CN102531835B - Method for synthesizing methanol through low-carbon technology - Google Patents
Method for synthesizing methanol through low-carbon technology Download PDFInfo
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims abstract description 303
- 238000000034 method Methods 0.000 title claims abstract description 58
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 47
- 238000005516 engineering process Methods 0.000 title claims abstract description 37
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 16
- 239000007789 gas Substances 0.000 claims abstract description 192
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 94
- 239000003245 coal Substances 0.000 claims abstract description 53
- 238000006243 chemical reaction Methods 0.000 claims abstract description 48
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 44
- 238000002309 gasification Methods 0.000 claims abstract description 34
- 230000008569 process Effects 0.000 claims abstract description 32
- 238000007906 compression Methods 0.000 claims abstract description 19
- 238000004519 manufacturing process Methods 0.000 claims abstract description 18
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 17
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 15
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 35
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 28
- 239000000203 mixture Substances 0.000 claims description 23
- 238000006477 desulfuration reaction Methods 0.000 claims description 16
- 229910052739 hydrogen Inorganic materials 0.000 claims description 16
- 239000001257 hydrogen Substances 0.000 claims description 15
- 230000023556 desulfurization Effects 0.000 claims description 14
- 238000002407 reforming Methods 0.000 claims description 14
- 230000009466 transformation Effects 0.000 claims description 14
- 239000011787 zinc oxide Substances 0.000 claims description 14
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 12
- 239000006227 byproduct Substances 0.000 claims description 12
- 230000000694 effects Effects 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 12
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 10
- 235000011089 carbon dioxide Nutrition 0.000 claims description 9
- 239000003054 catalyst Substances 0.000 claims description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 8
- 238000005261 decarburization Methods 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 8
- 229910052717 sulfur Inorganic materials 0.000 claims description 8
- 239000011593 sulfur Substances 0.000 claims description 8
- 150000002431 hydrogen Chemical class 0.000 claims description 7
- JJWKPURADFRFRB-UHFFFAOYSA-N carbonyl sulfide Chemical compound O=C=S JJWKPURADFRFRB-UHFFFAOYSA-N 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 239000003250 coal slurry Substances 0.000 claims description 5
- 230000006835 compression Effects 0.000 claims description 5
- 229930195733 hydrocarbon Natural products 0.000 claims description 5
- 150000002430 hydrocarbons Chemical class 0.000 claims description 5
- 238000011084 recovery Methods 0.000 claims description 5
- 239000005864 Sulphur Substances 0.000 claims description 4
- 230000009471 action Effects 0.000 claims description 4
- 239000003546 flue gas Substances 0.000 claims description 4
- 230000005855 radiation Effects 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 4
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 3
- 239000005083 Zinc sulfide Substances 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 150000001721 carbon Chemical group 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 claims description 3
- 238000010276 construction Methods 0.000 claims 1
- 239000003345 natural gas Substances 0.000 abstract description 12
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- 229910002092 carbon dioxide Inorganic materials 0.000 abstract 1
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- 239000000571 coke Substances 0.000 abstract 1
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- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 229910052728 basic metal Inorganic materials 0.000 description 2
- 150000003818 basic metals Chemical class 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
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- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明涉及甲醇的制造工艺，特别是一种低碳技术合成甲醇的方法，其特征是：包括甲烷气转化的合成气和煤气化生产的合成气通过比例混合,经合成压缩工艺后进入甲醇反应器生产甲醇；所述的甲烷气是天然气或石油伴生气、或煤层气、或焦炉煤气、或高炉煤气或石油炼制干气等富含CH4的混合气体；所述氢碳比或H:C是合成气中的（H2-CO）/(CO+CO2)的比例，H2、CO、CO2气体组分均为百分含量；所述的煤气化生产的合成气包括粗煤气生产和氢碳比调节过程。它提供了一种生产效率高、资源利用率高、二氧化碳排放量少的低碳技术合成甲醇的方法。
The invention relates to a methanol manufacturing process, especially a method for synthesizing methanol with low-carbon technology, which is characterized in that: the synthesis gas produced by methane gas conversion and the synthesis gas produced by coal gasification are mixed in proportion, and enter the methanol reaction after the synthesis and compression process The methanol is produced by the device; the methane gas is natural gas or petroleum associated gas, or coal bed methane, or coke oven gas, or blast furnace gas or petroleum refining dry gas, etc. rich in CH 4 mixed gas; the hydrogen-to-carbon ratio or H : C is the ratio of (H 2 -CO)/(CO+CO 2 ) in the syngas, and the gas components of H 2 , CO, and CO 2 are all percentages; the syngas produced by coal gasification includes crude Gas production and hydrogen-carbon ratio adjustment process. It provides a method for synthesizing methanol with high production efficiency, high resource utilization rate and low carbon dioxide emission.
Description
Technical field
?the present invention relates to a kind of method of the manufacturing process of methyl alcohol, particularly synthesizing methanol through low-carbon technology.
