CN115678615A - Method and apparatus for producing synthesis gas - Google Patents
Method and apparatus for producing synthesis gas Download PDFInfo
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- CN115678615A CN115678615A CN202110824663.5A CN202110824663A CN115678615A CN 115678615 A CN115678615 A CN 115678615A CN 202110824663 A CN202110824663 A CN 202110824663A CN 115678615 A CN115678615 A CN 115678615A
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- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 112
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 111
- 238000000034 method Methods 0.000 title claims abstract description 63
- 239000007789 gas Substances 0.000 claims abstract description 143
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 70
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 43
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 41
- 239000001257 hydrogen Substances 0.000 claims abstract description 38
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 117
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 117
- 239000003245 coal Substances 0.000 claims description 87
- 238000002309 gasification Methods 0.000 claims description 70
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 66
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 50
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 36
- 238000006477 desulfuration reaction Methods 0.000 claims description 36
- 230000023556 desulfurization Effects 0.000 claims description 36
- 229910052760 oxygen Inorganic materials 0.000 claims description 36
- 239000001301 oxygen Substances 0.000 claims description 36
- 239000001569 carbon dioxide Substances 0.000 claims description 25
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 25
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 22
- 238000006243 chemical reaction Methods 0.000 claims description 20
- 239000012530 fluid Substances 0.000 claims description 19
- 238000004519 manufacturing process Methods 0.000 claims description 19
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- 239000000126 substance Substances 0.000 claims description 11
- 150000001336 alkenes Chemical class 0.000 claims description 10
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims description 10
- 150000001345 alkine derivatives Chemical class 0.000 claims description 5
- -1 aromatics Substances 0.000 claims description 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 14
- 238000007599 discharging Methods 0.000 abstract description 4
- 238000011143 downstream manufacturing Methods 0.000 abstract description 2
- 150000002431 hydrogen Chemical class 0.000 description 18
- 238000000926 separation method Methods 0.000 description 18
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 13
- 229910052799 carbon Inorganic materials 0.000 description 13
- 229910052717 sulfur Inorganic materials 0.000 description 7
- 239000000428 dust Substances 0.000 description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 5
- 239000003034 coal gas Substances 0.000 description 5
- 238000011084 recovery Methods 0.000 description 5
- 239000011593 sulfur Substances 0.000 description 5
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 238000002485 combustion reaction Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 239000002918 waste heat Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 230000008030 elimination Effects 0.000 description 3
- 238000003379 elimination reaction Methods 0.000 description 3
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000005997 Calcium carbide Substances 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- CLZWAWBPWVRRGI-UHFFFAOYSA-N tert-butyl 2-[2-[2-[2-[bis[2-[(2-methylpropan-2-yl)oxy]-2-oxoethyl]amino]-5-bromophenoxy]ethoxy]-4-methyl-n-[2-[(2-methylpropan-2-yl)oxy]-2-oxoethyl]anilino]acetate Chemical compound CC1=CC=C(N(CC(=O)OC(C)(C)C)CC(=O)OC(C)(C)C)C(OCCOC=2C(=CC=C(Br)C=2)N(CC(=O)OC(C)(C)C)CC(=O)OC(C)(C)C)=C1 CLZWAWBPWVRRGI-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
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- 239000003502 gasoline Substances 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
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- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 1
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Images
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to a method and apparatus for producing synthesis gas. The method comprises using hydrogen produced by water electrolysis to convert H from synthesis gas 2 the/CO molar ratio is adjusted to not less than 1. Compared with the process of preparing the synthesis gas in the existing coal-to-olefin process, the method adds the hydrogen generated by water electrolysis into the synthesis gas to add H 2 the/CO molar ratio is adjusted to be suitable for the downstream process, the water gas shift scale can be reduced or the water gas shift step can be eliminated, and CO is reduced or eliminated 2 And (5) discharging.
Description
Technical Field
The invention belongs to the field of chemical synthesis. In particular, the present invention relates to a method and apparatus for producing synthesis gas.
Background
Coal is a compound with polycyclic aromatic hydrocarbons. Among all fossil fuels, coal has the lowest hydrogen to carbon ratio (<1) However, the chemicals produced from coal are typically olefins (C) n H 2n ) Alkyne (C) 2 H 2 ) Aromatic hydrocarbon (C) 6 H 6 、C 7 H 8 、C 8 H 10 Etc.), methanol (CH) 3 OH), acetic acid (CH) 3 COOH), etc., the hydrogen to carbon ratio of these chemicals is generally greater than 1.
