CN1325459C - Recovery method of tail gas light component in carbonylation production of acetic acid lanhydride - Google Patents
Recovery method of tail gas light component in carbonylation production of acetic acid lanhydride Download PDFInfo
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- CN1325459C CN1325459C CNB2004100161207A CN200410016120A CN1325459C CN 1325459 C CN1325459 C CN 1325459C CN B2004100161207 A CNB2004100161207 A CN B2004100161207A CN 200410016120 A CN200410016120 A CN 200410016120A CN 1325459 C CN1325459 C CN 1325459C
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- acetate
- pressure
- tail gas
- methyl
- aceticanhydride
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- 238000000034 method Methods 0.000 title claims abstract description 43
- 238000005810 carbonylation reaction Methods 0.000 title claims abstract description 31
- 230000006315 carbonylation Effects 0.000 title claims abstract description 30
- 238000011084 recovery Methods 0.000 title claims abstract description 15
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 title abstract description 30
- 238000004519 manufacturing process Methods 0.000 title abstract description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 133
- WFDIJRYMOXRFFG-UHFFFAOYSA-N acetic acid anhydride Natural products CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims abstract description 105
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 claims abstract description 48
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims abstract description 46
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 claims abstract description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 27
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 16
- 230000008569 process Effects 0.000 claims abstract description 13
- 239000003054 catalyst Substances 0.000 claims abstract description 10
- 238000005516 engineering process Methods 0.000 claims abstract description 7
- 229910052751 metal Inorganic materials 0.000 claims abstract description 7
- 239000002184 metal Substances 0.000 claims abstract description 6
- 229910001505 inorganic iodide Inorganic materials 0.000 claims abstract description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 82
- 238000010521 absorption reaction Methods 0.000 claims description 69
- 239000000470 constituent Substances 0.000 claims description 27
- 239000000203 mixture Substances 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 23
- 239000002250 absorbent Substances 0.000 claims description 12
- 230000002745 absorbent Effects 0.000 claims description 12
- 239000006096 absorbing agent Substances 0.000 claims description 7
- 238000007701 flash-distillation Methods 0.000 claims description 5
- 238000004140 cleaning Methods 0.000 claims description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims 3
- 239000000126 substance Substances 0.000 abstract description 2
- 239000012295 chemical reaction liquid Substances 0.000 abstract 2
- 238000001704 evaporation Methods 0.000 abstract 2
- 230000008020 evaporation Effects 0.000 abstract 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 abstract 1
- 230000007547 defect Effects 0.000 abstract 1
- 238000005265 energy consumption Methods 0.000 abstract 1
- 238000000605 extraction Methods 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 54
- 239000000463 material Substances 0.000 description 14
- 239000003795 chemical substances by application Substances 0.000 description 13
- 229910052703 rhodium Inorganic materials 0.000 description 9
- 239000010948 rhodium Substances 0.000 description 9
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 9
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 8
- 229910052741 iridium Inorganic materials 0.000 description 7
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 7
- 235000011089 carbon dioxide Nutrition 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 4
- 238000003889 chemical engineering Methods 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Chemical compound [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 description 4
- 229910052707 ruthenium Inorganic materials 0.000 description 4
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 3
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 229920013683 Celanese Polymers 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000006837 decompression Effects 0.000 description 2
- 229910000043 hydrogen iodide Inorganic materials 0.000 description 2
- 229940006461 iodide ion Drugs 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 150000004702 methyl esters Chemical class 0.000 description 2
- 238000013022 venting Methods 0.000 description 2
- XZXYQEHISUMZAT-UHFFFAOYSA-N 2-[(2-hydroxy-5-methylphenyl)methyl]-4-methylphenol Chemical compound CC1=CC=C(O)C(CC=2C(=CC=C(C)C=2)O)=C1 XZXYQEHISUMZAT-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- ZMZINYUKVRMNTG-UHFFFAOYSA-N acetic acid;formic acid Chemical compound OC=O.CC(O)=O ZMZINYUKVRMNTG-UHFFFAOYSA-N 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 229940107816 ammonium iodide Drugs 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 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