Background technology
Adopt Sweet natural gas or petroleum gas to manufacture methyl alcohol and have maturation process, because Sweet natural gas or petroleum gas are manufactured methyl alcohol and can be produced a large amount of excessive hydrogen, this can affect efficiency of conversion on the one hand, Sweet natural gas or petroleum gas are manufactured methyl alcohol as raw material on the other hand, owing to being subject to Sweet natural gas or the impact of oil international price, its cost is difficult to control.For this reason, a kind of technique by Coal Chemical Industry methanol is used in a large number.Due to the coal abundant information of China, the relative Sweet natural gas of methyl alcohol cost control of producing thus or oil are relatively easy.But, the problem of Coal Chemical Industry methanol maximum to discharge exactly a large amount of carbonic acid gas, this realizes to the whole world overall situation that low-carbon (LC) is produced, particularly China will be in today of the gross domestic product Carbon emission strength degradation 40-45% of the year two thousand twenty unit of realization, the producer has to consider this problem, and the present invention is also based on object energy-conservation, that reduce discharging.
Summary of the invention
The object of this invention is to provide the method for the synthesizing methanol through low-carbon technology that a kind of production efficiency is high, resource utilization is high, CO2 emissions is few.
The object of the present invention is achieved like this, and a kind of method of synthesizing methanol through low-carbon technology, is characterized in that: comprise that the synthetic gas of methane gas conversion and the synthetic gas passing ratio that gasification is produced mix, and enter methanol reactor methanol after synthetic compression process.
Described methane gas is that Sweet natural gas or oil field gas or coal-seam gas or coke-oven gas or blast furnace gas or refining of petroleum dry gas etc. are rich in CH
4mixed gas.
Described hydrogen-carbon ratio or H: C is (H in synthetic gas
2-CO)/(CO+CO
2) ratio, H
2, CO, CO
2gaseous fraction is percentage composition.
The synthetic gas that described gasification is produced comprises raw gas production and hydrogen-carbon ratio regulate process.
Described raw gas is produced and is completed by following chemical equation:
In formula: CmHn represents coal, C represents carbon atom, H
2represent hydrogen, O
2represent oxygen, CO represents carbon monoxide, CO
2represent carbonic acid gas, H
2o represents water, and m, n represent carbon, the number of hydrogen atoms in coal, lower same;
The raw gas typical case composition that described gasification is produced is: H
2: 35%, CO:45%, CO
2: 18%, other are 2% years old.
Described hydrogen-carbon ratio regulate process is: raw gas is again by reaction CO+H
2o-→ H
2+ CO
2complete hydrogen-carbon ratio regulate, the unpurifed gas being come by gasification washing tower falls the moisture of gas entrainment through gas-liquid separator separates, then be divided into two strands, the incoming stock air preheater of unstripped gas and conversion gas heat exchange to a 305 DEG C left and right of no more than 40% enter shift converter, carry out Partial Transformation react with self-contained water vapor under sulfur-resistant transformation catalyst effect; Go out the high temperature shift gas of shift converter after feed gas heater heat exchange, enter middle pressure steam producer, by-product 2.5MPa (G) saturation steam; Middle pressure steam generator exports gas be greater than total tolerance 60% not conversion gas mix, enter the low-pressure steam of low pressure steam generator by-product 1.0MPa (G), temperature is down to after 210 DEG C, enter low pressure steam generator by-product 0.5MPa (G) low-pressure steam through gas-liquid separation gas phase, temperature is down to 180 DEG C, then enter de-salted water preheater, watercooler and be finally cooled to 40 DEG C, deliver to desulfurization and decarburization unit and remove CO
2rear output hydrogen-carbon ratio H: C=1 producing synthesis gas from coal is to synthetic compression process.
Described Partial Transformation reactant gases typical case composition is H
2: 37%, CO:40%, CO
2: 21%, other are 2% years old.
Described desulfuration of shift gas decarburization can adopt the technique such as low-temperature rectisol or NHD, removes in gas the synthetic harmful H of methyl alcohol
2s, COS and unnecessary CO
2, its classical group becomes H
2: 48%, CO:51%, CO
2: 0.20%, other 1.8%, be characterized in hydrogen-carbon ratio=0.94, much smaller than the synthetic 2.05-2.15 requiring of methyl alcohol.
