synthesize the few feature of the many hydrogen of gas carbon, by both in conjunction with mutual supplement with each other's advantages, mixing by a certain percentage reaches by the suitable hydrogen-carbon ratio of synthesis gas through methanol synthetic oil, methane separation in unstripped gas is made compressed natural gas or natural gas liquids simultaneously, carbon dioxide in unstripped gas and liquefied ammonia are reacted obtained urea synthesis, improve the utilization ratio of unstripped gas, reduce synthetic oil production cost, be conducive to product diversification, regulate superfluous production capacity, promote energy-saving and emission-reduction, readjust the energy structure, significantly improve Business Economic Benefit and social environment benefit.
Embodiment
Below in conjunction with specific embodiment, the present invention is described in detail, and these embodiments are only for specifically describing the present invention more in detail, and the scope that should not be construed as the above-mentioned theme of the present invention is only limitted to the restriction of following embodiment.
Embodiment 1
(volume percent consists of H to the coke-oven gas produced by tamping coke furnace
2: 55%, CH
4: 24%, CO+CO
2: 16%, N
2: 5%) and lurgi gasifier produce coal based synthetic gas (volume percent consists of CO:53%, H
2: 24%, CO
2: 10%, CH
4: 13%, H
2s:0.21%) 1.5:1 passes into gas holder and is thoroughly mixed to form gas mixture by volume, and 15% gas of gas mixture volume enters the sulfur-resisting transformation that Qingdao connection letter QDB series catalysts is housed, and at pressure 3.0MPa, temperature 360 DEG C, air speed is 2800h
-1carry out sulfur-resisting transformation under condition, conversion gas is entered compression together with remaining gas mixture, form (the H:Cmoleratio H meeting and require through Methanol synthetic oil hydrogen-carbon ratio
2/ C=2.01) coarse raw materials gas;
Coarse raw materials gas enters low-temperature rectisol purification after compression, temperature-49 DEG C, removes H under pressure 3.5MPa condition
2the impurity such as S, obtain H
2s content is less than the unstripped gas of 0.1ppm, the hydrogen sulfide desulfuration removed reclaims, coarse raw materials gas after purification enters methane low temperature separation process, temperature-161 DEG C, pressure 3.5MPa isolates methane and makes LNG (natural gas liquids) product, and the clean unstripped gas isolating methane enters methanol synthesis in slurry reactor, adopt the C301 type high-pressure synthesis catalyst for methanol of Research Institute of Nanjing Chemical Industry Group, at pressure 20.0MPa, temperature 280 DEG C, air speed 9000h
-1obtained methyl alcohol under condition; Obtained methyl alcohol enters the catalyst fixed bed synthetic oil reactor of ZSM-5 molecular sieve Exxon-Mobil Corp. being housed and producing, at pressure 4.0MPa, and temperature 290 DEG C, methanol weight air speed 1.2h
-1obtained synthetic oil under operational condition; Periodic off-gases after methanol-fueled CLC is through being sorbent material with gac, and adsorptive pressure is 4.5MPa, and desorption pressures is that 0.3MPa PSA (pressure-variable adsorption) is separated, isolated CO, H
2turn back to purification, isolated CO
2enter urea synthesis with liquefied ammonia, temperature of reaction 168 DEG C, reaction pressure 15.0MPa, air speed is 6500h
-1, N/C mol ratio is obtained urea under 3.0 conditions.Embodiment 2
(volume percent consists of H to the coke-oven gas produced by dichotomic type coke oven
2: 62%, CH
4: 23%, CO+CO
2: 11%, N
2: 4%) and space flight stove produce coal based synthetic gas (volume percent consists of CO:59%, H
2: 21%, CO
2: 11%, CH
4: 9%, H
2s:0.23%) 0.1:1 passes into gas holder and is thoroughly mixed to form gas mixture by volume, and the gas of gas mixture volume 55% enters the sulfur-resisting transformation that Britain ICI company K8-11 model catalyzer is housed, and at pressure 4.0MPa, temperature 380 DEG C, air speed is 4100h
