CN107916145A - Low-temp methanol washes the method and device of journey mesohigh recycling carbon dioxide - Google Patents
Low-temp methanol washes the method and device of journey mesohigh recycling carbon dioxide Download PDFInfo
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- CN107916145A CN107916145A CN201810024147.2A CN201810024147A CN107916145A CN 107916145 A CN107916145 A CN 107916145A CN 201810024147 A CN201810024147 A CN 201810024147A CN 107916145 A CN107916145 A CN 107916145A
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims abstract description 223
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 216
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 106
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 105
- 238000004064 recycling Methods 0.000 title claims abstract description 35
- 238000000034 method Methods 0.000 title claims abstract description 28
- 239000007789 gas Substances 0.000 claims abstract description 93
- 238000003795 desorption Methods 0.000 claims abstract description 77
- 238000010521 absorption reaction Methods 0.000 claims abstract description 59
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims abstract description 54
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims abstract description 41
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 29
- GBMDVOWEEQVZKZ-UHFFFAOYSA-N methanol;hydrate Chemical compound O.OC GBMDVOWEEQVZKZ-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 26
- 239000011593 sulfur Substances 0.000 claims abstract description 26
- 238000005201 scrubbing Methods 0.000 claims abstract description 21
- 230000001172 regenerating effect Effects 0.000 claims abstract description 9
- 239000007788 liquid Substances 0.000 claims description 26
- 238000006477 desulfuration reaction Methods 0.000 claims description 21
- 230000023556 desulfurization Effects 0.000 claims description 21
- 238000005262 decarbonization Methods 0.000 claims description 18
- 238000001816 cooling Methods 0.000 claims description 17
- 238000007701 flash-distillation Methods 0.000 claims description 6
- 239000011261 inert gas Substances 0.000 claims description 6
- 229910002090 carbon oxide Inorganic materials 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 230000000694 effects Effects 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 230000008929 regeneration Effects 0.000 claims description 3
- 238000011069 regeneration method Methods 0.000 claims description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims 2
- 239000004408 titanium dioxide Substances 0.000 claims 1
- -1 absorption tower Chemical compound 0.000 abstract description 2
- 238000000926 separation method Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 85
- 229960004424 carbon dioxide Drugs 0.000 description 81
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 238000005261 decarburization Methods 0.000 description 10
- 238000005406 washing Methods 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- 239000003245 coal Substances 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 238000011084 recovery Methods 0.000 description 6
- 239000012071 phase Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 238000007906 compression Methods 0.000 description 4
- 230000009615 deamination Effects 0.000 description 4
- 238000006481 deamination reaction Methods 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 239000010865 sewage Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 239000005864 Sulphur Substances 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 230000006835 compression Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000002309 gasification Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- PVXVWWANJIWJOO-UHFFFAOYSA-N 1-(1,3-benzodioxol-5-yl)-N-ethylpropan-2-amine Chemical compound CCNC(C)CC1=CC=C2OCOC2=C1 PVXVWWANJIWJOO-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- 241000790917 Dioxys <bee> Species 0.000 description 2
- QMMZSJPSPRTHGB-UHFFFAOYSA-N MDEA Natural products CC(C)CCCCC=CCC=CC(O)=O QMMZSJPSPRTHGB-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- GCNLQHANGFOQKY-UHFFFAOYSA-N [C+4].[O-2].[O-2].[Ti+4] Chemical compound [C+4].[O-2].[O-2].[Ti+4] GCNLQHANGFOQKY-UHFFFAOYSA-N 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 230000006837 decompression Effects 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000005431 greenhouse gas Substances 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000002918 waste heat Substances 0.000 description 2
- 241000254173 Coleoptera Species 0.000 description 1
- 241000208125 Nicotiana Species 0.000 description 1
- 235000002637 Nicotiana tabacum Nutrition 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000006315 carbonylation Effects 0.000 description 1
- 238000005810 carbonylation reaction Methods 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003034 coal gas Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
- C10K1/00—Purifying combustible gases containing carbon monoxide
- C10K1/08—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors
- C10K1/16—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors with non-aqueous liquids
- C10K1/165—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors with non-aqueous liquids at temperatures below zero degrees Celsius
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
- C10K1/00—Purifying combustible gases containing carbon monoxide
- C10K1/002—Removal of contaminants
- C10K1/003—Removal of contaminants of acid contaminants, e.g. acid gas removal
- C10K1/004—Sulfur containing contaminants, e.g. hydrogen sulfide
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
- C10K1/00—Purifying combustible gases containing carbon monoxide
- C10K1/002—Removal of contaminants
- C10K1/003—Removal of contaminants of acid contaminants, e.g. acid gas removal
- C10K1/005—Carbon dioxide
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2210/00—Purification or separation of specific gases
- C01B2210/0001—Separation or purification processing
- C01B2210/0009—Physical processing
- C01B2210/0025—Physical processing by absorption in liquids
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Combustion & Propulsion (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Gas Separation By Absorption (AREA)
Abstract
The present invention relates to the method and device that a kind of low-temp methanol washes journey mesohigh recycling carbon dioxide, belong to gas separation technique field.A kind of method that low-temp methanol washes journey mesohigh recycling carbon dioxide, comprises the following steps：Absorption tower obtains the first rich solution by the carbon dioxide that lean solution is absorbed in unstripped gas, and absorption tower absorbs the hydrogen sulfide in unstripped gas by the first rich solution and obtains the first sulfur-bearing rich solution；First rich solution is carried out to the carbon dioxide of different pressures twice successively；And the first sulfur-bearing rich solution is subjected to hydrogen sulphide concentration desorption and Mathanol regenerating and recycling.The invention also discloses the device that a kind of low-temp methanol washes journey mesohigh recycling carbon dioxide, including absorption tower, high pressure desorption tower, scrubbing tower, low pressure desorber, flash column, concentration tower, regenerator and methanol-water separating.This method and device can desorb high-pressure carbon dioxide and recycle methanol by the hydrogen sulfide and carbon dioxide in methanol absorption unstrpped gas.
