CN109384646A - A kind of the synthesising gas systeming carbinol device and its technique of no transformation system - Google Patents
A kind of the synthesising gas systeming carbinol device and its technique of no transformation system Download PDFInfo
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- CN109384646A CN109384646A CN201811584952.7A CN201811584952A CN109384646A CN 109384646 A CN109384646 A CN 109384646A CN 201811584952 A CN201811584952 A CN 201811584952A CN 109384646 A CN109384646 A CN 109384646A
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims abstract description 605
- 238000000034 method Methods 0.000 title claims abstract description 39
- 230000009466 transformation Effects 0.000 title claims abstract description 38
- 239000007789 gas Substances 0.000 claims abstract description 260
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 122
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 119
- 239000001257 hydrogen Substances 0.000 claims abstract description 93
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 93
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 91
- 239000003245 coal Substances 0.000 claims abstract description 76
- 230000006835 compression Effects 0.000 claims abstract description 60
- 238000007906 compression Methods 0.000 claims abstract description 60
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 55
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 54
- 238000002309 gasification Methods 0.000 claims abstract description 46
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000001301 oxygen Substances 0.000 claims abstract description 44
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 44
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 claims abstract description 23
- 230000000737 periodic effect Effects 0.000 claims description 52
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 29
- 238000002955 isolation Methods 0.000 claims description 25
- 238000010926 purge Methods 0.000 claims description 25
- 239000008246 gaseous mixture Substances 0.000 claims description 12
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 11
- 239000007788 liquid Substances 0.000 claims description 7
- 239000012528 membrane Substances 0.000 claims description 7
- 239000000284 extract Substances 0.000 claims description 6
- 239000003546 flue gas Substances 0.000 claims description 6
- 238000000605 extraction Methods 0.000 claims description 5
- 238000000926 separation method Methods 0.000 claims description 4
- 238000007701 flash-distillation Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 15
- 238000010521 absorption reaction Methods 0.000 abstract description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 20
- 239000000047 product Substances 0.000 description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 10
- 229910021529 ammonia Inorganic materials 0.000 description 10
- 238000000746 purification Methods 0.000 description 10
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 9
- 229910002092 carbon dioxide Inorganic materials 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 8
- 229910002091 carbon monoxide Inorganic materials 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 239000003034 coal gas Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 239000001569 carbon dioxide Substances 0.000 description 3
- 230000000295 complement effect Effects 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000005262 decarbonization Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 239000010117 shenhua Substances 0.000 description 2
- 239000013589 supplement Substances 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- YZCKVEUIGOORGS-NJFSPNSNSA-N Tritium Chemical compound [3H] YZCKVEUIGOORGS-NJFSPNSNSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005261 decarburization Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000006052 feed supplement Substances 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 210000003205 muscle Anatomy 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 125000001741 organic sulfur group Chemical group 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
- C07C29/151—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases
- C07C29/1516—Multisteps
- C07C29/1518—Multisteps one step being the formation of initial mixture of carbon oxides and hydrogen for synthesis
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
- C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
- C07C29/80—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment by distillation
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
-
- 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
Abstract
The invention discloses a kind of synthesising gas systeming carbinol device of no transformation system and its techniques, the technique generates synthesis gas the following steps are included: oxygen made from coal and electrolysis water is carried out gasification reaction, by synthesis gas it is purified after, it is merged with hydrogen made from electrolysis water according to hydrogen-carbon ratio needed for methanol-fueled CLC, compression, prepares methanol.The oxygen that electrolysis water generates is sent directly into gasification unit by the technique, the hydrogen of electrolysis water is incorporated in purified synthesis gas, the situation of former synthesis gas converter unit and pressure-swing absorption apparatus is banned, not only the high production efficiency of methanol, but also realizes the comprehensive utilization of resource.
Description
Technical field
The present invention relates to methanol preparation technical fields, and in particular to a kind of synthesising gas systeming carbinol device of no transformation system
And its technique.
Background technique
Ammonia from coal industry development in China's is rapid in recent years.Currently, the existing ammonia from coal for turning to core with coal gas in China
There are about more than 230 families in manufacturer, and gross annual output can exceed that 22,000,000 tons.The large-scale ammonia from coal project gone into operation, such as Shenhua packet header
Produce 1800000 tons of coal-based methanol projects per year, the Datang world produces 1670000 tons of coal-based methanol projects per year and the peaceful coal of Shenhua produces 1200000 per year
Ton coal-based methanol project.
Gasification → carbon monodixe conversion → low-temp methanol the elution that is generally used of ammonia from coal device removes sour gas at present
The process flow of body → methanol-fueled CLC.The crude synthesis gas for carrying out self-gasifying device reacts CO and H2O in carbon monodixe conversion unit
Generate H2And CO2, and by the depth of control CO conversion reaction, and then control the H in synthesis gas2/ CO molar ratio；Then becoming
Unit is changed to H2The molar ratio of/CO does further adjustment, so that crude synthesis gas is obtained through low temperature washing device for methanol desulfurization, part decarburization
To with ideal H2The methyl methanol syngas of the molar ratio of/CO.