The synthetic gas that described methane gas transforms refers to: methane gas is pressurizeed afterwards and the CH of hydrogen recovery unit
4(methane) gas mixes, and is preheating to approximately 360 DEG C through the heating coil of converter convection zone, enters hydrogenator, organosulfur is wherein converted into inorganic sulfur, and enters zinc oxide desulfurization groove, removes contained sulphur, reacts as follows:
COS?+?H
2?→?CO?+?H
2S
ZnO?+?H
2S?→?ZnS?+?H
2O
In formula: COS represents carbon oxysulfide, H
2s represents hydrogen sulfide, and ZnO represents zinc oxide, and ZnS represents zinc sulphide, and other are the same;
Oil field gas after desulfurization mixes by steam/hydrocarbons ratio 2-4:1 with process steam, gas mixture is preheating to after approximately 600 DEG C through the gas mixture heating coil of converter convection zone, enter the conversion tube of converter radiation section, there is conversion reaction under the high-temperature flue gas heat effect of burner hearth in unstripped gas, two principal reactions are as follows in reformer tube outside catalyzer and reformer tube:
CH
4?+?H
2O?→?CO?+?3H
2
CO?+?H
2O?→?CO
2?+?H
2
CH in formula
4represent methane, other are the same;
Gas after conversion enters reforming gas boiler through lower gas gathering manifold, for the production of high pressure steam and low-pressure steam, enter again the feedwater of boiler water preheater heating boiler, reforming gas is cooled to 40 DEG C through de-salted water preheater, reforming gas water cooler again, after separating technology phlegma, (representative gases consists of the synthetic gas of formation H: C=2.92: H
2: 73%, CO:15%, CO
2: 7%, CH
4: 4%, other are 1% years old), enter synthetic gas compression section.Be characterized in that hydrogen-carbon ratio is much larger than the synthetic 2.05-2.15 requiring of methyl alcohol.
Described synthetic compression process be by the methane preparing synthetic gas proportioning of the producing synthesis gas from coal of hydrogen-carbon ratio H: C=1 and hydrogen-carbon ratio H: C=2.92 to H: C=2.05(representative gases consists of: H
2: 67.5%, CO:27.5%, CO
2: 3.5%, CH
4: 1%, other are 0.5% years old) and be compressed to the synthetic needed pressure of methyl alcohol.
Described methyl alcohol is synthetic refers to the technology of hydrogen and carbon monoxide, carbonic acid gas methanol under catalyst action, reacts as follows:
H
2?+?CO?→?CH
3OH
H
2?+?CO
2?→CH
3OH?+?H
2O
In formula, CH
3oH represents methyl alcohol, and methyl alcohol is synthetic requires (H in virgin gas
2-CO
2)/(CO+CO
2)=2.05-2.15.
Advantage of the present invention and effect are as follows:
1, the present invention is by coal, oil field gas, three kinds of combination of resources of dry gas methanol together, realize the comprehensive utilization of hydrocarbon complementation and the energy, alleviate the burden of coal methyl alcohol shift conversion step processed, make its mode at best proportioning state response, can effectively improve methyl alcohol Synthesis conversion, reduce the energy consumption of project, significantly increased the economic benefit of project.The present invention simultaneously has also reduced waste gas, waste water, waste residue and greenhouse gases CO in a large number
2discharge, when realizing economic benefit, also ensured environmental benefit.
2, the present invention, by the distributing rationally of the plurality of raw materials such as coal, oil field gas, methane, hydrogen, has reached the object that improves resource utilization.By calculating, resource utilization is high by 6.1% compared with international most advanced level, higher by 12.68% than advanced international level, higher by 25.3% than domestic common level.Compared with advanced international level, be equivalent to save every year Sweet natural gas 19,248 ten thousand Nm
3, or save coal 28.3 ten thousand t, whole project resource utilizes scheme advanced person, rational, effect highly significant.
3, energy-saving effect of the present invention is remarkable, and wherein methanol device energy consumption is significantly less than traditional coal methanol device processed, lower by 22.8～25.9% than the energy consumption of external and advanced international level coal methanol device processed, and a year saving mark coal reaches 67.3～79.6 ten thousand t; Energy Intensity Reduction 25.9～32.7% compared with domestic common level coal methanol device processed, a year saving mark coal reaches 79.6～110.3 ten thousand t.In addition, DMTO(methanol-to-olefins), DCC(residual oil degree of depth catalytic pyrolysis), the plant energy consumption such as polyethylene also reaches International or National advanced level.
4, water-saving result of the present invention is obvious, and wherein the water consumption value of t methyl alcohol is only 4.1 t, consume than the water of Foreign Advanced Lerel coal methanol device processed low by 48.8～59%, year save water reach 702～10,620,000 t; Consume than the water of advanced international level coal methanol device processed low by 59～72.6%, year save water reach 1062～19,620,000 t; Water consumption reduces by 79.5% compared with domestic common level coal methanol device processed, and year saving water reaches 2,862 ten thousand t.
5, CO of the present invention
2reduce discharging high-volume and significantly reduce, Methanol Device CO
2quantity discharged approximately 630,000 t/a, as adopted coal production methyl alcohol CO completely
2quantity discharged will reach 4,220,000 t/a, CO
2cER reaches 85%.In addition, methanol device fuel of the present invention and power section CO
2quantity discharged is about 980,000 t/a.As adopt coal production methyl alcohol, CO
2quantity discharged is about 1,930,000 t/a, fuel and power CO
2cER reaches 49%.