Description
Technical field
The present invention relates to the method and device that a kind of low-temp methanol washes journey mesohigh recycling carbon dioxide, belong to gas point
From technical field.
Background technology
Carbon dioxide is greenhouse gases common in air, is a kind of gaseous compound, density ratio air is big, is slightly soluble in
Water, reacts generation carbonic acid with water.
Carbon dioxide is widely used in the industries such as chemical industry, machinery, food, agricultural, tobacco, since carbon dioxide is greenhouse gas
Carbon dioxide, is delivered to rational position from source of the gas and is sealed up for safekeeping, can reduce carbon emission, while strengthen oil, page by body
The recovery ratio of rock gas etc..Therefore, carbon dioxide industrially has very high application value, at present in the production of carbon dioxide
In, what is obtained is all often the carbon dioxide that pressure is low, impurity component is complicated.In ammonia synthesis, methanol-fueled CLC, carbonylation synthesis, system
The industrial circles such as hydrogen, natural gas, often using absorption and desorption method carbon dioxide removal to meet post-order process requirement, at the same time
The carbon dioxide extremely low to pressure, then high-pressure carbon dioxide is obtained by way of compressor pressurization, fed downstream device utilizes
Or downstream user is delivered to after liquefaction, equipment volume needed for low pressure CO 2 compression process is huge, and work done during compression is high, power consumption
Greatly.Meanwhile factory usually there will be substantial amounts of 40 ~ 140 DEG C or so materials and need to be cooled with circulating water, and cause the waste of energy.
Low-temp methanol washing process is to utilize low-temp methanol by the H in unstripped gas2S、CO2Deng gas removal, since methanol is low
It is big to the absorptive capacity of carbon dioxide under temperature, the high gas products of degree can be purified, in ammonia synthesis, methanol-fueled CLC, city
The multiple fields such as city's coal gas, industrial hydrogen production are widely used, particularly using coal as the coal chemical technology of raw material in using wide
It is general.Usually carbon dioxide is desorbed under low pressure in current low-temp methanol washing process, then high pressure dioxy is obtained by compressor
Change carbon, consume a large amount of electric energy and recirculated cooling water, equipment investment is big.Strengthened and inert gas gas using factory's low temperature exhaust heat heating
Carrying makes carbon dioxide desorb under high pressure, and carbon dioxide desorbs the compression that can be saved needed for follow-up carbon dioxide and moves under high pressure
Power, reduces equipment size, but the technique of the recycling of CO 2 high pressure desorption at present is primarily adapted for use in what room temperature or high temperature absorbed
System, such as absorbs the carbon dioxide in unstrpped gas, displacement volume is low, internal circulating load with methyl diethanolamine aqueous solution amine liquid
Greatly, if using methanol as absorbent in above-mentioned technique, required methanol loop amount is big, and desorption tower top stripping gas can be taken away greatly
The methanol of amount, methanol loss amount is big, and semi lean solution and the substantial amounts of deep cooling low-temperature receiver of lean solution cooling required, energy consumption are very high；It is and above-mentioned
Method does not consider the situation of raw material sulfur-bearing, is not suitable for the processing of Sulfur Contained Raw Gas.
The content of the invention
In view of the foregoing defects the prior art has, the present invention proposes a kind of new low-temp methanol and washes journey mesohigh time
Receive the method and device of carbon dioxide.This method and device by the hydrogen sulfide and carbon dioxide in methanol absorption unstrpped gas,
High-pressure carbon dioxide can be desorbed.
The present invention is realized using following technical solution：
A kind of method that low-temp methanol washes journey mesohigh recycling carbon dioxide, comprises the following steps：
Absorption tower obtains the first rich solution by the carbon dioxide that lean solution is absorbed in unstripped gas, and absorption tower absorbs raw material by the first rich solution
Hydrogen sulfide in gas obtains the first sulfur-bearing rich solution；
First rich solution is carried out to the carbon dioxide of different pressures twice successively；And
First sulfur-bearing rich solution is subjected to hydrogen sulphide concentration desorption and Mathanol regenerating and recycling.