Its process is schematically as follows:
When using the process flow, in CO converter unit, due to the bed temperature of transformation furnace catalyst, reaction activity,
The reasons such as the degree of CO conversion reaction etc. is more difficult to control, not can guarantee H in synthesis gas2The molar ratio of/CO meets methanol-fueled CLC
It is required that.Also, in prior art, unit is washed in low-temp methanol, feeding gas only has one, i.e., contains what CO converter unit was adjusted
H2The crude synthesis gas of/CO.Such flow setting causes in large-scale coal chemical engineering equipment, and absorption tower size is larger, while one
Charging means that an absorption system is only arranged, can not optimize low-temp methanol and wash the methanol loop system for absorbing part, cooling capacity disappears
Consumption is high.
But from the point of view of the element of coal composition, hydrogen/carbon atomic ratio of coal is 0.2-1.0, and synthesis needed for methanol-fueled CLC
Gas is suitable for that hydrogen-carbon ratio (abbreviation H/C) is about 2.1-2.2, so adjustment of the ammonia from coal along with hydrogen-carbon ratio.Existing coal first
During alcohol, carbon monoxide therein is converted to hydrogen by water gas shift reaction by synthesis gas, and conversion process is aoxidized one
Carbon reaction is the carbon dioxide of the amount of same substance.These carbon dioxide are directly discharged to after acid gas removal unit
In environment.It does not only result in the loss of mass efficient carbon in this way, while environment is adversely affected.In addition, if introducing
If carbon tax, the cost advantage of ammonia from coal technique will not exist.
The adjustment of formula that synthesis gas from coal gasification is reduced or avoided with the smallest cost for a kind of scheme is found, it can be effectively real
The energy-saving and emission-reduction of existing production process.The co-feeding system of plurality of raw materials is the more effective approach for such issues that solve.Co-feeding system
Advantage be to carry out by the rich hydrogen-rich resource such as carbon resource and natural gas, oven gas such as coal by way of process integration
The Proper Match of material, energy and production process adjusts the hydrogen-carbon ratio of synthesis gas according to actual needs.
In traditional coal methanol process, oxygen is needed to gasify with coal, hydrogen and carbon monoxide in the synthesis gas of generation
Molar ratio is about 0.4 or so, and carbon monoxide and water vapour is needed to carry out conversion reaction, and methanol per ton need to discharge 1.6 after transformation
Ton carbon dioxide, enterprise's carbon emission amount increase, and environmental pressure increases, serious waste of resources.
Summary of the invention
The purpose of the present invention is to provide a kind of synthesising gas systeming carbinol device of no transformation system and its technique, the techniques gram
The deficiency for taking existing ammonia from coal provides a kind of higher efficiency, the ammonia from coal production technology of more energy efficient, safer environmental protection.
The present invention solves its technical problem and adopts the following technical solutions to realize.
The invention proposes a kind of synthesis gas of no transformation system to prepare methanol device, comprising: electrolysis water unit, coal gasification
Unit, clean unit, compression unit and methanol synthesis unit, the oxygen outlet of electrolysis water unit and the oxygen of coal gasification unit enter
Mouth is connected, and the syngas outlet of coal gasification unit is connected with the synthesis gas entrance of clean unit, the purified gas of clean unit
Outlet is connected with the purified gas entrance of compression unit, and the hydrogen outlet of electrolysis water unit is connected with the hydrogen inlet of compression unit
It connects, the compressed gas outlet of compression unit is connected with the compressed gas entrance of methanol synthesis unit.
The invention also provides a kind of synthesising gas systeming carbinol techniques of no transformation system, comprising the following steps:
Oxygen made from feed coal and electrolysis water unit is subjected to gasification reaction in coal gasification unit and generates synthesis gas, will be closed
The synthesis gas after purified treatment is purified is carried out in clean unit at gas, purified synthesis gas is made with electrolysis water unit
Hydrogen merged according to hydrogen-carbon ratio needed for methanol-fueled CLC, then in the compression unit carry out compression processing obtain compressed gas
Compressed gas is reacted in methanol synthesis unit, crude carbinol and methanol purge gas is prepared by body.
The beneficial effects of the present invention are:
The present invention provides a kind of synthesising gas systeming carbinol device of no transformation system and its technique, by electrolysis water in the present invention
The hydrogen of system is incorporated in purified synthesis gas, is banned in traditional ammonia from coal device and is needed synthesis gas converter unit and transformation
The situation of adsorbent equipment, preparing methanol using the device is a kind of green, environmentally friendly technique.
Detailed description of the invention
In order to illustrate the technical solution of the embodiments of the present invention more clearly, below will be to needed in the embodiment attached
Figure is briefly described, it should be understood that the following drawings illustrates only certain embodiments of the present invention, therefore is not construed as pair
The restriction of range for those of ordinary skill in the art without creative efforts, can also be according to this
A little attached drawings obtain other relevant attached drawings.