6, better economic benefit of the present invention, all kinds of tax revenues of normal year will exceed 24.5 hundred million yuan, can directly solve 1600 people's the problem of employment, yearly wage total value reaches 4,800 ten thousand yuan, local all kinds of consuming cost reach more than 8,200,000,000 yuan, and can drive the development of the industries such as local building materials, there are larger contribution and promotion for the development of this area economy, property tax and society.
7, the many combination of resources development of the present invention, realize oil/gas/coal/polybasic salt raw material route and build " integrated " and " optimization " of chemical project, fully demonstrate the circular economy concept of " minimizing, recirculation, recycling ", farthest improve resource utilization and distribute rationally, effects of energy saving and emission reduction is remarkable.Domestic oil, gas, coal, the development of salt resource place of production chemical industry are had to important reference.
Brief description of the drawings
Below in conjunction with embodiment accompanying drawing, the invention will be further described:
Fig. 1 is embodiment of the present invention structural representation.
In figure: 1, the technique of Coal Chemical Industry methanol; 2, CO conversion process; 3, low-temperature rectisol unit; 4, synthetic compression process; 5, Steam Reforming Process; 6, methanol synthesizing process; 7, methyl alcohol preparation technology.
Embodiment
As shown in Figure 1, technique 1 principle of Coal Chemical Industry methanol is: the raw gas that gasification generates is CO+H by CO conversion process 2
2o-→ H
2+ CO
2transformationreation generates H
2+ CO+CO
2complete: the moisture that is fallen gas entrainment by the unpurifed gas of gasification washing tower through gas-liquid separator separates, then be divided into two strands, the incoming stock air preheater of a part and conversion gas heat exchange to a 305 DEG C left and right enter shift converter, carry out Partial Transformation react with self-contained water vapor under sulfur-resistant transformation catalyst effect; Go out the high temperature shift gas of shift converter after feed gas heater heat exchange, enter middle pressure steam producer, by-product 2.5MPa (G) saturation steam.Middle pressure steam generator exports gas mixes with conversion gas not, enter the low-pressure steam of low pressure steam generator by-product 1.0MPa (G), temperature is down to after 210 DEG C, enter low pressure steam generator by-product 0.5MPa (G) low-pressure steam through gas-liquid separation gas phase, temperature is down to 180 DEG C, then enter de-salted water preheater, watercooler and be finally cooled to 40 DEG C, deliver to low-temperature rectisol unit 3, export H by low-temperature rectisol unit 3: C=1 producing synthesis gas from coal is delivered to synthetic compression process 4.
The reforming gas hydrogen-carbon ratio that methane gas produces by Steam Reforming Process 5 is 2.92: 1, also delivers to synthetic compression process 4.
Synthetic gas through pressurization produces thick methyl alcohol through methanol synthesizing process 6 under catalyst action.
In order to obtain MTO level methyl alcohol, both can adopt the method for rectifying, also can adopt additive method.The present invention adopts MTO methyl alcohol preparation technology 7 to reduce alkalimetal ion concentration in thick methyl alcohol, saves more than 50% steam consumption than traditional rectification method.
On the whole: the present invention includes the synthetic gas of methane gas conversion and the synthetic gas passing ratio mixing that gasification is produced, after synthetic compression process, enter methanol reactor methanol.
The synthetic gas that gasification is produced comprises raw gas production and hydrogen-carbon ratio regulate process.
Described raw gas is produced and is completed by following chemical equation:
In formula: CmHn represents coal, C represents carbon atom, H
2represent hydrogen, O
2represent oxygen, CO represents carbon monoxide, CO
2represent carbonic acid gas, H
2o represents water, and m, n represent carbon, the number of hydrogen atoms in coal, lower same;
The raw gas typical case composition that gasification of coal produces is: H
2: 35%, CO:45%, CO
2: 18%, other are 2% years old.
Described hydrogen-carbon ratio regulate process is: raw gas is again by reaction CO+H
2o-→ H
2+ CO
2complete hydrogen-carbon ratio regulate, the unpurifed gas being come by gasification washing tower falls the moisture of gas entrainment through gas-liquid separator separates, then be divided into two strands, a part (no more than 40%) incoming stock air preheater and conversion gas heat exchange to a 305 DEG C left and right enter shift converter, carry out Partial Transformation react with self-contained water vapor under sulfur-resistant transformation catalyst effect; Go out the high temperature shift gas of shift converter after feed gas heater heat exchange, enter middle pressure steam producer, by-product 2.5MPa (G) saturation steam; Middle pressure steam generator exports gas mixes with conversion gas (being greater than 60%) not, enter the low-pressure steam of low pressure steam generator by-product 1.0MPa (G), temperature is down to after 210 DEG C, enter low pressure steam generator by-product 0.5MPa (G) low-pressure steam through gas-liquid separation gas phase, temperature is down to 180 DEG C, then enter de-salted water preheater, watercooler and be finally cooled to 40 DEG C, deliver to desulfurization and decarburization unit and remove CO
2rear output hydrogen-carbon ratio H:C=1 producing synthesis gas from coal is to synthetic compression process.