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 230000010429 evolutionary process Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-M iodide Chemical compound [I-] XMBWDFGMSWQBCA-UHFFFAOYSA-M 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- WUHYYTYYHCHUID-UHFFFAOYSA-K iridium(3+);triiodide Chemical compound [I-].[I-].[I-].[Ir+3] WUHYYTYYHCHUID-UHFFFAOYSA-K 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- BLQJIBCZHWBKSL-UHFFFAOYSA-L magnesium iodide Chemical compound [Mg+2].[I-].[I-] BLQJIBCZHWBKSL-UHFFFAOYSA-L 0.000 description 1
- 229910001641 magnesium iodide Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 235000007715 potassium iodide Nutrition 0.000 description 1
- 229960004839 potassium iodide Drugs 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 235000009518 sodium iodide Nutrition 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
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Abstract
The present invention relates to a method for recovering light components in tail gas generated in the production of acetic acid/acetic anhydride through carbonylation, which overcomes the defects of high cost and large energy consumption of the existing recovery method. The method is suitable for the technology of preparing acetic acid/acetic anhydride through carbonylation. Carbon monoxide and methanol or active derivants of methanol are carbonylated in a reactor to prepare acetic acid/acetic anhydride in the presence of catalysts containing metal of the eighth group, methyl iodide, inorganic iodide, methyl acetate, water and reaction liquid of acetic acid/acetic anhydride. Simultaneously, the reaction liquid enters a flash evaporator for flash evaporation, volatile substances of the flash evaporation passes through a rectifying tower, and acetic acid/acetic anhydride is extracted. A secondary solution absorbing method is adopted to absorb and purify tail gas secondarily during the processes of recovering light components in non-condensable gas released from the extraction of acetic acid/acetic anhydride through rectification and recovering light components in air released from the reactor.
Description
Technical field
The present invention relates to the recovery method of tail gas in the acetic acid production, particularly a kind of carbonylation is produced the recovery method of tail gas light constituent in acetate/aceticanhydride.
Background technology
Early 1970s Pu Like has proposed the method with carbon monoxide and carbonylation of methanol in U.S. Pat 3769329, rhodium, methyl-iodide, methyl acetate, water and acetate are arranged in its catalyzer.In this way, can produce acetate with carbon monoxide and carbonylation of methanol.At last, this technology quilt industry fully, and in worldwide, obtain industrial application.
The eighties in 20th century, Celanese is applied for a patent the development that discloses among the CN85101460 carbonylation of methanol in China.The contribution of its maximum has been to invent to be added inorganic salt compounded of iodine and keeps the stability of Primary Catalysts and reduce water-content in the reaction solution.This patent disclosure the rhodium of reaction solution composition: 200～1000ppm, the methyl-iodide of 0.5%～20% (wt), the methyl acetate of 0.5%～30% (wt), the water-content of 0.1%～20% (wt), all the other are acetate.This certificate of patent is understood the possibility of carbonylation reaction under above-mentioned reaction solution condition, and has finally obtained industrial application.
Japan big plug road chemical industry Co., Ltd. also discloses the reaction solution of the 8th family's metallic element catalyzer, methyl-iodide, methyl acetate, water and acetate at Chinese patents CN 961904010 can be with carbon monoxide and methyl alcohol and reactive derivative methyl acetate thereof, carbonylations such as dme.Also proposed the acetic acid of carbon monoxide and methyl alcohol and reactive derivative carbonylation thereof in the reaction solution of iridium catalyst, methyl-iodide, methyl acetate and acetate in patents such as BP patent CN97120825 and CN00135537, this technology is referred to as Cativa
TMTechnology.Rhodium, the iridium iodide ion catalyst system of preparation acetate have also been proposed among the Celanese patent CN99812415.
Above-mentioned patent and document have proved that all the 8th family's metal catalyst, methyl-iodide, methyl acetate, water and acetate/aceticanhydride can form effective reaction solution (catalyzer), and carbon monoxide and methyl alcohol and derivative carbonylation thereof generate acetate/aceticanhydride.But patent and document have all illustrated carbon monoxide of reaction and methyl alcohol and can not reach 100% conversion.The transformation efficiency of carbon monoxide is 85%～95%, and conversion of methanol is 99%.And carbonylation process has water-gas reaction, generated hydrogen and carbonic acid gas.