Fig. 1 is the synthesising gas systeming carbinol device figure without transformation system in the embodiment of the present invention 1；
Fig. 2 is the synthesising gas systeming carbinol device figure without transformation system in the embodiment of the present invention 2；
Fig. 3 is the synthesising gas systeming carbinol device figure without transformation system in the embodiment of the present invention 3；
Fig. 4 is the synthesising gas systeming carbinol device figure without transformation system in the embodiment of the present invention 4；
Fig. 5 is that the isolation of purified unit of synthesising gas systeming carbinol device without transformation system in the embodiment of the present invention 2 and 4 shows
It is intended to；
Drawing reference numeral: 100- electrolysis water unit；200- coal gasification unit；300- clean unit；400- compression unit；500-
Methanol synthesis unit；600- isolation of purified unit；610- gas-liquid separator；620- heat exchanger；630- and membrane separator；700- speeds
Deflation mentions hydrogen unit；800- boiler；900- methanol rectification unit；The tank field 1000-.
Specific embodiment
It in order to make the object, technical scheme and advantages of the embodiment of the invention clearer, below will be in the embodiment of the present invention
Technical solution be clearly and completely described.The person that is not specified actual conditions in embodiment, according to normal conditions or manufacturer builds
The condition of view carries out.Reagents or instruments used without specified manufacturer is the conventional production that can be obtained by commercially available purchase
Product.
The synthesising gas systeming carbinol device to a kind of no transformation system provided in an embodiment of the present invention and its technique carry out below
It illustrates.
The synthesis gas that the embodiment of the present invention provides a kind of no transformation system prepares methanol device, comprising: electrolysis water unit
100, coal gasification unit 200, clean unit 300, compression unit 400 and methanol synthesis unit 500, the oxygen of electrolysis water unit 100
Gas outlet is connected with the oxygen intake of coal gasification unit 200, the syngas outlet and clean unit 300 of coal gasification unit 200
Synthesis gas entrance be connected, the clean gas outlet of clean unit 300 is connected with the purified gas entrance of compression unit 400, electricity
The hydrogen outlet of solution water unit 100 is connected with the hydrogen inlet of compression unit 400, the outlet of the compressed gas of compression unit 400 and
The compressed gas entrance of methanol synthesis unit 500 is connected.
The embodiment of the present invention provides a kind of synthesising gas systeming carbinol device of no transformation system, which uses water electrolysis hydrogen production
Produce methanol with oxygen and coal gas complementary coupled, by oxygen made from electrolysis water unit 100 be delivered in coal gasification unit 200 into
Row coal gasification reaction generates synthesis gas, reduces air separation unit oxygen scale；Hydrogen made from electrolysis water unit 100 is incorporated to purification
In synthesis gas after the purification of unit 300, hydrogen and carbon monoxide ratio in synthesis gas are adjusted, the suitable first of hydrogen-carbon ratio is made
Above-mentioned methanol feedstock gas is compressed in compression unit 400, then is delivered in methanol synthesis unit 500 by raw polyol gas, should
Process is not necessarily to transformation system, pressure-variable adsorption and decarbonization process, the CO of discharge2Amount is negligible.
It can be seen that methanol device processed provided in an embodiment of the present invention, which is banned in traditional ammonia from coal device, needs space division
The situation of oxygenerator, synthesis gas converter unit and pressure-swing absorption apparatus greatly reduces the complexity of device and corresponding
Technology difficulty, especially traditional coal are prepared in methanol process, in synthesis gas converter unit, due to converting the bed of furnace catalyst
The reasons such as temperature, the activity of reaction, the degree of CO conversion reaction etc. be more difficult to control, not can guarantee H in synthesis gas2Mole of/CO
Than the requirement for meeting methanol-fueled CLC.The difficulty that transformation is greatly reduced in the present invention, is simple and efficient, and will not introduce new impurity,
It only needs to adjust hydrogen and carbon monoxide ratio in synthesis gas, the unstrpped gas for being suitable for methanol preparation can be obtained, improve
The production efficiency of methanol is a kind of green hydrogen production process and environmentally friendly technique in addition, water electrolysis hydrogen production, in electrolytic process
Other pollutants are not generated, and carbon resource comprehensively utilizes in protection system.
In some embodiments, it further includes that isolation of purified unit 600 and periodic off-gases mention hydrogen that synthesis gas, which prepares methanol device,
The methanol purge gas outlet of unit 700, methanol synthesis unit 500 is connected with the entrance of isolation of purified unit 600, isolation of purified list
The outlet of member 600 is connected with the entrance that periodic off-gases mention hydrogen unit 700.
In some embodiments, isolation of purified unit 600 includes sequentially connected gas-liquid separator 610, heat exchanger 620
And membrane separator 630.
In some embodiments, the periodic off-gases that periodic off-gases mention hydrogen unit 700 extract hydrogen outlet and compression unit 400
Periodic off-gases extract hydrogen inlet and are connected.