Preferably, the first rich solution is carried out to concretely comprising the following steps for the carbon dioxide of different pressures twice successively：
The first rich solution of part in absorption tower enters high pressure desorption tower and carries out desorption carbon dioxide for the first time, will desorb two
Carbon oxide gas are incorporated into scrubbing tower and slough after methanol to obtain carbon dioxide, while the second rich solution after must desorbing；Second rich solution one
Part is used for hydrogen sulphide concentration and desorbs；Low pressure desorber is incorporated into after the cooling of the second rich solution of another part and carries out second of desorption two
Carbonoxide, while the lean solution after must desorbing, lean solution are recycled back to absorption tower.
Preferably, the first sulfur-bearing rich solution is subjected to hydrogen sulphide concentration desorption and Mathanol regenerating and the specific steps of recycling
For：
The first sulfur-bearing rich solution at absorbing tower bottom is incorporated into flash column to obtain flash gas, after flash distillation liquid enter concentration tower into
One step desorption carbon dioxide obtains stripping gas, and the second rich solution after being depressured with cooling absorbs the desorption that flash gas and concentration tower obtain
Hydrogen sulfide in gas；Concentration tower epimere absorbing liquid absorbs hydrogen sulfide back to flash column；Concentration tower hypomere absorbing liquid enters regeneration
Tower carries out the air lift of carbon dioxide and hydrogen sulfide；Part kettle liquid in regenerator enters methanol-water separating and carries out Methanol Recovery,
The methanol of recycling returns to regenerator.
Preferably, high pressure desorption tower desorbs carbon dioxide in the case where heating the collective effect with inert gas air lift.
Preferably, the desorption pressures of high pressure desorption tower are 0.5MPa (A)~10MPa (A), the outlet temperature of high pressure desorption tower
Spend for -10~140 DEG C, the ratio of inert gas air lift amount and high pressure desorption carbon dioxide is 0.001~0.3, and gas stripping gas enters
The temperature of high pressure desorption tower is -10~140 DEG C.
Preferably, the desorption pressures of low pressure desorber are 0.01MPa (A)~0.3MPa (A), inert gas air lift amount with
The ratio for desorbing carbon dioxide is 0.001~0.42, and the temperature that the second rich solution enters low pressure desorber is -55 DEG C ~ 0 DEG C, air lift
The temperature that gas enters low pressure desorber is -55 ~ 0 DEG C.
Preferably, the tower bottoms of flash column enter concentration tower after under the pressure of 0.01MPa (A)~0.3MPa (A) into
Row desorption carbon dioxide.
A kind of low-temp methanol washes the device of journey mesohigh recycling carbon dioxide, including absorption tower, high pressure desorption tower, washing
Tower, low pressure desorber, flash column, concentration tower, regenerator and methanol-water separating；
Absorption tower includes desulfurization section, stage casing and decarbonization section, is provided with cooler on stage casing, absorption tower respectively with high pressure desorption
Tower, scrubbing tower, low pressure desorber, flash column, regenerator and methanol-water separating connection；
High pressure desorption tower is also connected with low pressure desorber, scrubbing tower respectively；
Low pressure desorber is also connected with flash column, concentration tower respectively；
Flash column is also connected with concentration tower；
Concentration tower is also connected with regenerator；
Regenerator is also connected with methanol-water separating；
Absorption tower is provided with unstrpped gas pipeline, and knockout drum I is provided with unstrpped gas pipeline, and the top of regenerator is set
There is knockout drum II, knockout drum II is connected by knockout drum III with concentration tower, is further included and is arranged on absorption tower, height
Heat exchange is both provided with pressure desorber, scrubbing tower, low pressure desorber, flash column, concentration tower, regenerator and methanol-water separating
Device.
Preferably, the top of methanol-water separating is provided with condenser, condenser is used to carry out heat with high pressure desorption tower
Amount coupling.
The beneficial effects of the invention are as follows：
（1）The present invention is using the hydrogen sulfide in methanol simultaneous removing unstrpped gas and carbon dioxide and obtains high-pressure carbon dioxide,
Desulfurization and decarburization occasion are can be widely applied to, the present invention uses low-temp methanol washing process, since methanol is at low temperature to hydrogen sulfide
Big with the absorptive capacity of carbon dioxide, internal circulating load is small, the high desulfurization of degree, decarburization gas can be purified, using factory
Waste heat obtains high-pressure carbon dioxide, saves a large amount of power costs.
（2）The present invention absorbs hydrogen sulfide using the first rich solution after cooling, adds available for high pressure desorption carbon dioxide
Amount without sulphur rich methanol, improves the yield of high-pressure carbon dioxide.
（3）The present invention has carried out Methanol Recovery to the carbon dioxide of high pressure desorption, solves high pressure desorption tower in desorption two
The problem of a large amount of methanol are taken away during carbonoxide, substantially reduces the loss of methanol.
（4）The present invention carries out CO 2 high pressure desorption during low-temp methanol is washed, and absorbs and the high pressure desorption temperature difference is big,
Boosting is high, complicated, expensive compressor is not required in some application scenarios, or compressor series, occupation of land and investment is greatly decreased.