-1carry out sulfur-resisting transformation under condition, conversion gas is entered compression together with remaining gas mixture, form (the H:Cmoleratio H meeting and require through Methanol synthetic oil hydrogen-carbon ratio
2/ C=2.21) coarse raw materials gas;
Coarse raw materials gas enters the purification of NHD method after compression, at pressure 2.7MPa, removes the impurity such as H2S, obtain H under temperature 2 DEG C of conditions
2s content is less than the unstripped gas of 0.1ppm, the hydrogen sulfide desulfuration removed reclaims, coarse raw materials gas after purification enters methane low temperature separation process, temperature-164 DEG C, pressure 4.1MPa isolates methane and makes LNG (natural gas liquids) product, and the clean unstripped gas isolating methane enters synthesizing methanol by fluidized bed, adopt base pressure catalst for synthesis of methanol in the C307 type of Research Institute of Nanjing Chemical Industry Group, at pressure 9.0MPa, temperature 300 DEG C, air speed 17000h
-1obtained methyl alcohol under condition; Obtained methyl alcohol enter be equipped with Shanxi coalification the catalyst fixed bed synthetic oil reactor of ZSM-5 molecular sieve, at pressure 1.8MPa, temperature 270 DEG C, methanol weight air speed 1.3h
-1obtained synthetic oil under operational condition; Periodic off-gases after methanol-fueled CLC is through being sorbent material with Kiselgel A, and adsorptive pressure is 4.0MPa, and desorption pressures is that 0.2MPa PSA (pressure-variable adsorption) is separated, isolated CO, H
2turn back to purification, isolated CO
2enter urea synthesis with liquefied ammonia, temperature of reaction 163 DEG C, reaction pressure 19.0MPa, air speed is 20000h
-1, N/C mol ratio is obtained urea under 3.05 conditions.
Embodiment 3
(volume percent consists of H to the coke-oven gas produced by top dress coke oven
2: 59%, CH
4: 24%, CO+CO
2: 13%, N
2: 4%) and crushed coal pressure gasifying produce coal based synthetic gas (volume percent consists of CO:55%, H
2: 21%, CO
2: 13%, CH
4: 11%, H
2s:0.22%) 3.0:1 passes into gas holder and is thoroughly mixed to form gas mixture by volume, and the gas of gas mixture volume 5% enters the sulfur-resisting transformation that the graduate QCS-04 catalyzer of Qilu Petrochemical is housed, and at pressure 3.5MPa, temperature 330 DEG C, air speed is 4500h
-1carry out sulfur-resisting transformation under condition, conversion gas is entered compression together with remaining gas mixture, form (the H:Cmoleratio H meeting and require through Methanol synthetic oil hydrogen-carbon ratio
2/ C=2.52) coarse raw materials gas;
Coarse raw materials gas enters hot alkali purification after compression, at pressure 1.5MPa, removes the impurity such as H2S, obtain H under temperature 98 DEG C of conditions
2s content is less than the unstripped gas of 0.1ppm, the hydrogen sulfide desulfuration removed reclaims, coarse raw materials gas after purification enters supercritical extraction methane separation, at pressure 4.5MPa, the supercritical state separation of methane of temperature-77.5 DEG C obtains CNG (compressed natural gas) product, and the clean unstripped gas isolating methane enters fixed bed methanol-fueled CLC, adopt the XNC-98 type mesolow catalst for synthesis of methanol of sky, Sichuan one scientific & technical corporation, at pressure 8.0MPa, temperature 240 DEG C, air speed 20000h
-1obtained methyl alcohol under condition; Obtained methyl alcohol enter be equipped with Shanxi coalification the catalyst fixed bed synthetic oil reactor of ZSM-5 molecular sieve, at pressure 1.6MPa, temperature 280 DEG C, methanol weight air speed 1.5h
-1obtained synthetic oil under operational condition; Periodic off-gases after methanol-fueled CLC is through being sorbent material with activated alumina, and adsorptive pressure is 4.8MPa, and desorption pressures is that 0.5MPa PSA (pressure-variable adsorption) is separated, isolated CO, H
2turn back to purification, isolated CO
2enter urea synthesis with liquefied ammonia, temperature of reaction 169 DEG C, reaction pressure 17.0MPa, air speed is 27000h
-1, N/C mol ratio is obtained urea under 2.95 conditions.