It can be seen that the embodiment of the invention provides a kind of synthesising gas systeming carbinol device of no transformation system, the preparation first
Alcohol device further include: isolation of purified unit 600 and periodic off-gases mention hydrogen unit 700, for the periodic off-gases generated after methanol-fueled CLC
It is further processed, wherein the entrance of the methanol purge gas outlet and isolation of purified unit 600 of methanol synthesis unit 500
It is connected, periodic off-gases enter back into periodic off-gases and mention in hydrogen unit 700, periodic off-gases mention hydrogen unit 700 and mention hydrogen after isolation of purified is handled
The hydrogen that processing generates is incorporated to compression unit 400 as hydrogen feed and supplements gas, is effectively utilized hydrogen in methanol purge gas, mentions
High production efficiency.
In some embodiments, it further includes methanol rectification unit 900, methanol synthesis unit that synthesis gas, which prepares methanol device,
500 crude carbinol outlet is connected with the crude carbinol entrance of methanol rectification unit 900.
In some embodiments, it further includes boiler 800 that synthesis gas, which prepares methanol device, and methanol rectification unit 900 is discharged
Flashed vapour, periodic off-gases mention the stripping gas of the discharge of hydrogen unit 700 and be mixed into gaseous mixture pipeline, gaseous mixture pipeline and boiler 800
It is connected.
It can be seen that the embodiment of the invention provides a kind of synthesising gas systeming carbinol device of no transformation system, the preparation first
Alcohol device further include: the methanol generated after methanol-fueled CLC is further processed in methanol rectification unit 900, wherein
The crude carbinol of the reaction production of methanol synthesis unit 500 is delivered to methanol rectification unit 900, isolates refined methanol finished product and send to first
Alcohol tank field stores or sends outside, and the flashed vapour and periodic off-gases that methanol rectification unit 900 generates mention after the extraction hydrogen of hydrogen unit 700
Remaining stripping gas, which is sent together to boiler 800, to burn, and removes producing steam, realizes the comprehensive utilization of resource.
The embodiment of the present invention also provides the technique that a kind of device of utilization or more prepares methanol, comprising the following steps:
Oxygen made from feed coal and electrolysis water unit 100 is subjected to gasification reaction in coal gasification unit 200 and generates synthesis
Synthesis gas is carried out the synthesis gas after purified treatment is purified in clean unit 300, by purified synthesis gas and electrolysis by gas
Hydrogen made from water unit 100 is merged according to hydrogen-carbon ratio needed for methanol-fueled CLC, then is compressed in compression unit 400
Processing obtains compressed gas, and compressed gas is reacted in methanol synthesis unit 500, crude carbinol is prepared and methanol speeds to put
Gas.
As it can be seen that the device for providing a kind of utilization or more in the embodiment of the present invention prepares the technique of methanol, the preparation process packet
Include following steps: oxygen made from coal and electrolysis water being subjected to gasification reaction and generates synthesis gas, by synthesis gas it is purified after, with
Hydrogen made from electrolysis water is merged according to hydrogen-carbon ratio needed for methanol-fueled CLC, and compression prepares methanol.It can be seen that the embodiment institute
The technology utilization water electrolysis hydrogen production and oxygen and coal gas complementary coupled of use produce methanol, take full advantage of the hydrogen of electrolysis water generation
Gas and oxygen, above-mentioned gas do not contain impurity, avoid and need making oxygen by air separation during current coal prepares methanol, and transformation is inhaled
The complicated technologies such as attached hydrogen manufacturing, so that the preparation of the synthesis gas in methanol preparation process is simple and efficient, impurity content is small, hence it is evident that improves
The purity and yield of the methanol of preparation.
In some embodiments, the mass ratio of the feed coal in coal gasification unit 200 and oxygen is 0.8:2-1.5:2,
The treatment temperature of clean unit 300 is 200-260 DEG C, pressure 3.5-5MpaG, and the treatment temperature of compression unit 400 is 24-
120 DEG C, pressure 4.5-7MpaG, the hydrogen-carbon ratio in methanol synthesis unit 500 is 2.0-4.5.
The purified unit 300 of the synthesis gas generated in coal gasification unit 200 in the embodiment of the present invention removes in gas
Dust, tar, and it is pressurized removing hydrogen sulfide and organic sulfur, so that the sulfur content of synthesis gas is less than 0.2ppm, by purified treatment
Synthesis gas is re-fed into compression unit 400 and carries out compression processing, and hydrogen made from synthesis gas and electrolysis water is according to needed for methanol-fueled CLC
Carbon ratio merges, and is compressed into 4.5~7Mpa of pressure needed for synthesizing methanol together, higher or lower than above-mentioned pressure
Power is unfavorable for making full use of for synthesis gas and hydrogen, then carries out the gas after compression in methanol synthesis unit 500
Methanol synthesis reaction, the hydrogen-carbon ratio in the synthesis unit are 2.0-4.5.