（5）Compared with the decarbonization solvent of the achievable CO 2 high pressure desorption such as MDEA, the present invention makes the method for the present invention
Methanol property is stablized, and cheap and easy to get, solvent cost of investment is low.
Brief description of the drawings
Fig. 1 is the structure and method for the device embodiment one that low-temp methanol of the present invention washes journey mesohigh recycling carbon dioxide
Flow chart.
Fig. 2 is the structure and method for the device embodiment two that low-temp methanol of the present invention washes journey mesohigh recycling carbon dioxide
Flow chart.
Embodiment
In order to which the object of the invention, technical solution is more clearly understood, below in conjunction with the accompanying drawings, the present invention is made further detailed
Describe in detail bright.
Embodiment one：
By taking 1,650,000 tons/year of methanol devices as an example, the operating time in year is 8000h, coal by gasifying, convert, enter low temperature after deamination
Methanol washes workshop section, and pressure is 3.14MPa (A), and purification section unstripped gas treating capacity is 776720 Nm3/h, the main group of unstrpped gas
Point concentration is that hydrogen is 45.9%, carbon monoxide 20.4%, carbon dioxide 32.9%, nitrogen 0.3%, water 0.3%, hydrogen sulfide
For 0.2%.
As shown in Figure 1, a kind of method that low-temp methanol washes journey mesohigh recycling carbon dioxide, comprises the following steps：Inhale
Receive tower and the first rich solution is obtained by the carbon dioxide that lean solution is absorbed in unstripped gas, absorption tower is absorbed in unstripped gas by the first rich solution
Hydrogen sulfide obtains the first sulfur-bearing rich solution；First rich solution is carried out to the carbon dioxide of different pressures twice successively；And by first
Sulfur-bearing rich solution carries out hydrogen sulphide concentration desorption and Mathanol regenerating and recycling.Also disclose a kind of low-temp methanol and wash journey mesohigh time
Receive carbon dioxide device, including absorption tower 1, high pressure desorption tower 2, scrubbing tower 4, low pressure desorber 3, flash column 5, concentration tower 6,
Regenerator 7 and methanol-water separating 8；Absorption tower 1 includes desulfurization section, decarbonization section, and cooler is provided with the stage casing of decarbonization section
9, absorption tower 1 is separated with high pressure desorption tower 2, scrubbing tower 4, low pressure desorber 3, flash column 5, regenerator 7 and methanol-water respectively
Tower 8 connects；High pressure desorption tower 2 is also connected with low pressure desorber 3, scrubbing tower 4 respectively；Low pressure desorber 3 also respectively with flash column
5th, concentration tower 6 connects；Flash column 5 is also connected with concentration tower 6；Concentration tower 6 is also connected with regenerator 7；Regenerator 7 is gone back and methanol-water
Knockout tower 8 connects；Absorption tower 1 is provided with unstrpped gas pipeline, and knockout drum I 21 is provided with unstrpped gas pipeline, regeneration
The top of tower is provided with knockout drum II 22, and knockout drum II 22 is connected by knockout drum III 23 with concentration tower 6, inhales
Receive tower 1, high pressure desorption tower 2, scrubbing tower 4, low pressure desorber 3, flash column 5, concentration tower 6, regenerator 7 and methanol-water separating
Heat exchanger 10 is both provided with 8, heat exchanger 10, as needed, connecting pipe are also equipped with the connecting pipe between tower and tower
On be additionally provided with it is multiple pump 11.
With continued reference to Fig. 1, absorption tower absorbs the carbon dioxide in unstripped gas by lean solution and obtains the first rich solution, and absorption tower passes through
The hydrogen sulfide that first rich solution is absorbed in unstripped gas obtains concretely comprising the following steps for the first sulfur-bearing rich solution：Unstripped gas 101 after deamination
Spray methanol to remove water, obtain gas phase 102 into knockout drum I 21 after cooling, gas phase 102 enters absorption tower 1, and absorption tower 1 is including upper
The decarbonization section and desulfurization section of lower setting, desulfurization section are located at the lower section of decarbonization section, and lean solution is passed through on the top of decarbonization section, the lean solution bag
- 45 DEG C of smart lean solution 105 and -46 DEG C of semi lean solution 106 are included, the first rich solution, 1 decarburization of absorption tower are obtained after lean solution absorbing carbon dioxide
Obtained the first rich solution of section is partly into desulfurization section and absorbs hydrogen sulfide in unstripped gas, after absorbing the hydrogen sulfide in unstripped gas
The first sulfur-bearing rich solution is obtained, the first rich solution of decarbonization section remainder enters high pressure desorption tower 2.The stage casing on absorption tower 1 is provided with cold
But device 9, the cooler 9 be in order to increase assimilation effect, after desulfurization and decarburization, what absorption tower 1 obtained after desulfurization and decarburization
Purified gas 104 is discharged after reaching methanol-fueled CLC requirement.