Partial Transformation reaction gas typical case composition after conversion is H
2: 37%, CO:40%, CO
2: 21%, other are 2% years old; And the classical group of the unstripped gas of the simple methyl alcohol taking coal as raw material gas after CO conversion becomes H
2: 46%, CO:20%, CO
2: 32%, other are 2% years old.No matter which kind of technique, final CO
2content is no more than 5%, and all the other carbonic acid gas must enter atmosphere after purifying.
From transformationreation formula CO+H
2o-→ H
2+ CO
2can clearly can find out, generate 2 tons of hydrogen, need to consume 28 tons of CO and 18 tons of water, generate 44 tons of CO simultaneously
2, interconversion rate is higher, CO
2discharge larger.Interconversion rate of the present invention be only 8% and separately the methanol device interconversion rate taking coal as raw material up to 47-53%, CO
2discharge larger more than 60% than this project.
Described desulfuration of shift gas decarburization refers to removes in gas the synthetic harmful H of methyl alcohol
2s, COS and unnecessary CO
2, generally can adopt the technique such as low-temperature rectisol, NHD, after this technology purifies, the classical group of gas becomes H
2: 48%, CO:51%, CO
2: 0.20%, other 1.8%, and the Purge gas classical group of traditional technology becomes H
2: 68%, CO:27%, CO
2: 3%, CH
4: 1%, other are 1% years old.
The synthetic gas that described methane gas transforms is: methane gas is pressurizeed afterwards and the CH of hydrogen recovery unit
4(methane) gas mixes, and is preheating to approximately 360 DEG C through the heating coil of converter convection zone, enters hydrogenator, organosulfur is wherein converted into inorganic sulfur, and enters zinc oxide desulfurization groove, removes contained sulphur, reacts as follows:
COS?+?H
2?→?CO?+?H
2S
ZnO?+?H
2S?→?ZnS?+?H
2O
In formula: COS represents carbon oxysulfide, H
2s represents hydrogen sulfide, and ZnO represents zinc oxide, and ZnS represents zinc sulphide, and other are the same;
Oil field gas after desulfurization and process steam are by steam/hydrocarbons ratio 2-4: 1 mixes, gas mixture is preheating to after approximately 600 DEG C through the gas mixture heating coil of converter convection zone, enter the conversion tube of converter radiation section, there is conversion reaction under the high-temperature flue gas heat effect of burner hearth in unstripped gas, two principal reactions are as follows in reformer tube outside catalyzer and reformer tube:
CH
4?+?H
2O?→?CO?+?3H
2
CO?+?H
2O?→?CO
2?+?H
2
In formula: CH
4represent methane, other are the same;
Gas after conversion enters reforming gas boiler through lower gas gathering manifold, for the production of high pressure steam and low-pressure steam, enter again the feedwater of boiler water preheater heating boiler, reforming gas is cooled to 40 DEG C through de-salted water preheater, reforming gas water cooler again, after separating technology phlegma, (representative gases consists of the synthetic gas of formation H: C=2.92: H
2: 73%, CO:15%, CO
2: 7%, CH
4: 4%, other are 1% years old), enter synthetic gas compression section.If methane content in reforming gas is reduced to more than 3%, can also transform (CH through pure oxygen
4+ O
2→ CO
2+ 2H
2).And in raw material methanol technics processed, can only isolate redundance H taking Sweet natural gas merely
2doing fuel could meet the synthetic gas composition of methyl alcohol and require H after methane gas steam reforming
2many).
Described synthetic compression process 4 be by the methane preparing synthetic gas proportioning of synthetic the coal system of hydrogen-carbon ratio H: C=1 and hydrogen-carbon ratio H: C=2.92 to H: C=2.05(representative gases consists of: H
2: 67.5%, CO:27.5%, CO
2: 3.5%, CH
4: 1%, other are 0.5% years old).The synthetic gas H that Sweet natural gas and coal are produced traditionally: C is 2.05, Sweet natural gas need to discharge hydrogen (make fuel or other, resource utilization is low), and gasification needs a large amount of CO conversion and has increased CO
2discharge.
Described methyl alcohol is synthetic refers to the technology of hydrogen and carbon monoxide, carbonic acid gas methanol under catalyst action, reacts as follows:
H
2?+?CO?→?CH
3OH
H
2?+?CO
2→CH
3OH?+?H
2O
In formula: CH
3oH represents methyl alcohol, and other are the same, and methyl alcohol is synthetic requires (H in virgin gas
2-CO
2)/(CO+CO
2)=2.05-2.15.