There are two main routes for producing chemicals from coal.
i) Calcium carbide-acetylene route
The mixture of lime and coal generates calcium carbide in an electric arc furnace at a temperature of about 2,200 ℃:
CaO + 3C → CaC 2 + CO
calcium carbide reacts with water to form acetylene:
CaC 2 + 2H 2 O → C 2 H 2 + Ca(OH) 2
acetylene can be used to make other chemicals.
ii) coal gasification-syngas-methanol route
Synthesis gas production from coal gasification:
C + O 2 →CO 2
3C + O 2 + H 2 O → H 2 + 3CO
preparation of methanol from synthesis gas:
CO + 2H 2 → CH 3 OH
chemicals can be produced from methanol via Methanol To Olefins (MTO), methanol To Gasoline (MTG), or Methanol To Aromatics (MTA) processes.
In the existing coal gasification-syngas-methanol route, coal is first gasified to produce syngas (with CO and H) 2 As the major component) of the coal gasification process, part of the CO will be generated in the coal gasification process 2 And H in the synthesis gas 2 The mol ratio of/CO is only 0.4-0.7, which is far lower than the H required by the downstream methanol synthesis process 2 The molar ratio of/CO (about 2), therefore the need to add a water gas shift process after the synthesis gas to the CO and H in the synthesis gas 2 Conversion of O to H 2 And CO 2 To increase H 2 the/CO molar ratio.
CO+H 2 O →H 2 +CO 2
In the water gas shift process, there will be a large amount of CO 2 And (4) generating. Thus, in a coal to chemical route, there will be a significant amount of CO 2 And is discharged to the atmosphere.
The world commitment of china in 2020 will lead to carbon neutralization in 2060, and in order to achieve this goal, it is desirable to reduce or eliminate CO emissions to the atmosphere 2 。
Thus, there is a need for a process for producing hydrogen (H) carbon 2 Method for synthesis gas with a/CO) molar ratio not lower than 1, with elimination or great reduction of CO 2 And (5) discharging.
Disclosure of Invention
It is an object of the present invention to provide a process for the production of synthesis gas while eliminating or greatly reducing CO 2 And (5) discharging.
It is another object of the present invention to provide a system for carrying out the above method.
It is a further object of the present invention to provide a process for the production of chemicals such as methanol using the above synthesis gas.
Thus, according to a first aspect, the present invention provides a process for the production of synthesis gas, characterized in that it comprises the steps of:
i) Gasification of coal to H 2 Synthesis gas with a/CO molar ratio in the range of 0.4 to 0.7;
ii) removal of hydrogen sulphide (H) from the synthesis gas obtained in step i) 2 S)；
iii) Subjecting a portion of the carbon monoxide (CO) and water (H) in the synthesis gas obtained in step ii) 2 O) reaction to produce hydrogen (H) 2 ) With carbon dioxide (CO) 2 ) To remove H from the synthesis gas 2 The mol ratio of/CO is improved by 20 to 40 percent,
iv) removing hydrogen sulphide (H) from the synthesis gas obtained in step iii) 2 S) and carbon dioxide (CO) 2 ) (ii) a And
v) use of hydrogen (H) generated by electrolysis of water 2 ) H of the synthesis gas obtained in step iv) 2 the/CO molar ratio is adjusted to not less than 1.
According to a second aspect, the present invention provides a process for producing synthesis gas, characterised in that it comprises the steps of:
a) Gasification of coal to H 2 Synthesis gas with a/CO molar ratio in the range of 0.4 to 0.7;
b) Removing hydrogen sulphide (H) from the synthesis gas obtained in step a) 2 S); and
c) Using hydrogen (H) generated by electrolysis of water 2 ) H of the synthesis gas obtained in step b) 2 the/CO molar ratio is adjusted to not less than 1.