Embodiment 4
(volume percent consists of H to the coke-oven gas produced by tamping coke furnace
2: 56%, CH
4: 21%, CO+CO
2: 18%, N
2: 5%) and texaco coal-water slurry gasification stove produce coal based synthetic gas (volume percent consists of CO:57%, H
2: 22%, CO
2: 11%, CH
4: 10%, H
2s:0.27%) 2.0:1 passes into gas holder and is thoroughly mixed to form gas mixture by volume, the gas of gas mixture volume 55% enters and the sulfur-resisting transformation that Hubei chemistry institute produces B303Q model catalyzer is housed, at pressure 5.0MPa, temperature 450 DEG C, air speed is 6000h
-1carry out sulfur-resisting transformation under condition, conversion gas is entered compression together with remaining gas mixture, form (the H:Cmoleratio H meeting and require through Methanol synthetic oil hydrogen-carbon ratio
2/ C=2.36) coarse raw materials gas;
Coarse raw materials gas enters low-temperature rectisol purification after compression, temperature-50 DEG C, removes H under pressure 4.8MPa condition
2the impurity such as S, obtain H
2s content is less than the unstripped gas of 0.1ppm, the hydrogen sulfide desulfuration removed reclaims, coarse raw materials gas after purification enters methane low temperature separation process, temperature-163 DEG C, pressure 4.8MPa isolates methane and makes LNG (natural gas liquids) product, and the clean unstripped gas isolating methane enters trickle bed methanol-fueled CLC, adopt the NC501 type high-pressure synthesis catalyst for methanol of Research Institute of Nanjing Chemical Industry Group, at pressure 26.0MPa, temperature 290 DEG C, air speed 12000h
-1obtained methyl alcohol under condition; Obtained methyl alcohol enter be equipped with Shanxi coalification the catalyst fixed bed synthetic oil reactor of ZSM-5 molecular sieve, at pressure 1.8MPa, temperature 310 DEG C, methanol weight air speed 1.7h
-1obtained synthetic oil under operational condition; Periodic off-gases after methanol-fueled CLC is through being sorbent material with X-type molecular sieve, and adsorptive pressure is 5.0MPa, and desorption pressures is that 0.45MPa PSA (pressure-variable adsorption) is separated, isolated CO
2enter urea synthesis with liquefied ammonia, temperature of reaction 173 DEG C, reaction pressure 21.0MPa, air speed is 19000h
-1, N/C mol ratio is obtained urea under 3.15 conditions.
Claims (15)
1. a method for synthesis gas through methanol synthetic oil, is characterized in that comprising the steps:
(1) coke-oven gas and coal based synthetic gas are passed into gas holder and be thoroughly mixed to form gas mixture, a part gas mixture compress together with remaining gas mixture through sulfur-resisting transformation, formed meet through Methanol synthetic oil hydrogen-carbon ratio be 0.8-3.0 require coarse raw materials gas;
(2) coarse raw materials gas enters purification after compression, removes H
2the impurity such as S, the hydrogen sulfide desulfuration removed reclaims, coarse raw materials gas after purification enters methane separation and obtains clean unstripped gas, isolated methane makes liquefied natural gas product, clean unstripped gas carries out methanol-fueled CLC and obtains methyl alcohol, methyl alcohol carries out synthetic oil synthesis after being separated, and the periodic off-gases that separating methanol obtains is separated through pressure-variable adsorption, isolated CO, H
2turn back to purification, isolated CO
2carry out urea synthesis with liquefied ammonia and obtain urea.
2. the method for a kind of synthesis gas through methanol synthetic oil as claimed in claim 1, is characterized in that the mol ratio of described coke-oven gas and coal based synthetic gas is between 0.05-5.0:1.
3. the method for a kind of synthesis gas through methanol synthetic oil as claimed in claim 1, is characterized in that volume percent that described gas mixture carries out sulfur-resisting transformation accounts for the 5-95% of total gas mixture.
4. the method for a kind of synthesis gas through methanol synthetic oil as claimed in claim 1, it is characterized in that the catalyzer of described resistant to sulfur water-gas shift adopts Qingdao connection letter QDB series catalysts, B302Q, B303Q model catalyzer that Hubei chemistry institute is produced, the one of the K8-11 model catalyzer that ICI company of Britain produces or QCS-01, QCS-02, QCS-04 catalyzer that Qilu Petrochemical research institute produces, operational condition is pressure 1.0-8.0MPa, temperature 200-700 DEG C, air speed is 2000-7000h
-1.
5. the method for a kind of synthesis gas through methanol synthetic oil as claimed in claim 1, is characterized in that the source of described coke-oven gas is tamping coke furnace, top dress coke oven, dichotomic type coke oven or twin coke oven.