With continued reference to Fig. 1, first rich solution is subjected to the specific of the carbon dioxide of different pressures twice successively and is walked
Suddenly it is：It is high pressure desorption first, the first rich solution of part of 1 decarbonization section bottom of absorption tower is used as the absorbing liquid of desulfurization section, its remaining part
Carbon dioxide is set to exist by way of heating, nitrogen air lift in high pressure desorption tower 2 after the first rich solution boosting heat exchange divided
Desorbed under 5.8MPa (A) pressure, desorb air cooling after enter scrubbing tower 4 and in scrubbing tower 4 with water by stripping gas
Methanol absorption gets off, and obtains the high-pressure carbon dioxide 72500Nm of 5.8MPa (A)3/ h, the high-pressure carbon dioxide can be used for coal gasification
The powder coal gasification furnace carrier gas of device；Then low pressure desorption is carried out, high pressure desorption tower 2 obtains the second rich solution, the second rich solution after desorbing
After being cooled to -30 DEG C, a part is used for hydrogen sulphide concentration, and the second rich solution of another part 114 exists as the charging of low pressure desorber 3
Desorbed under 0.13MPa (A) pressure, obtain the carbon dioxide of 0.13MPa (A), meanwhile, bottom of towe low-pressure nitrogen is into promoting the circulation of qi
Carry, obtain -48 DEG C of semi lean solution, obtained semi lean solution 106 returns to absorption tower 1 after pump pressurizes and is continuing with as absorbing liquid.
With continued reference to Fig. 1, the first sulfur-bearing rich solution is subjected to hydrogen sulphide concentration desorption and Mathanol regenerating and the tool of recycling
Body step is：1 desulfurization section the first sulfur-bearing rich solution of absorption tower enters flash column 5 after being cooled to -33 DEG C, by titanium dioxide carbon flash therein
It is steamed out, flash gas is obtained after flash distillation, contain a small amount of hydrogen sulfide in flash gas, the hydrogen sulfide in flash gas is with cold
But the second rich solution 115 after being depressured absorbs.Liquid in flash column 5 after flash distillation then enters the hypomere of concentration tower 6, in 0.13MPa
(A) further by carbon dioxide under pressure, 122 air lift of low-pressure nitrogen of concentration tower 6, the hydrogen sulfide flash distillation in stripping gas
5 epimere liquid 120 of tower and the second rich solution 116 after being depressured with cooling are absorbed, the tower top tail gas 119 of flash column 5 and concentration
Hydrogen sulfide content in the tower top tail gas 123 of tower 6 is below environmental protection standard setting.124 cold of epimere absorbing liquid of concentration tower 6
Flash column 5 is returned after utilization and absorbs hydrogen sulfide.Enter regenerator 7 after 125 cryogenic energy utilization of hypomere kettle liquid of concentration tower 6, by dioxy
Change carbon and hydrogen sulfide is stripped out by the tower reactor reboiler in regenerator 7, the overhead gas of regenerator 7 recycle first by cooling down
The concentration of alcohol after cure hydrogen is 29.9%, and the overhead gas of regenerator 7 are sent to sulfur recovery workshop section and recycle hydrogen sulfide, and tower bottoms is big
Part pressurizes, cools down as smart poor methanol 105, exchange heat returns to absorption tower 1 after extremely -45 DEG C, remaining kettle liquid enters methanol moisture
Water methanol is removed from tower 8 and unstripped gas, washing tower reactor containing alcohol water returns again in the recycling methanol of methanol-water separating 8, the methanol of recycling
Raw tower 7, the tower reactor sewage of methanol-water separating 8 is then to sewage treatment plant.
Embodiment two：
By taking 500,000 tons/year of synthetic ammonia installations as an example, the operating time in year is 8000h, is entered after coal gasification, conversion, deamination low
Warm washing device for methanol unstripped gas treating capacity is 245000Nm3/h, and pressure is 5.87MPa (A).The method that high pressure recycles carbon dioxide
As shown in Figure 2.101 key component concentration of unstripped gas is that hydrogen is 54.2%, carbon monoxide 1.0%, carbon dioxide 43.7%,
Nitrogen is 0.3%, hydrogen sulfide 0.5%, argon gas 0.09%, methane 0.02%, water 0.19%.