In some embodiments, technique further include: pass through the methanol purge gas that the reaction of methanol synthesis unit 500 generates
The processing of isolation of purified unit 600 enters back into periodic off-gases and mentions the hydrogen of the extraction generation of hydrogen unit 700 as hydrogen in compression unit 400
Periodic off-gases are mentioned in the stripping gas and methanol rectification unit 900 for extracting in hydrogen unit 700 and generating after hydrogen and being produced by the make-up gas of gas
The gaseous mixture that raw flashed vapour merges generation is transported to burning in boiler 800 and generates flue gas outlet, by methanol synthesis unit
500 reaction generate crude carbinols is delivered in methanol rectification unit 900, by the refined methanol generated in methanol rectification unit 900 at
Product are stored or are sent outside.
In the technique provided in an embodiment of the present invention for preparing methanol, methanol synthesis unit 500 generate methanol purge gas into
Row recycles, since ton methanol generates about 120-160m during synthesizing methanol3(main component has periodic off-gases: H2: 68-
73%, CO:2-5%, CO2: 0.5-2.3%, N2: 12-16.5% and CH4: 5.4-8.5% etc.), periodic off-gases are successively through gas-liquid point
Hydrogen (i.e. PSA mentions hydrogen) is extracted from pressure-variable adsorption is carried out after device 610, heat exchanger 620 and membrane separator 630, by what is extracted
(according to 1,500,000 tons of methanol meters are produced per year, the amounts of hydrogen extracted in periodic off-gases is 5000-8000m to hydrogen3/ h) it is incorporated to compression unit
400 as hydrogen feed supplement gas, and the above process not only realizes the effective use of the hydrogen in periodic off-gases, but also does not generate dirt
Dye, is advantageously implemented recycling for resource.
Feature and performance of the invention are described in further detail with reference to embodiments.
Embodiment 1
Referring to attached drawing 1, a kind of synthesising gas systeming carbinol device of no transformation system, comprising:
Electrolysis water unit 100, coal gasification unit 200, clean unit 300, compression unit 400 and methanol synthesis unit 500,
Electrolysis water unit 100 includes oxygen outlet and hydrogen outlet, and coal gasification unit 200 includes coal entrance, oxygen intake and synthesis gas
Outlet, clean unit 300 include synthesis gas entrance and clean gas outlet, and compression unit 400 includes hydrogen inlet, purified gas entrance
It is exported with compressed gas, methanol synthesis unit 500 includes compressed gas entrance and methanol purge gas outlet, crude carbinol outlet.
The oxygen intake of coal gasification unit 200 is connect with the oxygen outlet of electrolysis water unit 100, coal gasification unit 200
Syngas outlet is connected with the synthesis gas entrance of clean unit 300, clean gas outlet, the electrolysis water unit of clean unit 300
100 hydrogen outlet is connected with purified gas entrance, the hydrogen inlet of compression unit 400 respectively, the compressed gas of compression unit 400
Outlet is connected with the compressed gas entrance of methanol synthesis unit 500.
Embodiment 2
Referring to attached drawing 2 and 5, a kind of synthesising gas systeming carbinol device of no transformation system, comprising:
Electrolysis water unit 100, coal gasification unit 200, clean unit 300, compression unit 400, methanol synthesis unit 500,
Isolation of purified unit 600, periodic off-gases mention hydrogen unit 700 and boiler 800, and electrolysis water unit 100 includes that oxygen outlet and hydrogen go out
Mouthful, coal gasification unit 200 includes coal entrance, oxygen intake and syngas outlet, and clean unit 300 is including synthesis gas entrance and only
Change gas outlet, compression unit 400 includes hydrogen inlet, purified gas entrance and compressed gas outlet, and methanol synthesis unit 500 includes pressure
Contracting gas entrance and methanol purge gas outlet, crude carbinol outlet, isolation of purified unit 600 include methanol purge gas entrance and exit,
Periodic off-gases mention hydrogen unit 700 include purification methanol purge gas entrance, purification methanol purge gas mention hydrogen outlet and stripping gas go out
Mouthful, boiler 800 includes gaseous mixture entrance and exhanst gas outlet；With further reference to Fig. 5, isolation of purified unit 600 includes being sequentially connected
Gas-liquid separator 610, heat exchanger 620 and membrane separator 630.
The oxygen intake of coal gasification unit 200 is connect with the oxygen outlet of electrolysis water unit 100, coal gasification unit 200
Syngas outlet is connected with the synthesis gas entrance of clean unit 300, clean gas outlet, the electrolysis water unit of clean unit 300
100 hydrogen outlet and periodic off-gases mention hydrogen outlet respectively with purified gas entrance, hydrogen inlet and the periodic off-gases of compression unit 400
It mentions hydrogen inlet to be connected, the compressed gas outlet of compression unit 400 is connected with the compressed gas entrance of methanol synthesis unit 500.