The technical specification that in the present invention, embodiment adopts:
1, Coal Gasification Technology:
Dried coal powder pressurized gasification technology and water coal slurry pressure gasification technology are state-of-the-art Coal Gasification Technology in the world at present, are air flow bed pressurized gasification technology, and the present invention adopts coal water slurry entrained flow bed pressurized gasification technology.Water coal slurry pressure gasification technology is wider to the subject range of coal, and separate unit vapourizing furnace coal feeding amount is larger, and gasification operation temperature is high, slag tap.Efficiency of carbon conversion is high, does not produce the pollutents such as tar, naphthalene, phenol, and the three wastes are processed simple, are easy to meet the requirement of environmental protection, and plant automation level is higher.The present invention can select the technology such as dry powder pressurized gasification, broken coal gasification equally.
(1) vapor pressure
Coal slurry pressurized gasification pressure can adopt bis-kinds of 4.0 Mpa and 6.5 Mpa.All service experience of existing large-scale plant of two kinds of vapor pressures.Adopt 6.5 Mpa pressure coal slurry gasifications, because vapor pressure is high, after purifying, synthetic gas pressure still remains on 5.3 Mpa, closer to the methyl alcohol synthesis pressure of 8.0 Mpa, than adopting, 4.0 Mpa methanol energy consumption of compressor are low, therefore the present invention selects 6.5 Mpa pressure gasifications.
(2) vapourizing furnace specification
The specification of vapourizing furnace has 3,200 two kinds of φ 2800, φ, can be according to synthetic gas make out the scale.Processing coal amount due to day of the present invention is 2711t(butt), intend selecting 3 of φ 3200 vapourizing furnaces, 2 open 1 standby.Consider continuous operating time and the restriction in gasification oven refractory life-span of vapourizing furnace process burner, for the safe and stable operation that ensures gasification installation needs a vapourizing furnace for subsequent use.
(3) grey water handing
Three grades of flash distillations of grey water handing process using of the present invention, wherein high pressure flash separately carries out vapourizing furnace Heisui River and carbon Xi Ta Heisui River, and clarifying tank precipitation, vacuum filter separate thin slag.
The raw gas that gasification is produced is except containing CO, H
2, CO
2also has a small amount of H outward,
2s, COS, CH
4, N
2, the chlorine of HCN, trace, the compositions such as ammonia.Sulfide, chlorine, heavy metal nickel etc. are poisonous substances to methanol synthesis catalyst, must remove, in addition H
2can not meet the synthetic needs of methyl alcohol with the ratio of CO, thereby raw gas need be adjusted H through Partial Transformation
2/ CO, then remove CO
2, H
2after the gas such as S, COS, enter methanol reactor synthesizing methanol.
2, CO conversion
Unpurifed gas is adjusted to methyl methanol syngas, and CO conversion has two kinds of flow processs, i.e. Partial Transformation and all conversion.
According to rough coal tolerance, the present invention adopts Partial Transformation flow process, makes like this equipment size reduce, and is convenient to manufacture and transport.The bright spot of this device is that CO interconversion rate is only 7-10%, and 80% water-gas enters low-temperature rectisol after converting bypass recovery of heat, has greatly reduced CO
2discharge.
3, desulfurization and decarburization technique
Low-temp methanol washing process technology maturation is reliable, and energy consumption is lower, and gas purification degree is high, can be by the CO in synthetic gas
2take off to 10 ppm H
2s is less than 0.1 ppm.And solvent absorbing ability is large, internal circulating load is little, saving energy, and solvent low price, process cost is low is also the superiority place of this method.This method shortcoming is to operate at low temperatures, and equipment major part is cryogenic material, and whole technology investment is higher.Therefore, low-temp methanol washing process is selected in acid gas removal suggestion of the present invention, but does not get rid of other desulfurization and decarburization technology of selecting.
4, methane gas conversion process
The technique that Sweet natural gas or oil are manufactured methyl alcohol is exactly steam methane conversion process 5: raw material oil field gas pressurizes afterwards and the methane CH of hydrogen recovery unit
4gas mixes, and is preheating to approximately 360 DEG C through the heating coil of converter convection zone, enters hydrogenator, organosulfur is wherein converted into inorganic sulfur, and enters zinc oxide desulfurization groove, removes contained sulphur, reacts as follows:
COS?+?H
2?→?CO?+?H
2S
ZnO?+?H
2S?→?ZnS?+?H
2O
In formula, molecular formula meaning is the same.
Oil field gas after desulfurization mixes by steam/hydrocarbons ratio 2-4:1.0 with process steam, gas mixture is preheating to after approximately 600 DEG C through the gas mixture heating coil of converter convection zone, enter the conversion tube of converter radiation section, there is conversion reaction under the high-temperature flue gas heat effect of burner hearth in unstripped gas, two principal reactions are as follows in reformer tube outside catalyzer and reformer tube:
CH
4?+?H
2O?→?CO?+?3H
2
CO?+?H
2O?→?CO
2?+?H
2
In formula, molecular formula meaning is the same.