Therefore, produce in acetate/aceticanhydride process, must discharge tail gas at carbonylation.These tail gas comprised in unreacted carbon monoxide, the raw material with H
2, N
2, CH
4The titanium dioxide and the H that bring with carbonic acid gas, side reaction
2Deng.These tail gas divide two tunnel dischargings: the one tunnel is to pass through cooling back emptying from the reactor venting port, is referred to as high pressure exhaust gas; Another road is entrained in the reaction solution of flasher, takes rectification zone to volatile matter when flash distillation, in rectification zone as noncondensable gas emptying. be referred to as low-pressure tail gas.In the gas of this two tunnel emptying, have materials such as methyl-iodide, methyl acetate, acetate/aceticanhydride with the form of saturation steam.Especially the lower light constituent of boiling point such as methyl-iodide, methyl acetate, the amount of carrying secretly in tail gas is bigger, and these light constituents are the important component that constitute reaction solution, and human body is had certain toxicity.Therefore before these tail gas enter burning and enter atmosphere, need to reclaim these light constituents, cleaning of off-gas.
The method of industrial common recovery tail gas as absorption agent, is washed the light constituent that absorbs in the tail gas with acetate as shown in Figure 1.The acetate that absorbs light constituent obtains purifying by (also so-called stripping) in the rectifying of having only stripping section, circulates once more as absorption agent after the acetate cooling of purifying, reclaims after the condensation of gas of rectifying tower top.Such processing method needs the acetate circulation and the steam of more amount, and usually, the acetate device that an industrial cover is 400,000 tons/year needs 20 tons/hour internal circulating load, consumes the steam of about 5t/h.
Summary of the invention
The technical issues that need to address of the present invention are: can reach and reclaim reactive material, save the purpose of producing subsidiary material, also can make that the Toxic material is purified in the tail gas simultaneously, make the needs that can satisfy environment protection and safety and sanitation.Providing a kind of can absorb light constituent, air cleaning method in the emptying end gas of acetate/aceticanhydride carbonylation production, the method for secondary purification tail gas provided by the invention can not only satisfy above-mentioned requirements, also has energy-conservation effect simultaneously.
The present invention adopts carbonylation to prepare acetate/aceticanhydride: the reaction solution that contains the 8th family's metal catalyst, methyl-iodide, inorganic iodide, methyl acetate, water and acetate/aceticanhydride exists down, in reactor, carry out carbonylation with carbon monoxide and prepare acetate/aceticanhydride with the reactive derivative of methyl alcohol or methyl alcohol, simultaneously, reaction solution is advanced the flasher flash distillation, from the flash distillation volatile matter, pass through to extract acetate/aceticanhydride at rectifying tower.The 8th family of family metal catalyst is meant: rhodium, iridium, ruthenium, nickel etc., especially rhodium, iridium and rhodium and iridium mixture, rhodium and ruthenium mixture, rhodium and iridium mixture, iridium and ruthenium mixture.The concentration of rhodium, iridium can be 300～5000ppm, and the concentration of mixture ruthenium can be joined arbitrarily.Methyl-iodide is 5%wt～25%wt in the concentration of reaction solution.Inorganic iodide is meant and can be dissolved in reaction solution, the simplification compound and the mixture of iodide ion are provided, hydrogen iodide, lithium iodide, potassiumiodide, sodium iodide, magnesium iodide, ammonium iodide etc. and they two or more mixture, most preferably lithium iodide and hydrogen iodide and their mixture arbitrarily preferably.These iodide shared concentration in reaction is 3.5%wt～25%wt.The concentration of water can be 0～14% in the reaction solution.Acetate/aceticanhydride in the reaction solution is the remainder of removing in the reaction solution outside family's metal catalyst, methyl-iodide, inorganic iodide, methyl acetate, the water.The content of methyl acetate can be 0%wt～30%wt in the reaction solution.Can contain a certain amount of impurity in any absorption liquid, these impurity can be the raw materials that carbonylation is produced, the impurity of product catalyst constituent intermediate and some carbonylations.The raw material of carbonylation production is meant methyl alcohol and reactive derivative thereof.Product is meant acetate or aceticanhydride.The catalyzer constituent comprises: methyl-iodide, methyl acetate.Carbonylation impurity is meant aldehyde and derivative thereof, and high carboxylic acid, ketone.
Technical scheme of the present invention is: a kind of new acetate emptying end gas light constituent absorption process provided by the invention, adopt successively the acetate emptying end gas to be absorbed as absorption agent with two kinds of different solutions.Just adopt the secondary absorption techniques that tail gas is absorbed.