The methanol purge gas outlet of methanol synthesis unit 500 is connected with the entrance of isolation of purified unit 600, isolation of purified list
The outlet of member 600 is connected with the methanol purge gas entrance for the purification that periodic off-gases mention hydrogen unit 700, and periodic off-gases mention hydrogen unit 700
The methanol purge gas of purification propose hydrogen outlet and be connected with the periodic off-gases of compression unit 400 extraction hydrogen inlet, periodic off-gases mention hydrogen
The stripping gas outlet of unit 700 is connected with the gaseous mixture entrance of boiler 800, and flue gas is discharged in the exhanst gas outlet of boiler 800.
Embodiment 3
Referring to attached drawing 3, a kind of synthesising gas systeming carbinol device of no transformation system, comprising:
Electrolysis water unit 100, coal gasification unit 200, clean unit 300, compression unit 400, methanol synthesis unit 500,
Methanol rectification unit 900 and tank field 1000, electrolysis water unit 100 include oxygen outlet and hydrogen outlet, and coal gasification unit 200 is wrapped
Coal entrance, oxygen intake and syngas outlet are included, compression unit 400 includes that hydrogen inlet, purified gas entrance and compressed gas export,
Methanol synthesis unit 500 includes compressed gas entrance and methanol purge gas outlet, crude carbinol outlet, and methanol rectification unit 900 includes
Crude carbinol entrance and refined methanol product outlet, tank field 1000 include refined methanol finished-product entrance and refined methanol product outlet.
The oxygen intake of coal gasification unit 200 is connect with the oxygen outlet of electrolysis water unit 100, coal gasification unit 200
Syngas outlet is connected with the synthesis gas entrance of clean unit 300, clean gas outlet, the electrolysis water unit of clean unit 300
100 hydrogen outlet and periodic off-gases mention hydrogen outlet respectively with purified gas entrance, hydrogen inlet and the periodic off-gases of compression unit 400
It mentions hydrogen inlet to be connected, the compressed gas outlet of compression unit 400 is connected with the compressed gas entrance of methanol synthesis unit 500.
The crude carbinol outlet of methanol synthesis unit 500 is connected with the crude carbinol entrance of methanol rectification unit 900, methanol essence
It evaporates 900 refined methanol product outlet of unit to be connected with the refined methanol finished-product entrance of tank field 1000, the refined methanol finished product of tank field 1000
Outlet obtains refined methanol finished product.
Embodiment 4
Referring to attached Figure 4 and 5, a kind of synthesising gas systeming carbinol device of no transformation system, comprising:
Electrolysis water unit 100, coal gasification unit 200, clean unit 300, compression unit 400 and methanol synthesis unit 500,
Isolation of purified unit 600, periodic off-gases mention hydrogen unit 700, boiler 800, methanol rectification unit 900 and tank field 1000, electrolysis water list
Member 100 includes oxygen outlet and hydrogen outlet, and coal gasification unit 200 includes coal entrance, oxygen intake and syngas outlet, purification
Unit 300 includes synthesis gas entrance and clean gas outlet, and compression unit 400 is mentioned including hydrogen inlet, purified gas entrance, periodic off-gases
Hydrogen inlet and compressed gas outlet, methanol synthesis unit 500 include that compressed gas entrance and methanol purge gas outlet, crude carbinol go out
Mouthful, isolation of purified unit 600 includes methanol purge gas entrance and exit, and it is net that periodic off-gases propose separation of the hydrogen unit 700 including purification
Change gas access, the methanol purge gas of purification mentions hydrogen outlet reconciliation suction outlet, boiler 800 includes that gaseous mixture entrance and flue gas go out
Mouthful, methanol rectification unit 900 includes crude carbinol entrance and refined methanol product outlet, flash distillation vapor outlet, and tank field 1000 includes smart first
Alcohol finished-product entrance and refined methanol product outlet, with further reference to Fig. 5, isolation of purified unit 600 includes sequentially connected gas-liquid point
From device 610, heat exchanger 620 and membrane separator 630.
The oxygen intake of coal gasification unit 200 is connect with the oxygen outlet of electrolysis water unit 100, coal gasification unit 200
Syngas outlet is connected with the synthesis gas entrance of clean unit 300, clean gas outlet, the electrolysis water unit of clean unit 300
The periodic off-gases that 100 hydrogen outlet, periodic off-gases mention hydrogen unit 700 extract the hydrogen outlet purified gas with compression unit 400 respectively
Entrance, hydrogen inlet, periodic off-gases extract hydrogen inlet and are connected, the compressed gas outlet of compression unit 400 and methanol synthesis unit
500 compressed gas entrance is connected.
The methanol purge gas outlet of methanol synthesis unit 500 is connected with the entrance of isolation of purified unit 600, isolation of purified list
The outlet of member 600 is connected with the methanol purge gas entrance for the purification that periodic off-gases mention hydrogen unit 700, and periodic off-gases mention hydrogen unit 700
Periodic off-gases propose hydrogen outlet and be connected with the periodic off-gases of compression unit 400 extraction hydrogen inlet, periodic off-gases mention to be mentioned in hydrogen unit 700
The gaseous mixture pipeline and boiler 800 for taking the flash steam in the stripping gas generated after hydrogen and methanol rectification unit 900 to be mixed to get
Gaseous mixture entrance be connected, flue gas is discharged in the exhanst gas outlet of boiler 800.