As shown in Fig. 2, a kind of method that low-temp methanol washes journey mesohigh recycling carbon dioxide, comprises the following steps：Inhale
Receive tower and the first rich solution is obtained by the carbon dioxide that lean solution is absorbed in unstripped gas, absorption tower is absorbed in unstripped gas by the first rich solution
Hydrogen sulfide obtains the first sulfur-bearing rich solution；First rich solution is carried out to the carbon dioxide of different pressures twice successively；And by first
Sulfur-bearing rich solution carries out hydrogen sulphide concentration desorption and Mathanol regenerating and recycling.Also disclose a kind of low-temp methanol and wash journey mesohigh time
Receive carbon dioxide device, including absorption tower 1, high pressure desorption tower 2, scrubbing tower 4, low pressure desorber 3, flash column 5, concentration tower 6,
Regenerator 7 and methanol-water separating 8；Absorption tower 1 includes desulfurization section, decarbonization section, and cooler is provided with the stage casing of decarbonization section,
Absorption tower 1 respectively with high pressure desorption tower 2, scrubbing tower 4, low pressure desorber 3, flash column 5, regenerator 7 and methanol-water separating 8
Connection；High pressure desorption tower 2 is also connected with low pressure desorber 3, scrubbing tower 4 respectively；Low pressure desorber 3 also respectively with flash column 5, dense
Contracting tower 6 connects；Flash column 5 is also connected with concentration tower 6；Concentration tower 6 is also connected with regenerator 7；Regenerator 7 is also separated with methanol-water
Tower 8 connects；Absorption tower 1 is provided with unstrpped gas pipeline, and knockout drum I 21 is provided with unstrpped gas pipeline, regenerator 7
Top is provided with knockout drum II 22, and knockout drum II 22 is connected by knockout drum III 23 with concentration tower 6, absorption tower
1st, on high pressure desorption tower 2, scrubbing tower 4, low pressure desorber 3, flash column 5, concentration tower 6, regenerator 7 and methanol-water separating 8
Heat exchanger 10 is both provided with, heat exchanger 10 is also equipped with the connecting pipe between tower and tower, as needed, on connecting pipe also
It is provided with multiple pumps 11.In the present embodiment, the top of methanol-water separating 8 is provided with condenser 91, and condenser 91 is used for and institute
State high pressure desorption tower 2 and carry out heat coupling.
With continued reference to Fig. 2, absorption tower absorbs the carbon dioxide in unstripped gas by lean solution and obtains the first rich solution, and absorption tower passes through
The hydrogen sulfide that first rich solution is absorbed in unstripped gas obtains concretely comprising the following steps for the first sulfur-bearing rich solution：Unstripped gas 101 after deamination
Spray methanol to remove water, obtain gas phase 102 into knockout drum I 21 after cooling, gas phase 102 enters absorption tower 1, and absorption tower 1 is including upper
The decarbonization section and desulfurization section of lower setting, desulfurization section are located at the lower section of decarbonization section, and lean solution is passed through on the top of decarbonization section, the lean solution bag
- 62 DEG C of smart lean solution 105 and -65 DEG C of semi lean solution 106 are included, the first rich solution, 1 decarburization of absorption tower are obtained after lean solution absorbing carbon dioxide
The first rich solution that section obtains is partly into desulfurization section as the hydrogen sulfide in absorbing liquid absorption unstripped gas, and the first rich solution absorbs former
Expect to obtain the first sulfur-bearing rich solution after the hydrogen sulfide in gas, the first rich solution of decarbonization section remainder enters high pressure desorption tower 2.Absorb
The stage casing of tower 1 is provided with cooler 9, which can increase assimilation effect, and after desulfurization and decarburization, absorption tower 1 is de-
The purified gas 104 obtained after sulphur decarburization is discharged after reaching methanol-fueled CLC requirement.
With continued reference to Fig. 2, first rich solution is subjected to the specific of the carbon dioxide of different pressures twice successively and is walked
Suddenly it is：It is high pressure desorption first, the first rich solution of part of 1 decarbonization section bottom of absorption tower is used as the absorbing liquid of desulfurization section, its remaining part
Carbon dioxide is made at 5.5MPa (A) by heat exchanger 9 and heater 38 in high pressure desorption tower 2 after dividing the boosting heat exchange of the first rich solution
Pressure under desorbed, stripping gas wherein under methanol absorption, will be obtained after being cooled to 40 DEG C in scrubbing tower 4 with water
5.5MPa (A) high-pressure carbon dioxide 91.7t/h, obtained high-pressure carbon dioxide can be routed directly to the compression of urea workshop section, can also
After liquefaction needed for pump boosts to urea workshop section pressure；Then low pressure desorption is carried out, high pressure desorption tower 2 obtains second after desorbing rich
Liquid, after the second rich solution is cooled to -40 DEG C, a part is used for hydrogen sulphide concentration, and the second rich solution of another part 114 is desorbed as low pressure
The charging of tower 3 is desorbed under 0.13MPa (A) pressure, and bottom of towe carries out air lift with low-pressure nitrogen, obtains -65 DEG C of semi lean solution,
Obtained semi lean solution 106 returns to absorption tower 1 after pump pressurizes and is continuing with as absorbing liquid.