Secondary absorption techniques key of the present invention is meant successively carries out purifying treatment with two kinds of different absorbents to tail gas, and so-called secondary just second aqueous absorbs.First step absorbent solution is any or two or more mixture of methyl acetate, methyl alcohol and acetate, and first step optimal absorption solution is methyl alcohol.Second stage absorbent solution is the mixture of any or two kinds of acetate and water, and the second stage all is best with the mixture of acetate or acetate and water.Secondary is absorbed as in-line secondary and absorbs, and high pressure exhaust gas and low-pressure tail gas enter the second stage after absorbing by the first step.By solution tail gas being carried out secondary under certain pressure and temperature requires absorbs.And be not to be subjected to considerable restraint to pressure, the first step absorbs and does not limit a tower, can be two towers, also can be a tower, and it can be a low pressure absorption tower that the first step absorbs, and also can be that a low pressure absorption tower and high-pressure absorber are formed.The first step absorbs when having only a low pressure absorption tower, and the absorption tower optimum pressure is approaching with rectifying zone low-pressure tail gas emptying pressure.When first step absorption was made up of low pressure absorption tower and high-pressure absorber, low pressure absorption tower optimum pressure was approaching with rectifying zone low-pressure tail gas emptying pressure, and the high-pressure absorber optimum pressure is approaching with the high pressure exhaust gas pressure of reactor emptying.The first step absorbs and also not to limit a pressure, can high pressure and low pressure and deposit, and also can a low pressure.No matter be any pressure change, the present invention can be suitable for.But still to point out in the present invention, first step absorption pressure is preferably greater than 1atm (a), second stage absorption pressure is a little less than first step absorption pressure, only absorption pressure is in technology, high pressure absorption pressure and reactor tail gas emptying pressure are in a basic balance, and first step mesolow tower absorption pressure is in a basic balance in rectification zone low-pressure tail gas emptying pressure.Low pressure absorption tower, second stage pressure is a little less than first step absorption tower pressure, and the pressure that is reduced only provides power for gas flow.First step absorption pressure 〉=1atm (a), first step absorption agent temperature≤45 ℃ is preferably 15 ℃～20 ℃, second stage absorption pressure 〉=1atm (a), second stage absorption temperature≤45 ℃ are preferably 15 ℃～25 ℃.
The invention has the beneficial effects as follows: the method that the secondary that the present invention proposes absorbs, can significantly reduce, absorb the acetate amount of usefulness, only 10% acetate amount less than above-mentioned one-level absorption just can satisfy industrial needs.Significantly reduced the consumption of power and shared engineering.Both obtained reclaiming light constituent, the purpose that purifies air, the purpose of energy saving of having got back.
Description of drawings
Fig. 1 is the process flow sheet of the recovery method of tail gas in the prior art acetic acid production
Fig. 2 absorbs the process flow sheet that has only a lower pressure column for one-level of the present invention
Flow process shown in Figure 2, be meant that the first step absorbs and to have only a lower pressure column (first step lower pressure column), acetic acidreaction district high pressure emptying end gas mixes the back and carries out first step absorption with two kinds of methyl alcohol, methyl acetate, acetate or they or two or more mixtures after decompression with rectification zone lp venting tail gas.Carrying out the second stage with acetate, water or their mixture through the tail gas after the rough purification in the lower pressure column of the second stage absorbs.
Fig. 3 is absorbed with the process flow sheet of a lower pressure column and high-pressure tower for one-level of the present invention
Flow process shown in Figure 3, be that the first step is absorbed with a high-pressure tower and lower pressure column (first step lower pressure column), the high pressure exhaust gas of acetic acidreaction district emptying absorbs the high pressure exhaust gas decompression after the rough purification with two or more mixture of methyl alcohol, methyl esters, acetate or they in high-pressure tower; The low-pressure tail gas of acetate rectification zone emptying is used in first step lower pressure column and is carried out the first step with the same absorption agent of high-pressure tower and absorb, the low-pressure tail gas after the first step absorbs with purify after the post-decompression gas of high pressure exhaust gas mix laggard second stage lower pressure column and carry out second stage absorption with acetate, water or their mixture.
Fig. 4 is a processing unit schema of the present invention
Among Fig. 4: 1. gas cylinder, 2. methyl-iodide, methyl acetate producer, 3. first step low pressure absorption tower, 4. low pressure absorption tower, first step absorption agent rich solution storage tank 5. second stage 6. second stage absorption agent rich solution storage tank 7. first step absorption agents groove 8. second stage absorption agent storage tanks 9. first step absorption agent water coolers 10. second stage absorber coolers that incline.