Gas after conversion enters reforming gas boiler through lower gas gathering manifold, for the production of high pressure steam and low-pressure steam, enter again the feedwater of boiler water preheater heating boiler, reforming gas is cooled to 40 DEG C through de-salted water preheater, reforming gas water cooler again, after separating technology phlegma, form the synthetic gas of H: C=2.92, enter synthetic gas compression section 4, synthetic compression process 4 is by H: synthetic and H: the C=2.92 of the coal system of C=1 through synthetic H: the C=2.05 that is compressed to of synthetic compression process 4 synthetic gas.
Steam methane conversion process 5 is the methyl alcohol product installations taking methane gas as main raw material, and steam methane conversion process 5 is selected investment one section of Steam Reforming Process low, that can mend carbon, simple to operate.One section of steam reforming for Gas Exploitation, hydrogen-carbon ratio was up to 2.92: 1, do not need to discharge hydrogen, also need to not mend carbon from the external world, but steam methane conversion process 5 mixes and reaches the synthetic needed hydrogen-carbon ratio (2.05: 1) of methyl alcohol through synthetic compression process 4 with gas maked coal.
The present invention adopts one section of steam reforming technology, can select equally other methane conversion technology.
5, methanol synthesizing process
Hydrogen-carbon ratio is the synthesis gas through methanol synthesis technique 6 of (2.05: 1), methanol synthesizing process 6 is mainly realized in methanol sythesis reactor, the form of methanol sythesis reactor has determined the system setting of methanol synthesizing process substantially, in selection methanol synthesizing process, consider the flexibility of operation of synthesis reactor, manual dexterity, the production intensity of catalyzer, the accessibility of operating maintenance, the factors such as reaction pick up the heat, for large-scale single series methanol device, also must consider the accessibility problem of transport, through considering, selected Britain wears radially synthesis technique of dimension ultra-large type steam rising formula methyl alcohol, do not get rid of and adopt other methyl alcohol synthetic technologys yet.
6, methyl alcohol preparation technology
It is raw material that methyl alcohol preparation technology 7 both can adopt refined methanol also can adopt thick methyl alcohol.Very not strict to composition requirements such as moisture in raw material because of DMTO device, but basic metal, some light constituent be there are certain requirements, be raw material therefore the present invention adopts thick methyl alcohol.Thick methyl alcohol removes the detrimental impurity such as light constituent and basic metal by stabilizer tower and triple-effect evaporator, and the discharging of triple-effect evaporator gas phase is DMTO level methyl alcohol after cooling, sends battery limit (BL) as the raw material of DMTO device.
Coal Chemical Industry methanol and methane gas are manufactured methanol process ripe technical process, during now commercial scale has been used, does not do too much explanation for technique more specifically.
Claims (2)
1. a method for synthesizing methanol through low-carbon technology, is characterized in that: comprise that the synthetic gas of methane gas conversion and the synthetic gas passing ratio that gasification is produced mix, and enter methanol reactor methanol after synthetic compression process; The synthetic gas that described gasification is produced comprises raw gas production and hydrogen-carbon ratio regulate process; Described raw gas is produced and is completed by following formula:
C+O
2==CO
2
C+CO
2==2CO
CO+H
2O—→H
2+CO
2
In formula: CmHn represents coal, C represents carbon atom, H
2represent hydrogen, O
2represent oxygen, CO represents carbon monoxide, CO
2represent carbonic acid gas, H
2o represents water, and m, n represent carbon, the number of hydrogen atoms in coal, lower same; Adopt water coal slurry pressure gasification technology, the raw gas typical case composition that gasification of coal produces is: H
2: 35%, CO:45%, CO
2: 18%, other are 2% years old;
Described hydrogen-carbon ratio regulate process is: raw gas is again by reaction CO+H
2o-→ H
2+ CO
2complete hydrogen-carbon ratio regulate, the unpurifed gas being come by gasification washing tower falls the moisture of gas entrainment through gas-liquid separator separates, then be divided into two strands, the incoming stock air preheater of unstripped gas and conversion gas heat exchange to a 305 DEG C left and right of no more than 40% enter shift converter, carry out Partial Transformation react with self-contained water vapor under sulfur-resistant transformation catalyst effect; Go out the high temperature shift gas of shift converter after feed gas heater heat exchange, enter middle pressure steam producer, by-product 2.5MPa saturation steam; Middle pressure steam generator exports gas be greater than total scale of construction 60% not conversion gas mix, enter the low-pressure steam of low pressure steam generator by-product 1.0MPa, temperature is down to after 210 DEG C, enter low pressure steam generator by-product 0.5MPa low-pressure steam through gas-liquid separation gas phase, temperature is down to 180 DEG C, then enter de-salted water preheater, watercooler and be finally cooled to 40 DEG C, deliver to desulfurization and decarburization unit and remove CO