According to a third aspect, the present invention provides a system for producing synthesis gas, comprising:
coal gasification apparatus for gasifying coal to generate H 2 Synthesis gas with a/CO molar ratio in the range of 0.4 to 0.7;
a coarse desulfurization tower in fluid communication with the coal gasification unit for removing hydrogen sulfide (H) from the syngas 2 S)；
A water gas shift unit in fluid communication with the coarse desulfurization tower to convert a portion of the carbon monoxide (CO) and water (H) in the syngas from the coal gasification unit 2 O) reaction to produce hydrogen (H) 2 ) With carbon dioxide (CO) 2 ) To remove H from the synthesis gas 2 The mol ratio of/CO is improved by 20-40%;
a shifted gas desulfurization unit in fluid communication with the water gas shift unit to remove hydrogen sulfide (H) from the syngas from the water gas shift unit 2 S)；
Carbon dioxide (CO) in fluid communication with the desulfurization unit 2 ) A removal unit to remove carbon dioxide from the synthesis gas from the desulfurization unit; and
with said carbon dioxide (CO) 2 ) Removing means in fluid communication with the electrolysis means for removing hydrogen (H) produced by electrolysis of water 2 ) With carbon dioxide (CO) from 2 ) The synthesis gas from the stripping unit is combined.
According to a fourth aspect, the present invention provides a system for producing synthesis gas, comprising:
coal gasification apparatus for gasifying coal to generate H 2 Synthesis gas with a/CO molar ratio in the range of 0.4 to 0.7;
a desulfurization unit in fluid communication with the coal gasification unit to remove hydrogen sulfide (H) from the syngas from the coal gasification unit 2 S); and
an electrolysis device in fluid communication with the desulfurization device to electrolyze hydrogen (H) produced by the electrolysis of water 2 ) Is combined with the synthesis gas from the desulfurization unit.
According to a fifth aspect, the present invention provides a process for the production of a chemical selected from the group consisting of alkenes, alkynes, aromatics, methanol and acetic acid, characterised in that the process uses the above synthesis gas as feedstock.
Compared with the prior art for preparing hydrogen and carbon (H) in the process of preparing olefin by coal 2 CO) Process of Synthesis gas with molar ratio not less than 1, the method of the invention adds hydrogen produced by the electrolysis of water to the Synthesis gas to add H 2 the/CO molar ratio is adjusted to be suitable for downstream processes, the water gas shift scale can be reduced or the water gas shift step can be eliminated, the air separation device scale can be reduced or the air separation step can be eliminated, and CO can be reduced or eliminated 2 And (5) discharging.
Drawings
The present invention will be described and explained with additional specificity and detail through the use of the accompanying drawings in which like reference numerals refer to like elements throughout.
FIG. 1 shows the production of hydrogen carbon (H) according to one embodiment of the present invention 2 Schematic diagram of a plant for synthesis gas with a/CO) molar ratio not lower than 1,wherein, 1: air separation plant, 2: a coal gasification device; 3: a water gas shift device; 4: desulfurization device and CO 2 A removal device; 5: an electrolysis device; 6: and (4) a coarse desulfurization tower.
FIG. 2 shows the production of hydrogen carbon (H) according to one embodiment of the present invention 2 /CO) molar ratio not less than 1, wherein 1: air separation plant, 2: a coal gasification unit; 3: a desulfurization unit; 4: an electrolysis device.
Detailed description of the preferred embodiments
Some specific embodiments of the present invention will now be described for illustrative purposes, but not for limitation, with reference to the accompanying drawings.
The description of the various features of the present application may be combined without contradiction to each other and fall within the scope of the claims of the present application.
The terms "comprising" and "including" as used herein encompass the case where other elements not explicitly mentioned are also included or included and the case where they consist of the mentioned elements.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. To the extent that the definitions of terms used in this specification conflict with meanings commonly understood by those skilled in the art to which this invention pertains, the definitions set forth herein control.
Unless otherwise indicated, all numbers expressing quantities of process parameters and so forth used in the specification and claims are to be understood as being modified by the term "about". Accordingly, unless indicated to the contrary, the numerical parameters set forth herein are approximations that can vary depending upon the desired properties to be obtained.
In the present application, hydrogen carbon (H) 2 The ratio of/CO is equivalent to hydrogen to carbon (H) 2 /CO) molar ratio, which refers to the molar ratio of hydrogen to CO.