Embodiment
With reference to Fig. 2,3, the light constituent that contains in the acetate tail gas is materials such as methyl-iodide and methyl acetate, mainly is methyl-iodide.The emptying gas composition is carbon monoxide, H
2, N
2And a spot of carbonic acid gas.In absorbing evolutionary process, carbon monoxide, H
2, N
2And carbonic acid gas itself is the inert media not have influence to absorbing, and just how many amounts of these gases can influence the engineering size of absorption equipment.From the knowledge in the known field of chemical engineering, learn carbon monoxide, H in the gas
2, N
2And these media of carbonic acid gas and light constituent methyl-iodide, methyl acetate the saturation steam mixed gas and the pure N that form
2With the mixed gas of light constituent methyl-iodide, methyl acetate saturation steam test be consistent, have with all effects.When methyl-iodide, methyl acetate were kept certain volumetric concentration, under the fixed pressure condition, methyl-iodide, methyl acetate were at N
2Dividing potential drop and carbon monoxide, H
2, N
2And the dividing potential drop of carbon dioxide mix gas is the same, and just the volume content of methyl-iodide, methyl acetate (or molar content) is the same.Therefore, according to the known domain knowledge of chemical engineering, it can be N that test is implemented
2Gas replaces carbon monoxide, H
2, N
2And carbonic acid gas is used as gaseous media.The known knowledge that absorbs from the relevant separation engineering of chemical engineering can be learnt, absorption of the present invention is a physical absorption, it is favourable that pressure improves absorption, experimental example of the present invention is only carried out first step absorption test under the condition of low pressure, the result of test is that the known knowledge that absorbs in can the relevant separation engineering of applied chemistry engineering is generalized to high pressure conditions.
Implementing procedure, as shown in Figure 4:
First step low pressure absorption tower 3, low pressure absorption tower, the second stage 5 employing diameters are 50mm in the experiment, and tower packing adopts the special porcelain ring of 3mm, and packed height is equivalent to 5 theoretical stages.
A
1～A
4Be different analysis sites
P
1～P
6Be different pressure indication points
T
1～T
3Be different temperature indication points
F
1Be N
2Under meter
F2 is a first step absorption agent flow meter
F3 is the under meter of second stage absorption agent
Embodiment 1,2, and 3,4,5,6,7,8,9:
, carry out one-level and absorb as first step absorbent solution with acetate, do not carry out the test that the second stage absorbs.Use a certain amount of N
2By methyl-iodide, methyl acetate producer, will contain the N of methyl-iodide, methyl acetate saturated air
2Gas absorbs with acetate by first step low pressure absorption tower.Testing under the different absorption temperature conditions with acetate under methyl-iodide, the methyl acetate producer differing temps.Data see Table 1.
Acetate freezes at 16.7 ℃, so temperature can not be low again.
Embodiment 10～24:
Embodiment 10～24th, the embodiment that the first step absorbs with acetate with methyl alcohol absorption, the second stage.10～24th, by methyl-iodide, methyl acetate producer, the different data that change of absorption agent temperature.See Table 2.
Embodiment 25～28:
Embodiment 25～28th, and the first step absorbs with methyl acetate and absorbs the embodiment with acetate as absorbent solution, the second stage, and data see Table 3.
Embodiment 29～32:
Embodiment 29～32nd, and the first step absorbs with the embodiment of methyl alcohol as absorbent solution, second stage absorption water, and data see Table 4.
Embodiment 33～36
Embodiment 33～36th, and the first step absorbs the embodiment that absorbs the mixture of water and acetate with the mixture of methyl alcohol and methyl esters, the second stage, data see Table 5 from embodiment 1～9 and embodiment 10～24 relatively, etc. the methyl alcohol of quality the receptivity of methyl-iodide, methyl acetate are better than the receptivity of acetic acid to methyl-iodide, methyl acetate.Simultaneously, acetate is during as absorbent solution, and pure acetate will solidify at 16.7 ℃, so be subjected to the restriction of acetate zero pour, the absorption temperature of acetate can not be lower than 16.7 ℃, and the suffered restriction of methyl alcohol is just little.Because the volatility of methyl alcohol and methyl acetate is greater than acetate, secondary of the present invention absorbs main effect and is to absorb methyl alcohol and methyl acetate, and embodiment 10～24 can find, be equivalent among the embodiment 1～9 0/once acetic acid can satisfy the absorption needs.Can find that from embodiment 25～28 methyl acetate has good assimilation effect to methyl-iodide, but because its boiling point is lower, so need under lower temperature, absorb.Find out from embodiment 1～28, the assimilation effect of methyl-iodide is weakened successively to acetate from the methyl acetate to methyl alcohol, but first step absorption temperature can improve successively, consume angle from comprehensive energy and consider that it is best that first step absorption liquid is selected methyl alcohol for use.