With continued reference to Fig. 2, the first sulfur-bearing rich solution is subjected to hydrogen sulphide concentration desorption and Mathanol regenerating and the tool of recycling
Body step is：1 desulfurization section the first sulfur-bearing rich solution of absorption tower enters flash column 5 after being cooled to -33 DEG C, by titanium dioxide carbon flash therein
It is steamed out, contains a small amount of hydrogen sulfide in flash gas, the hydrogen sulfide in flash gas is used with the second rich solution after cooling decompression
115 absorb, and the liquid in flash column 5 after flash distillation then enters the hypomere of concentration tower 6, further by two under 0.13MPa (A) pressure
Carbonoxide desorbs, 122 air lift of low-pressure nitrogen of concentration tower 6, and the hydrogen sulfide in stripping gas is with 5 epimere liquid 120 of flash column and uses
The second rich solution 116 after cooling decompression is absorbed, in the tower top tail gas 119 of flash column 5 and the tower top tail gas 123 of concentration tower 6
Hydrogen sulfide content be below environmental protection standard setting.Flash column 5 is returned after 124 cryogenic energy utilization of epimere absorbing liquid of concentration tower 6
Absorb hydrogen sulfide.Enter regenerator 7 after 125 cryogenic energy utilization of hypomere kettle liquid of concentration tower 6, carbon dioxide and hydrogen sulfide are passed through again
Tower reactor reboiler in raw tower 7 strips out, and the overhead gas of regenerator 7 are by cooling down the concentration of recycling methanol after cure hydrogen
29.9%, the overhead gas of regenerator 7 are sent to sulfur recovery workshop section and recycle hydrogen sulfide, tower bottoms is mostly as smart poor methanol 105
Absorption tower 1 is returned to after extremely -45 DEG C of pressurization, cooling, heat exchange, remaining kettle liquid enters methanol-water separating 8 and removes water beetle with unstripped gas
Alcohol, washing tower reactor containing alcohol water recycle methanol in methanol-water separating 8, and the top of methanol-water separating 8 is provided with condenser 91, cold
Condenser 91 is used to couple with the progress heat of high pressure desorption tower 2.A methanol part for condensation is as reflux, uncooled gas phase and one
Partial Liquid Phase methanol returns to regenerator 7, and the tower reactor sewage of methanol-water separating 8 is then to sewage treatment plant.
The present invention is using the hydrogen sulfide in methanol simultaneous removing unstrpped gas and carbon dioxide and obtains high-pressure carbon dioxide,
Desulfurization and decarburization occasion are can be widely applied to, the present invention uses low-temp methanol washing process, since methanol is at low temperature to hydrogen sulfide
Big with the absorptive capacity of carbon dioxide, internal circulating load is small, the high desulfurization of degree, decarburization gas can be purified, using factory
Waste heat obtains high-pressure carbon dioxide, saves a large amount of power costs.The present invention absorbs hydrogen sulfide using the first rich solution after cooling, increases
Add and can be used for amount of the high pressure desorption carbon dioxide without sulphur rich methanol, improved the yield of high-pressure carbon dioxide.The present invention is to height
The carbon dioxide of pressure desorption has carried out Methanol Recovery, solves high pressure desorption tower and takes away a large amount of methanol when desorbing carbon dioxide
Problem, substantially reduces the loss of methanol.The present invention during low-temp methanol is washed carry out CO 2 high pressure desorption, absorb and
The high pressure desorption temperature difference is big, and boosting is high, and complicated, expensive compressor is not required in some application scenarios, or be greatly decreased compressor series,
Take up an area and invest.
The method of the present invention compared with the decarbonization solvent of the achievable CO 2 high pressure such as MDEA desorption, what the present invention used
Methanol property is stablized, and cheap and easy to get, solvent cost of investment is low.
Basic principle, main feature and the advantages of the present invention of the present invention has been shown and described above.The technology of the industry
Personnel are it should be appreciated that the present invention is not limited to the above embodiments, and the above embodiments and description only describe this
The principle of invention, various changes and modifications of the present invention are possible without departing from the spirit and scope of the present invention, these changes
Change and improvement all fall within the protetion scope of the claimed invention.The claimed scope of the invention by appended claims and its
Equivalent defines.
Claims (9)
1. a kind of method that low-temp methanol washes journey mesohigh recycling carbon dioxide, it is characterised in that comprise the following steps：
Absorption tower absorbs the carbon dioxide in unstripped gas by lean solution and obtains the first rich solution, and absorption tower is absorbed by first rich solution
Hydrogen sulfide in unstripped gas obtains the first sulfur-bearing rich solution；
First rich solution is carried out to the carbon dioxide of different pressures twice successively；And
The first sulfur-bearing rich solution is subjected to hydrogen sulphide concentration desorption and Mathanol regenerating and recycling.
2. the method that low-temp methanol according to claim 1 washes journey mesohigh recycling carbon dioxide, it is characterised in that institute
State and the first rich solution is carried out to concretely comprising the following steps for the carbon dioxide of different pressures twice successively：
The first rich solution of part in absorption tower enters high pressure desorption tower and carries out desorption carbon dioxide for the first time, will desorb two
Carbon oxide gas are incorporated into scrubbing tower and slough after methanol to obtain carbon dioxide, while the second rich solution after must desorbing；Described second is rich
A liquid part is used for hydrogen sulphide concentration and desorbs；Low pressure desorber is incorporated into after the cooling of the second rich solution of another part and carries out second of solution
Carbon dioxide is inhaled, while the lean solution after must desorbing, the lean solution are recycled back to absorption tower.