The crude carbinol outlet of methanol synthesis unit 500 is connected with the crude carbinol entrance of methanol rectification unit 900, methanol essence
It evaporates 900 refined methanol product outlet of unit to be connected with the refined methanol finished-product entrance of tank field 1000, the refined methanol finished product of tank field 1000
Outlet obtains refined methanol finished product.
Embodiment 5
A kind of synthesising gas systeming carbinol technique of no transformation system, comprising the following steps:
Gasification reaction occurs in coal gasification unit 200 and generates synthesis for the oxygen that coal and electrolysis water electrolysis cells 1 are generated
Gas, wherein the mass ratio of feed coal and oxygen is 0.8:2-1.5:2, and synthesis gas is generated rich in CO, H2And CO2Synthesis gas.
Above-mentioned synthesis gas is sent into clean unit 300 and carries out purified treatment, the temperature of purified treatment is 200-260 DEG C, pressure
Power is 3.5-5MpaG, and the hydrogen that the decontaminating syngas and electrolysis water unit 100 after purified treatment generate enters compression unit jointly
400 carry out compression processing, and the temperature of compression processing is 24-120 DEG C, pressure 4.5-7MpaG, and methanol is sent into after compression processing
It is reacted in synthesis unit 500, adjusting hydrogen-carbon ratio is 2.0-4.5, carries out reaction and generates crude carbinol and methanol purge gas.
Embodiment 6
A kind of synthesising gas systeming carbinol technique of no transformation system, comprising the following steps:
Gasification reaction occurs in coal gasification unit 200 and generates synthesis for the oxygen that coal and electrolysis water electrolysis cells 1 are generated
Gas, wherein the mass ratio of feed coal and oxygen is 0.8:2-1.5:2, and synthesis gas is generated rich in CO, H2And CO2Synthesis gas.
Above-mentioned synthesis gas is sent into clean unit 300 and carries out purified treatment, the temperature of purified treatment is 200-260 DEG C, pressure
Power is 3.5-5MpaG, and the hydrogen that the decontaminating syngas and electrolysis water unit 100 after purified treatment generate enters compression unit jointly
400 carry out compression processing, and the temperature of compression processing is 24-120 DEG C, pressure 4.5-7MpaG, and methanol is sent into after compression processing
It is reacted in synthesis unit 500, adjusting hydrogen-carbon ratio is 2.0-4.5, carries out reaction and generates crude carbinol and methanol purge gas.
The methanol purge gas that the reaction of methanol synthesis unit 500 generates is transported to isolation of purified unit 600 separate only
Change and then input periodic off-gases mention in hydrogen unit 700, periodic off-gases are mentioned into the hydrogen extracted in hydrogen unit 700 as compression unit
The make-up gas of hydrogen in 400, since ton methanol generates about 120-160m during synthesizing methanol3Periodic off-gases (main component has:
H2: 68-73%, CO:2-5%, CO2: 0.5-2.3%, N2: 12-16.5% and CH4: 5.4-8.5% etc.), periodic off-gases successively pass through
Pressure-variable adsorption is carried out after gas-liquid separator 610, heat exchanger 620 and membrane separator 630 and extracts hydrogen (i.e. PSA mentions hydrogen), will be extracted
(according to 1,500,000 tons of methanol meters are produced per year, the amounts of hydrogen extracted in periodic off-gases is 5000-8000m to hydrogen out3/ h) it is incorporated to compression
Unit 400 supplements gas as hydrogen feed.
Periodic off-gases are mentioned to the sudden strain of a muscle extracting the stripping gas generated after hydrogen and methanol rectification unit 900 in hydrogen unit 700 and generating
The gaseous mixture that steam merges generation is transported to burning in boiler 800 and generates flue gas outlet.
The crude carbinol that the reaction of methanol synthesis unit 500 generates is delivered in methanol rectification unit 900, by methanol rectification list
The refined methanol finished product generated in member 900 delivers into the storage of tank field 1000 or sends outside.
To sum up, the embodiment of the present invention provides the synthesising gas systeming carbinol device and its technique of a kind of no transformation system, the implementation
Device used by example produces methanol using water electrolysis hydrogen production and oxygen and coal gas complementary coupled, the device without transformation system,
Pressure-variable adsorption and decarbonization system are carried out in Production of methanol using the device, the oxygen and hydrogen directly generated using electrolysis water
Gas, electrolysis water oxygen and hydrogen do not generate other pollutants in electrolytic process, not only environmentally protective, but also significantly reduce
The problem of complexity and environmental pollution in raw coal methanol process, improve the purity and yield of methanol.
Embodiments described above is a part of the embodiment of the present invention, instead of all the embodiments.Reality of the invention
The detailed description for applying example is not intended to limit the range of claimed invention, but is merely representative of selected implementation of the invention
Example.Based on the embodiments of the present invention, obtained by those of ordinary skill in the art without making creative efforts
Every other embodiment, shall fall within the protection scope of the present invention.