According to a first aspect, the present invention provides a process for producing synthesis gas, characterised in that it comprises the steps of:
i) Gasification of coal to H 2 Synthesis gas with a/CO molar ratio in the range of 0.4 to 0.7;
ii) Removing hydrogen sulphide (H) from the synthesis gas obtained in step i) 2 S)；
iii) Subjecting a portion of the carbon monoxide (CO) and water (H) in the synthesis gas obtained in step ii) to 2 O) reaction to produce hydrogen (H) 2 ) With carbon dioxide (CO) 2 ) To remove H from the synthesis gas 2 The mol ratio of/CO is improved by 20 to 40 percent,
iv) removing hydrogen sulphide (H) from the synthesis gas obtained in step iii) 2 S) and carbon dioxide (CO) 2 ) (ii) a And
v) use of hydrogen (H) generated by electrolysis of water 2 ) H of the synthesis gas obtained in step iv) 2 the/CO molar ratio is adjusted to not less than 1.
As known to those skilled in the art, coal gasification refers to a process of converting combustible components in coal or coal char into combustible gas (syngas, also called coal gas) by chemical reaction under high temperature conditions using coal or coal char as a raw material and oxygen and steam as a gasifying agent.
Wherein the oxygen can be air, oxygen-enriched oxygen or industrial pure oxygen.
The reactions that occur in coal gasification include pyrolysis, gasification, and combustion reactions of coal.
Pyrolysis of coal refers to the process by which coal changes from a solid phase to a gas, solid, liquid three-phase product.
The gasification and combustion reactions of coal include two reaction types, namely heterogeneous gas-solid reactions and homogeneous gas-phase reactions.
The process parameters used in steps i) -iv) may be those commonly used in existing coal-to-olefin processes.
Preferably, in step i), at least a portion of the oxygen used for coal gasification is derived from oxygen separated from air.
Preferably, in step i), at least a portion of the oxygen used for coal gasification is derived from oxygen produced by electrolysis of water.
Preferably, in step iv), the hydrogen sulphide content is removed to below 0.2 ppm.
Preferably, in step iv), carbon dioxide (CO) is introduced 2 ) Removing to below 5000 ppm.
Preferably, the electricity used for the electrolysis of the water in step v) is generated from renewable resources. For example, the renewable resource may be a solar and wind energy resource.
Preferably, in step v), the H of the synthesis gas obtained in step iv) is 2 the/CO molar ratio is adjusted to not less than 1.4, more preferably in the range of 1.5 to 4.
H of the synthesis gas obtained according to step v) 2 The molar ratio/CO, the synthesis gas obtained can be sent to a suitable subsequent section.
E.g. H when synthesis gas obtained in step v) is 2 At a molar ratio/CO of about 2, the synthesis gas obtained in step iv) may be sent to a methanol synthesis section for the production of methanol, ethanol, etc. The methanol thus produced can be sent to an MTO section for the production of light olefins or subjected to dehydration to produce dimethyl ether.
E.g. H when synthesis gas obtained in step v) is 2 At a molar ratio/CO of about 1.5, the synthesis gas obtained in step iv) can be passed to an ethylene glycol synthesis section for the production of ethylene glycol.
CO due to reduced water gas shift scale 2 The amount of emissions is significantly reduced. The scale of the air separation unit is also reduced due to the introduction of oxygen generated by the electrolysis of water.
According to a second aspect, the present invention provides a process for producing synthesis gas, characterised in that it comprises the steps of:
a) Gasification of coal to H 2 Synthesis gas with a/CO molar ratio in the range of 0.4 to 0.7,
b) Removing hydrogen sulphide (H) from the synthesis gas obtained in step i) 2 S); and
c) Using hydrogen (H) generated by electrolysis of water 2 ) H of the synthesis gas obtained in step ii) 2 the/CO molar ratio is adjusted to not less than 1.
The process parameters used in steps a) -b) may be those commonly used in existing coal-to-olefin processes.
Preferably, in step a), at least a portion of the oxygen used for coal gasification is derived from oxygen separated from air.
Preferably, in step a), at least a portion of the oxygen used for coal gasification is derived from oxygen produced by electrolysis of water.
Preferably, in step b), the hydrogen sulphide content is removed to below 0.2 ppm.
Preferably, in step b), carbon dioxide (CO) is added 2 ) Removing to below 5000 ppm.