Embodiment 1～36, though with the full scale plant flow process certain difference is arranged, provided the ability of various solution to methyl-iodide in the tail gas and methyl acetate absorption, thereby proved that the present invention is in industrial Application feasibility.By the data acknowledgement of embodiment 1～36,, just can carry out systems simulation and engineering design to full scale plant according to the known knowledge that absorbs in the relevant separation engineering in the chemical engineering.
By method of the present invention, the light constituent absorbent solution of first step absorption process is directly advanced reactor, and the second stage absorbs the solution that produces can advance reactor, also can advance rectifying.Compared with the method (Fig. 1) that originally absorbs with acetate, method of the present invention circulates no longer in a large number, thereby the present invention can save a large amount of steams, does not also increase power consumption.Use the present invention, can save a certain amount of steam acetate/aceticanhydride device.Therefore, the present invention has advanced meaning with respect to the method that absorbs with acetate originally.
Table 1
*Remaining material component is N
2
CH
3I: methyl-iodide; MEAC: methyl acetate; HAC: acetate; MEOH: methyl alcohol; H
2O: water; M+M: methyl acetate+methyl alcohol; H+H: acetate+water.
Table 2
| Embodiment | F1 g/h | P5 kPa | P6 kPa | T 1℃ | T 2℃ | T 3 ℃ | Analyze material component %wt * | F2 g/h | F3 g/h | ||||||||
| A 1 | A 2 | A 3 | |||||||||||||||
| CH 3I | MEAC | CH 3I | MEAC | MEOH | CH 3I | MEAC | HAC | MEOH | |||||||||
| 10 | 28 | 30 | 27 | 45 | 45 | 20 | 15.41 | 1.31 | 0.421 | 54ppm | 33.34 | 0.34 | 32ppm | 31.10 | 11.78 | 256 | 30 |
| 11 | 28 | 30 | 27 | 45 | 45 | 30 | 26.39 | 2.25 | 0.94 | 0.013 | 33.58 | 0.77 | 79ppm | 30.96 | 12.04 | 256 | 30 |
| 12 | 28 | 30 | 27 | 45 | 45 | 40 | 34.61 | 2.96 | 1.59 | 0.024 | 33.85 | 1.28 | 0.014 | 32.06 | 11.45 | 256 | 32.9 |
| 13 | 28 | 30 | 27 | 25 | 45 | 20 | 15.41 | 1.31 | 0.088 | 4ppm | 15.32 | 0.071 | 2ppm | 22.78 | 1.74 | 256 | 30 |
| 14 | 28 | 30 | 27 | 25 | 45 | 30 | 26.39 | 2.25 | 0.21 | 11ppm | 15.45 | 0.17 | 4ppm | 22.83 | 1.79 | 256 | 30 |
| 15 | 28 | 30 | 27 | 25 | 45 | 40 | 34.61 | 2.96 | 0.37 | 21ppm | 15.61 | 0.30 | 7ppm | 23.37 | 1.32 | 256 | 35.9 |
| 16 | 28 | 30 | 27 | 15 | 45 | 20 | 15.41 | 1.31 | 0.018 | ＜1ppm | 8.91 | 0.018 | ＜1ppm | 16.27 | 0.24 | 256 | 30 |
| 17 | 28 | 30 | 27 | 15 | 45 | 30 | 26.39 | 2.25 | 0.041 | 1.5ppm | 8.94 | 0.033 | ＜1ppm | 15.95 | 0.25 | 256 | 30 |