Claims (10)
1. a kind of synthesis gas of no transformation system prepares methanol device characterized by comprising electrolysis water unit, coal gasification list
Member, clean unit, compression unit and methanol synthesis unit, the oxygen outlet of the electrolysis water unit and the coal gasification unit
Oxygen intake is connected, and the syngas outlet of the coal gasification unit is connected with the synthesis gas entrance of the clean unit, institute
The clean gas outlet for stating clean unit is connected with the purified gas entrance of the compression unit, and the hydrogen of the electrolysis water unit goes out
Mouth is connected with the hydrogen inlet of the compression unit, compressed gas outlet and the methanol synthesis unit of the compression unit
Compressed gas entrance is connected.
2. the synthesis gas of no transformation system according to claim 1 prepares methanol device, which is characterized in that the synthesis gas
Preparing methanol device further includes that isolation of purified unit and periodic off-gases mention hydrogen unit, and the methanol purge gas of the methanol synthesis unit goes out
Mouth is connected with the entrance of the isolation of purified unit, and the outlet of the isolation of purified unit mentions entering for hydrogen unit with the periodic off-gases
Mouth is connected.
3. the synthesis gas of no transformation system according to claim 2 prepares methanol device, which is characterized in that the separation is net
Changing unit includes sequentially connected gas-liquid separator, heat exchanger and membrane separator.
4. the synthesis gas of no transformation system according to claim 2 prepares methanol device, which is characterized in that the periodic off-gases
The periodic off-gases for mentioning hydrogen unit extract hydrogen outlet and are connected with the periodic off-gases of compression unit extraction hydrogen inlet.
5. the synthesis gas of no transformation system according to claim 1-4 prepares methanol device, which is characterized in that institute
Stating synthesis gas and preparing methanol device further includes methanol rectification unit, crude carbinol outlet and the methanol of the methanol synthesis unit
The crude carbinol entrance of rectification cell is connected.
6. the synthesis gas of no transformation system according to claim 5 prepares methanol device, which is characterized in that the synthesis gas
Preparing methanol device further includes boiler, and flashed vapour, the periodic off-gases of the methanol rectification unit discharge propose the discharge of hydrogen unit
Stripping gas is mixed into gaseous mixture pipeline, and the gaseous mixture pipeline is connected with the boiler.
7. a kind of technique that device according to claim 1-6 prepares methanol, which is characterized in that including following step
It is rapid:
Oxygen made from feed coal and the electrolysis water unit is subjected to gasification reaction in the coal gasification unit and generates synthesis gas,
The synthesis gas is subjected to the synthesis gas after purified treatment is purified in the clean unit, by the purified synthesis gas
It is merged with hydrogen made from the electrolysis water unit according to hydrogen-carbon ratio needed for methanol-fueled CLC, then in the compression unit
It carries out compression processing and obtains compressed gas, the compressed gas is reacted in the methanol synthesis unit, thick first is prepared
Pure and mild methanol purge gas.
8. technique according to claim 7, which is characterized in that the quality of feed coal and oxygen in the coal gasification unit
Than being 200-260 DEG C for the treatment temperature of 0.8:2-1.5:2, the clean unit, pressure 3.5-5MpaG, the compression list
The treatment temperature of member is 24-120 DEG C, pressure 4.5-7MpaG.
9. technique according to claim 7, which is characterized in that the hydrogen-carbon ratio in the methanol synthesis unit is 2.0-
4.5。
10. technique according to claim 7, which is characterized in that the methanol that methanol synthesis unit reaction generates is speeded
It deflates through isolation of purified cell processing, mentions the hydrogen for extracting generation in hydrogen unit as hydrogen in compression unit subsequently into periodic off-gases
Periodic off-gases are proposed the flash distillation for extracting that the stripping gas generated after hydrogen and methanol rectification unit generate in hydrogen unit by the make-up gas of gas
The gaseous mixture that gas merges generation is transported to burning in boiler and generates flue gas outlet, and the methanol synthesis unit is reacted and is generated
Crude carbinol be delivered in methanol rectification unit, by the refined methanol finished product generated in methanol rectification unit store or send outside.
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| CN112457159A (en) * | 2019-09-09 | 2021-03-09 | 中国科学院大连化学物理研究所 | Device for preparing methanol based on coal and methanol preparation process |
| CN113527052A (en) * | 2021-06-17 | 2021-10-22 | 中石化宁波工程有限公司 | Process for preparing methanol from methane |
| CN113563159A (en) * | 2021-08-27 | 2021-10-29 | 陕西润中清洁能源有限公司 | Process and device for preparing methanol from water gas |
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| CN114752418A (en) * | 2022-05-20 | 2022-07-15 | 陕西煤业化工技术研究院有限责任公司 | Coal quality-based utilization system and process for realizing zero carbon emission |
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| CN115959970A (en) * | 2021-10-11 | 2023-04-14 | 新奥科技发展有限公司 | Zero-carbon-emission coal-to-methanol system and method for preparing methanol from coal |
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