Preferably, the electricity used for the electrolysis of the water in step c) is generated from renewable resources. For example, the renewable resource may be a solar and wind energy resource.
Preferably, in step c), the H of the synthesis gas obtained in step b) is 2 the/CO molar ratio is adjusted to not less than 1.4, more preferably, in the range of 1.5 to 4.
H of the synthesis gas obtained according to step c) 2 The molar ratio/CO, the synthesis gas obtained can be sent to a suitable subsequent section.
For example, when the synthesis gas obtained in step c) has H 2 At a molar ratio/CO of about 2, the synthesis gas obtained in step c) may be sent to a methanol synthesis section for the production of methanol, ethanol, etc. The methanol thus produced can be sent to an MTO section to produce light olefins or subjected to dehydration to produce dimethyl ether.
For example, when the synthesis gas obtained in step c) has H 2 At a molar ratio/CO of about 1.5, the synthesis gas obtained in step c) can be sent to an ethylene glycol synthesis section for the production of ethylene glycol.
CO due to elimination of the water gas shift step 2 The amount of emissions is significantly reduced.
According to a third aspect, the present invention provides a system for producing synthesis gas, comprising:
coal gasification apparatus for gasifying coal to generate H 2 Synthesis gas with a/CO molar ratio in the range of 0.4 to 0.7;
a crude desulfurization tower in fluid communication with the coal gasification unit for removing hydrogen sulfide (H) from the syngas 2 S)；
A water gas shift unit in fluid communication with the coarse desulfurization tower to convert a portion of the carbon monoxide (CO) and water (H) in the syngas from the coal gasification unit 2 O) reaction to produce hydrogen (H) 2 ) With carbon dioxide (CO) 2 ) To remove H from the synthesis gas 2 The mol ratio of/CO is improved by 20-40%;
a shifted gas desulfurization unit in fluid communication with the water gas shift unit to remove hydrogen sulfide (H) from the syngas from the water gas shift unit 2 S)；
Carbon dioxide (CO) in fluid communication with the desulfurization unit 2 ) A removal unit to remove carbon dioxide from the synthesis gas from the desulfurization unit; and
with said carbon dioxide (CO) 2 ) Removing means fluidly connected to the electrolysis means for removing hydrogen (H) produced by electrolysis of water 2 ) With carbon dioxide (CO) from the gas 2 ) The synthesis gas from the stripping unit is combined.
The coal gasification apparatus, the rough desulfurization tower, the water gas shift apparatus, the desulfurization apparatus, and the carbon dioxide (CO) 2 ) The removal device is the same as the device used in the existing coal-to-olefin system.
Hydrogen sulfide (H) removed by a crude desulfurization tower 2 S) can be recycled to prepare sulfur by industrially mature sulfur recovery processes (such as Claus process, super Claus process and the like).
Preferably, the system further comprises an oxygen supply to provide oxygen to the coal gasification unit.
In some embodiments, the oxygen supply device is an air separation device.
Preferably, the electrolysis device is further connected to the coal gasification device to supply oxygen produced by electrolysis of water to the coal gasification device.
FIG. 1 shows the production of hydrogen carbon (H) according to one embodiment of the present invention 2 Schematic plant for synthesis gas with a/CO) ratio not lower than 1, wherein 1: air separation plant, 2: a coal gasification unit; 3: a water gas shift device; 4: desulfurization device and CO 2 A removal device; 5: an electrolysis device; 6: and (4) a coarse desulfurization tower.
In the system of the third aspect of the invention CO reduction is achieved by adding hydrogen produced by electrolysis of water to the synthesis gas compared to prior art systems 2 The discharge amount of oxygen produced by electrolyzing water is fed to the coal gasification process, so that the air separation device, the water gas shift device and CO can be reduced 2 Scale of the removal unit.
According to a fourth aspect, the present invention provides a system for producing synthesis gas, comprising:
coal gasification apparatus for gasifying coal to generate H 2 Synthesis gas with a/CO molar ratio in the range of 0.4 to 0.7;
a desulfurization unit in fluid communication with the coal gasification unit to remove hydrogen sulfide (H) from the syngas from the coal gasification unit 2 S); and
an electrolysis device in fluid communication with the desulfurization device to electrolyze hydrogen (H) produced by the electrolysis of water 2 ) Is combined with the synthesis gas from the desulfurization unit.