3. the method that low-temp methanol according to claim 1 washes journey mesohigh recycling carbon dioxide, it is characterised in that institute
State and concretely comprise the following steps the progress hydrogen sulphide concentration desorption of the first sulfur-bearing rich solution and Mathanol regenerating with what is recycled：
The first sulfur-bearing rich solution at absorbing tower bottom is incorporated into flash column and obtains flash gas, the liquid after flash distillation enters concentration tower
Further desorption carbon dioxide obtains stripping gas, and the second rich solution after being depressured with cooling absorbs the solution that flash gas and concentration tower obtain
Hydrogen sulfide in air-breathing；Concentration tower epimere absorbing liquid absorbs hydrogen sulfide back to flash column；Concentration tower hypomere absorbing liquid enters again
Raw tower carries out the air lift of carbon dioxide and hydrogen sulfide；Part kettle liquid in regenerator enters methanol-water separating and carries out methanol time
Receive, the methanol of recycling returns to regenerator.
4. the method that low-temp methanol according to claim 2 washes journey mesohigh recycling carbon dioxide, it is characterised in that high
Pressure desorber desorbs carbon dioxide in the case where heating the collective effect with inert gas air lift.
5. the method that low-temp methanol according to claim 4 washes journey mesohigh recycling carbon dioxide, it is characterised in that high
The desorption pressures of pressure desorber are 0.5MPa (A)~10MPa (A), and the outlet temperature of high pressure desorption tower is -10~140 DEG C, inertia
Gas air lift amount and the ratio of high pressure desorption carbon dioxide are 0.001~0.3, gas stripping gas enter the temperature of high pressure desorption tower for-
10~140 DEG C.
6. the method that low-temp methanol according to claim 2 washes journey mesohigh recycling carbon dioxide, it is characterised in that low
The desorption pressures of pressure desorber are 0.01MPa (A)~0.3MPa (A), inert gas air lift amount and the ratio of desorption carbon dioxide
For 0.001~0.42, the temperature that the second rich solution enters low pressure desorber is -55 DEG C ~ 0 DEG C, and gas stripping gas enters low pressure desorber
Temperature is -55 ~ 0 DEG C.
7. the method that low-temp methanol according to claim 3 washes journey mesohigh recycling carbon dioxide, it is characterised in that
The tower bottoms of flash column carries out desorption titanium dioxide after entering concentration tower under the pressure of 0.01MPa (A)~0.3MPa (A)
Carbon.
8. a kind of low-temp methanol washes the device of journey mesohigh recycling carbon dioxide, it is characterised in that including absorption tower, high pressure solution
Inhale tower, scrubbing tower, low pressure desorber, flash column, concentration tower, regenerator and methanol-water separating；
The absorption tower includes desulfurization section, stage casing and decarbonization section, and cooler, the absorption tower difference are provided with the stage casing
Connected with the high pressure desorption tower, scrubbing tower, low pressure desorber, flash column, regenerator and methanol-water separating；
The high pressure desorption tower is also connected with the low pressure desorber, scrubbing tower respectively；
The low pressure desorber is also connected with the flash column, concentration tower respectively；
The flash column is also connected with the concentration tower；
The concentration tower is also connected with the regenerator；
The regenerator is also connected with the methanol-water separating；
The absorption tower is provided with unstrpped gas pipeline, and knockout drum I, the regeneration are provided with the unstrpped gas pipeline
The top of tower is provided with knockout drum II, and the knockout drum II is connected by knockout drum III with the concentration tower,
Further include be arranged on the absorption tower, high pressure desorption tower, scrubbing tower, low pressure desorber, flash column, concentration tower, regenerator and
Heat exchanger is both provided with methanol-water separating.
9. low-temp methanol according to claim 8 washes the device of journey mesohigh recycling carbon dioxide, it is characterised in that institute
The top for stating methanol-water separating is provided with condenser, and the condenser is used to couple with high pressure desorption tower progress heat.
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| CN111453703A (en) * | 2020-03-31 | 2020-07-28 | 陕西聚能新创煤化科技有限公司 | Method and device for producing high-concentration hydrogen sulfide by low-temperature methanol purification |
| CN111715033A (en) * | 2019-03-22 | 2020-09-29 | 国家能源投资集团有限责任公司 | CO (carbon monoxide)2Trapping device and method |
| CN113144831A (en) * | 2021-03-08 | 2021-07-23 | 灵谷化工集团有限公司 | Device and method for performing low-temperature methanol double washing based on heat exchange and modified methanol |
| CN113336193A (en) * | 2021-06-24 | 2021-09-03 | 中石化南京化工研究院有限公司 | Decarburization device and method for preparing reducing gas from oxygen blast furnace gas |
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| CN113144831A (en) * | 2021-03-08 | 2021-07-23 | 灵谷化工集团有限公司 | Device and method for performing low-temperature methanol double washing based on heat exchange and modified methanol |
| CN113336193A (en) * | 2021-06-24 | 2021-09-03 | 中石化南京化工研究院有限公司 | Decarburization device and method for preparing reducing gas from oxygen blast furnace gas |
| CN113336193B (en) * | 2021-06-24 | 2023-09-19 | 中石化南京化工研究院有限公司 | Decarburization device and method for preparing reducing gas from oxygen blast furnace gas |
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