6. the method for a kind of synthesis gas through methanol synthetic oil as claimed in claim 1, is characterized in that the source of described coal based synthetic gas is crushed coal pressurized-gasification furnace, Lurgi gasifier, ash agglomerating stove, texaco coal-water slurry gasification stove, multi-nozzle coal slurry gasifier or space flight stove.
7. the method for a kind of synthesis gas through methanol synthetic oil as claimed in claim 1, is characterized in that described raw material gas purifying is tannin process, ADA method, thermokalite method, NHD method, low-temperature rectisol method or complex iron.
8. the method for a kind of synthesis gas through methanol synthetic oil as claimed in claim 7, it is characterized in that described raw material gas purifying adopts low-temperature rectisol technology, service temperature is-35 ~-55 DEG C, and working pressure is 2.0-6MPa, H in the coarse raw materials gas after low-temperature rectisol
2s<0.1ppm.
9. the method for a kind of synthesis gas through methanol synthetic oil as claimed in claim 1, it is characterized in that described methane separation adopts supercritical gas extraction isolation technique or adopts the cold separation technology of the U.S. safe this and the neat company of Bock Lightware, separation temperature-150 DEG C to-170 DEG C, separating pressure 3-8Mpa.
10. the method for a kind of synthesis gas through methanol synthetic oil as claimed in claim 9, is characterized in that described separation temperature is-155 DEG C to-165 DEG C, and separating pressure is 4.0-5.5Mpa.
The method of 11. a kind of synthesis gas through methanol synthetic oils as claimed in claim 1, is characterized in that described methanol-fueled CLC adopts fixed bed, slurry bed system, trickle bed or fluidized-bed reactor.
The method of 12. a kind of synthesis gas through methanol synthetic oils as claimed in claim 1, it is characterized in that described methanol synthesis catalyst adopts the C301 type of Research Institute of Nanjing Chemical Industry Group, C207-1 type, NC501 type high-pressure synthesis catalyst for methanol, or adopt the C301-1 type of Research Institute of Nanjing Chemical Industry Group, NC501-1 type, C307 type, or adopt the one in the XNC-98 type mesolow catalst for synthesis of methanol of sky, Sichuan one scientific & technical corporation, high-pressure type catalyst reaction pressure 15.0-30.0MPa, mesolow type catalyst reaction pressure is 2.5 ~ 15.0MPa, temperature of reaction is all 180 ~ 360 DEG C, reaction velocity is all 4000 ~ 30000h
-1.
The method of 13. a kind of synthesis gas through methanol synthetic oils as claimed in claim 1, it is characterized in that the sorbent material of described pressure-variable adsorption is the one in X/Y molecular sieve, gac, Kiselgel A, activated alumina, adsorptive pressure is 1.5-5.0MPa, desorption pressures is 0.1-0.8MPa, and service temperature is less than 40 DEG C.
The method of 14. a kind of synthesis gas through methanol synthetic oils as claimed in claim 1, it is characterized in that described synthetic oil adopts fixed-bed reactor, the ZSM-5 molecular sieve catalyzer that catalyzer is Shanxi coalification, or the ZSM-5 molecular sieve catalyzer that Exxon-Mobil Corp. produces, operational condition is: reaction pressure is 1.0-4.0MPa, temperature of reaction is 260-490 DEG C, methanol weight air speed 0.8-2.0h
-1.
The method of 15. a kind of synthesis gas through methanol synthetic oils as claimed in claim 1, it is characterized in that described urea synthesis reaction temperature 160 ~ 175 DEG C, reaction pressure 14.0 ~ 24.0MPa, air speed is 3000-35000h
-1, N/C mol ratio is 2.6 ~ 3.3.
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| CN1935765A (en) * | 2006-10-19 | 2007-03-28 | 太原理工天成科技股份有限公司 | Method for concurrently producing dimethyl ether, liquefied natural gas and urea |
| CN101434879A (en) * | 2008-12-15 | 2009-05-20 | 四川天一科技股份有限公司 | Method for preparing methyl alcohol synthesis gas and compressed natural gas from coke oven gas and coal |
| CN103232870A (en) * | 2013-04-26 | 2013-08-07 | 赛鼎工程有限公司 | Method for manufacturing natural gas by utilizing low-rank coal |
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