The coal gasification apparatus and the desulfurization apparatus are the same as those used in the conventional system for producing olefins from coal.
Preferably, the system further comprises an oxygen supply to provide oxygen to the coal gasification unit.
In some embodiments, the oxygen supply device is an air separation device.
Preferably, the electrolysis device is further connected to the coal gasification device to supply oxygen produced by electrolysis of water to the coal gasification device.
FIG. 2 shows the production of hydrogen carbon (H) according to one embodiment of the present invention 2 Schematic plant for synthesis gas with a/CO) ratio not lower than 1, in which 1: air separation plant, 2: a coal gasification unit; 3: a desulfurization unit; 4: an electrolysis device.
The system of the fourth aspect of the invention provides for CO reduction by adding hydrogen produced by electrolysis of water to the synthesis gas as compared to prior art systems 2 The discharge amount of oxygen produced by electrolyzing water is fed into the coal gasification process and the water gas change process is eliminated, so that the scale of the air separation plant can be reduced and the water gas shift unit and CO can be eliminated 2 And a removing device.
According to a fifth aspect, the present invention provides a process for the production of a chemical selected from the group consisting of alkenes, alkynes, aromatics, methanol and acetic acid, characterised in that the process uses the above-described synthesis gas as a feedstock.
The olefin may be derived from C n H 2n Wherein n is an integer of 2 to 5.
The alkyne is, for example, acetylene (C) 2 H 2 )。
The aromatic hydrocarbon is, for example, benzene (C) 6 H 6 ) Toluene (C) 7 H 8 ) Xylene (C) 8 H 10 ) And the like.
The method for preparing chemicals can be performed with reference to the methods in the prior art.
Examples
The conception, specific structure, and technical effects of the present invention will be further described with reference to the following embodiments so that those skilled in the art can fully understand the objects, features, and effects of the present invention. Those skilled in the art will appreciate that the embodiments herein are for illustrative purposes only and that the scope of the present invention is not so limited.
Example 1
The present example was carried out using the following apparatus: a 180 ten thousand tons/year coal-to-ethylene glycol plant, which is provided with a coal gasification plant with the coal gasification capacity of 100 ten thousand tons/year, 4 (3 running and 1 standby) large-scale gasification furnaces with the scale of 4000 tons/day and an air separation plant with the oxygen capacity of 240 ten thousand tons/year;
an industrially mature Shell gasification furnace is adopted, oxygen, pulverized coal and a small amount of water vapor enter the gasification furnace under the pressurized condition, the gasification temperature is 1450-1600 ℃, the coal finishes a series of physical changes and chemical reaction processes such as temperature rise, volatile component removal, cracking, combustion and conversion in a very short time, the carbon conversion rate is about 99 percent, and CO in synthesis gas 2 And H 2 Are 618 t/H, 486 t/H and 27 t/H, respectively, in this case H 2 The molar ratio/CO was 0.6. The high-temperature coal gas at about 1500 ℃ at the top of the gasification furnace is quenched to about 900 ℃ by the cooled coal gas after dust removal and then enters the waste heat boiler. The synthetic gas after heat recovery by the waste heat boiler enters a dry dust removal and wet washing system, and the treated synthetic gas (the dust content is less than 1 mg/m) 3 ) Sending the mixture to a crude desulfurization tower for removing H 2 S，H 2 S can be recovered from industrially mature sulfurRecovering sulfur by a recovery process (such as Claus process, super Claus process, etc.).
By industrially mature water gas shift process, the H is removed 2 Synthesis gas and H after S 2 O is subjected to water gas shift reaction, the water gas shift adopts a full low-temperature shift process, and a three-section Co-Mo-based sulfur-tolerant low-shift catalyst is adopted. The temperature of the first section inlet is 200-220 ℃, and the temperature of the hot spot is 380-400 ℃; the inlet temperature of the second section is 200-220 ℃, the inlet temperature of the third section is 180-200 ℃ and the outlet temperature is 210-230 ℃ so as to lead CO to be condensed 2 And H 2 Reaction of O to H 2 The conversion of CO was controlled to 11.11 mol% to convert H 2 the/CO was adjusted to 0.8. CO and CO in synthetic gas after steam shift reaction 2 And H 2 The amount of the active ingredients is 550 t/h, 594 t/h and 32 t/h respectively;
the industrially mature low-temperature methanol washing process is adopted to remove H in the synthesis gas 2 S and CO 2 In the synthesis gas, H 2 The S content is controlled to be less than 0.2ppm 2 The content is controlled to be lower than 5000 ppm; CO due to reduced steam reforming scale relative to conventional processes of the prior art 2 The emission is reduced by 136.8 t/h.