2rear output hydrogen-carbon ratio H:C=1 producing synthesis gas from coal is to synthetic compression work
Skill;
The gas typical case composition of described Partial Transformation reaction is H
2: 37%, CO:40%, CO
2: 21%, other are 2% years old; Described desulfurization and decarburization adopts low-temperature rectisol or NHD technique, removes in gas the synthetic harmful H of methyl alcohol
2the CO of S, COS
2, classical group becomes H
2: 48%, CO:51%, CO
2: 0.20%, other 1.8%, hydrogen-carbon ratio is much smaller than 2;
The synthetic gas that described methane gas transforms is: after methane gas pressurization, mix with the methane gas of hydrogen recovery unit, be preheating to approximately 360 DEG C through the heating coil of converter convection zone, enter hydrogenator, organosulfur is wherein converted into inorganic sulfur, and enter zinc oxide desulfurization groove, remove contained sulphur, react as follows:
COS+H
2→CO+H
2S
ZnO+H
2S→ZnS+H
2O
In formula: COS represents carbon oxysulfide, H
2s represents hydrogen sulfide, and ZnO represents zinc oxide, and ZnS represents zinc sulphide;
Methane gas after desulfurization is mixed by steam/hydrocarbons ratio 2-4:1 with process steam, gas mixture is preheating to after approximately 600 DEG C through the gas mixture heating coil of converter convection zone, enter the conversion tube of converter radiation section, there is conversion reaction under the high-temperature flue gas heat effect of burner hearth in unstripped gas, two principal reactions are as follows in reformer tube outside catalyzer and reformer tube:
CH
4+H
2O→CO+3H
2
CO+H
2O→CO
2+H
2
In formula: CH
4represent methane;
Gas after conversion enters reforming gas boiler through lower gas gathering manifold, for the production of high pressure steam and low-pressure steam, enter again the feedwater of boiler water preheater heating boiler, reforming gas is cooled to 40 DEG C through de-salted water preheater, reforming gas water cooler again, after separating technology phlegma, the synthetic gas that generation hydrogen-carbon ratio is 2.92, representative gases consists of: H
2: 73%, CO:15%, CO
2: 7%, CH
4: 4%, other 1%, enter synthetic gas compression section.
2. the method for a kind of synthesizing methanol through low-carbon technology according to claim 1, is characterized in that: described methyl alcohol is synthetic refers to the technology of hydrogen and carbon monoxide, carbonic acid gas methanol under catalyst action, reacts as follows:
H
2+CO→CH
3OH
H
2+CO
2→CH
3OH+H
2O
In formula: CH
3oH represents methyl alcohol, and methyl alcohol is synthetic requires (H in virgin gas
2-CO
2)/(CO+CO
2)=2.05-2.15.
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| CN103113927A (en) * | 2013-03-15 | 2013-05-22 | 金川集团股份有限公司 | Method of improving utilization rate of heat in desulfurizing process of raw gas |
| CN104667696B (en) * | 2013-11-27 | 2017-09-29 | 七台河宝泰隆甲醇有限公司 | Methanol conversion and synthesis compression section system equipped with plate type heat exchanger |
| CN109384647A (en) * | 2018-10-25 | 2019-02-26 | 中石化南京工程有限公司 | A kind of transformation methanolizing integrated production equipment and method |
| EP3647264B1 (en) * | 2018-10-31 | 2023-10-11 | L'air Liquide, Société Anonyme Pour L'Étude Et L'exploitation Des Procédés Georges Claude | Method and system for the production of a purified and converted synthesis gas |
| CN110357035A (en) * | 2019-08-29 | 2019-10-22 | 陕西聚能新创煤化科技有限公司 | The total transform system and transform method of coal gasification |
| CN111548251B (en) * | 2020-04-08 | 2022-01-25 | 华南农业大学 | Method for preparing methanol by catalyzing methane all-component low-temperature plasma |
| CN113548945A (en) * | 2021-07-29 | 2021-10-26 | 中国石油天然气股份有限公司 | Low-temperature activity utilization process of catalyst |
| CN114394883A (en) * | 2021-11-02 | 2022-04-26 | 华陆工程科技有限责任公司 | Method for preparing methanol by coupling gasification of pulverized coal waste boiler with green electricity and green hydrogen to achieve near-zero carbon emission |
| CN114110424B (en) * | 2021-11-26 | 2023-09-01 | 鲁西化工集团股份有限公司煤化工二分公司 | Optimizing resource to prepare synthetic gas (CO: H) 2 =1:1) system and process |
| CN114921269B (en) * | 2022-06-09 | 2023-10-27 | 蒲城清洁能源化工有限责任公司 | Ammonia nitrogen reducing process for coal-to-methanol |
| CN119352946A (en) * | 2024-12-23 | 2025-01-24 | 安徽蓝氢能源科技有限公司 | Coal in-situ gasification and deep processing system and method |
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