Use 310 units of 1000 Nm 3 The hydrogen production devices by alkaline water electrolysis are connected in parallel, H 2 The generation amount is 27.8 t/h, and a byproduct O is generated 2 The amount of the produced oxygen was 442.3 t/h, and 2 to the oxygen outlet of the air separation unit for coal gasification. O generated due to the electrolyzed water 2 The scale of the air separation device is reduced from 600 ten thousand tons per year to 300 ten thousand tons per year, thereby reducing the equipment investment and the operation cost of the air separation device. Make up 27.8 t/H hydrogen generated by electrolysis of water to synthesis gas to obtain synthesis gas H 2 the/CO molar ratio was further adjusted from 0.8 to 1.5.
Using H 2 CO-adjusted syngas ethylene glycol is prepared via the industrially mature oxalate process.
Example 2
The following apparatus was used to carry out the present example: a200 ten thousand tons/year coal-to-methanol plant is equipped with a coal gasification device with the coal gasification capacity of 180 ten thousand tons/year, and 2 (1 running and 1 standby) 3000 tons/day large-scale gasification furnaces.
An industrially mature Shell gasification furnace is adopted, oxygen, pulverized coal and a small amount of water vapor enter the gasification furnace under the pressurization condition, the gasification temperature is 1450-1600 ℃, the coal finishes a series of physical changes and chemical reaction processes such as temperature rise, volatile component removal, cracking, combustion and conversion and the like in a very short time, the carbon conversion rate is about 99 percent, and CO in synthesis gas 2 And H 2 The amounts of production of (a) are 194 t/H, 153 t/H and 8 t/H, respectively, in this case H 2 The molar ratio/CO was 0.6. High-temperature coal gas at about 1500 ℃ at the top of the gasification furnace is quenched to about 900 ℃ by the cooled coal gas after dust removal and enters a waste heat boiler. The synthetic gas after heat recovery by the waste heat boiler enters a dry dust removal and wet washing system, and the treated synthetic gas (the dust content is less than 1 mg/m) 3 ) Sending the mixture to a crude desulfurization tower for removing H 2 S。H 2 S can be recovered and prepared into sulfur by industrially mature sulfur recovery processes (such as Claus process, super Claus process and the like).
Removing H in synthesis gas by adopting industrially mature low-temperature methanol washing process 2 S and CO 2 From the synthesis gas H 2 The S content is controlled to be less than 0.2ppm 2 The content is controlled to be less than 5000 ppm; CO due to elimination of water gas shift, relative to conventional processes in the prior art 2 The emission is reduced by 142.5 t/h.
220 stands of 1000 Nm are used 3 The hydrogen production devices by alkaline water electrolysis are connected in parallel, H 2 The generated amount is 19.6 t/h, and simultaneously a byproduct O is generated 2 The amount of O produced was 312.5 t/h 2 Delivering to the oxygen outlet of the air separation unit for coal gasification with excess O 2 Sending the product outside the battery limits. O generated due to the electrolyzed water 2 The air separation unit size is reduced from 124 ten thousand tons/year to 0 ten thousand tons/year, and 157 t/h O is additionally generated 2 As a by-product, the investment in equipment and the operating cost of an air separation plant are avoided. Make up 19.6 t/H hydrogen generated by electrolysis of water to synthesis gas to obtain synthesis gas H 2 the/CO molar ratio was further adjusted from 0.6 to 2.
Using H 2 The CO-conditioned syngas is used to prepare methanol via an industrially mature syngas to methanol process.
Claims (12)
1. A process for producing synthesis gas, comprising the steps of:
i) Gasification of coal to H 2 Synthesis gas with a/CO molar ratio in the range of 0.4 to 0.7;
ii) removal of hydrogen sulphide (H) from the synthesis gas obtained in step i) 2 S)；
iii) Subjecting a portion of the carbon monoxide (CO) and water (H) in the synthesis gas obtained in step ii) 2 O) reaction to produce hydrogen (H) 2 ) With carbon dioxide (CO) 2 ) To remove H from the synthesis gas 2 The mol ratio of/CO is improved by 20-40%;
iv) removing hydrogen sulphide (H) from the synthesis gas obtained in step iii) 2 S) and carbon dioxide (CO) 2 ) (ii) a And
v) use of hydrogen (H) generated by electrolysis of water 2 ) H of the synthesis gas obtained in step iv) 2 the/CO molar ratio is adjusted to not less than 1.
2. A process for producing synthesis gas, comprising the steps of:
a) Gasification of coal to H 2 Synthesis gas with a/CO molar ratio in the range of 0.4 to 0.7;
b) Removing hydrogen sulphide (H) from the synthesis gas obtained in step i) 2 S); and
c) Using hydrogen (H) generated by electrolysis of water 2 ) H of the synthesis gas obtained in step ii) 2 the/CO molar ratio is adjusted to not less than 1.
3. The method according to claim 1 or 2,
in step i) or a), at least a portion of the oxygen used for coal gasification is derived from oxygen separated from air.
4. The method according to any one of claims 1 to 3,
in step i) or a), at least a portion of the oxygen used for coal gasification is derived from oxygen produced by electrolysis of water.
5. The method according to any one of claims 1 to 4,
in step iv) or b), the hydrogen sulphide content is removed to below 0.2 ppm.
6. The method according to any one of claims 1 to 5,
in step iv) or b), carbon dioxide (CO) 2 ) Removing to below 5000 ppm.
7. The method according to any one of claims 1 to 6,
h of the synthesis gas obtained in step iv) or b) 2 the/CO molar ratio is adjusted to not less than 1.4, more preferably in the range of 1.5 to 4.
8. A system for producing syngas, comprising:
coal gasification apparatus for gasifying coal to generate H 2 Synthesis gas with a/CO molar ratio in the range of 0.4 to 0.7;
a crude desulfurization tower in fluid communication with the coal gasification unit for removing hydrogen sulfide (H) from the syngas 2 S)；
A water gas shift unit in fluid communication with the coarse desulfurization tower to convert a portion of the carbon monoxide (CO) and water (H) in the syngas from the coal gasification unit 2 O) reaction to produce hydrogen (H) 2 ) With carbon dioxide (CO) 2 ) To remove H from the synthesis gas 2 The mol ratio of/CO is improved by 20-40%;
a shifted gas desulfurization unit in fluid communication with the water gas shift unit to remove hydrogen sulfide (H) from the syngas from the water gas shift unit 2 S)；
Carbon dioxide (CO) in fluid communication with the desulfurization unit 2 ) A removal unit to remove carbon dioxide from the synthesis gas from the desulfurization unit; and
with said carbon dioxide (CO) 2 ) Removing means fluidly connected to the electrolysis means for removing hydrogen (H) produced by electrolysis of water 2 ) With carbon dioxide (CO) from 2 ) The synthesis gas from the stripping unit is combined.
9. A system for producing syngas, comprising:
coal gasification apparatus for gasifying coal to produce H 2 Synthesis gas with a/CO molar ratio in the range of 0.4 to 0.7;
a desulfurization unit in fluid communication with the coal gasification unit to remove hydrogen sulfide (H) from the syngas from the coal gasification unit 2 S); and
an electrolysis device in fluid communication with the desulfurization device to electrolyze hydrogen (H) produced by the electrolysis of water 2 ) Is combined with the synthesis gas from the desulfurization unit.
10. The apparatus of claim 8 or 9, wherein the system further comprises an oxygen supply to provide oxygen to the coal gasification apparatus.
11. The apparatus according to any one of claims 8 to 10, wherein the electrolysis apparatus is further connected to the coal gasification apparatus to supply oxygen produced by electrolysis of water to the coal gasification apparatus.
12. A process for the production of a chemical selected from the group consisting of alkenes, alkynes, aromatics, methanol and acetic acid, characterized in that it uses as feedstock the synthesis gas produced by the process according to any one of claims 1 to 7.
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