| 18 | 28 | 30 | 27 | 15 | 45 | 40 | 34.61 | 2.96 | 0.072 | 2.4ppm | 8.98 | 0.056 | ＜1ppm | 16.12 | 0.06 | 265 | 44.9 |
| 19 | 28 | 30 | 27 | 25 | 20 | 20 | 15.41 | 1.31 | 0.088 | 4ppm | 15.32 | 0.077 | 2ppm | 16.51 | 1.33 | 256 | 30 |
| 20 | 28 | 30 | 27 | 25 | 20 | 30 | 26.39 | 2.25 | 0.21 | 11ppm | 15.44 | 0.18 | 4ppm | 16.56 | 1.38 | 256 | 30 |
| 21 | 28 | 30 | 27 | 25 | 20 | 40 | 34.61 | 2.96 | 0.37 | 21ppm | 15.61 | 0.33 | 6ppm | 15.48 | 0.89 | 586 | 35.9 |
| 22 | 28 | 30 | 27 | 15 | 20 | 20 | 15.41 | 1.31 | 0.018 | ＜1ppm | 8.91 | 0.016 | ＜1ppm | 8.47 | 0.33 | 256 | 30 |
| 23 | 28 | 30 | 27 | 15 | 20 | 30 | 26.39 | 2.25 | 0.041 | 1.3ppm | 8.94 | 0.036 | ＜1ppm | 8.53 | 0.17 | 256 | 30 |
| 24 | 28 | 30 | 27 | 15 | 20 | 40 | 34.61 | 2.96 | 0.072 | 2.4ppm | 8.98 | 0.062 | ＜1ppm | 6.41 | 0.015 | 256 | 38.9 |
*Remaining material component is N
2
CH
3I: methyl-iodide; MEAC: methyl acetate; HAC: acetate; MEOH: methyl alcohol; H
2O: water; M+M: methyl acetate+methyl alcohol; H+H: acetate+water.
Table 3
| Embodiment | F1 g/h | P5 kPa | P6 kPa | T 1 ℃ | T 2 ℃ | T 3 ℃ | Analyze material component %wt * | F2 g/h | F3 g/h | ||||||||
| A 1 | A 2 | A 3 | |||||||||||||||
| CH 3I | MEAC | CH 3I | MEAC | CH 3I | MEAC | HAC | |||||||||||
| 25 | 28 | 30 | 27 | 25 | 20 | 30 | 26.39 | 2.25 | 0.22 | 43.29 | 0.22 | 31.90 | 7.54 | 368 | 59.8 | ||
| 26 | 28 | 30 | 27 | 15 | 20 | 30 | 26.39 | 2.25 | 0.048 | 30.59 | 0.046 | 18.79 | 7.21 | 368 | 59.8 | ||
| 27 | 28 | 30 | 27 | 15 | 20 | 20 | 15.4 | 1.31 | 0.021 | 30.54 | 0.021 | 18.74 | 7.21 | 368 | 59.8 | ||
| 28 | 28 | 30 | 27 | 0 | 20 | 20 | 15.4 | 1.31 | 10ppm | 15.56 | 5.4ppm | 0.19 | 4.33 | 368 | 67.9 | ||
*Surplus little material component is N
2
CH
3I: methyl-iodide; MEAC: methyl acetate; HAC: acetate; MEOH: methyl alcohol; H
2O: water; M+M: acetate formic acid+methyl alcohol; H+H: acetate+water.
Table 4
| Embodiment | F1 g/h | P5 kPa | P6 kPa | T 1 ℃ | T 2 ℃ | T 3 ℃ | Analyze material component %wt * | F2 g/h | F3 g/h | ||||||||
| A 1 | A 2 | A 3 | |||||||||||||||
| CH 3I | MEAC | CH 3I | MEAC | MEOH | CH 3I | MEAC | MEOH | ||||||||||
| 29 | 28 | 30 | 27 | 25 | 20 | 20 | 15.4 | 1.31 | 0.088 | 4.4ppm | 15.32 | 0.077 | 4.4ppm | 0.028 | 256 | 54 | |
| 30 | 28 | 30 | 27 | 25 | 20 | 30 | 26.39 | 2.25 | 0.21 | 11ppm | 15.44 | 0.18 | 11ppm | 0.029 | 256 | 54 | |
| 31 | 28 | 30 | 27 | 15 | 20 | 20 | 15.4 | 1.31 | 0.018 | ＜1ppm | 8.91 | 0.016 | ＜1ppm | 0.069 | 256 | 36 | |
| 32 | 28 | 30 | 27 | 15 | 20 | 30 | 26.39 | 2.25 | 0.041 | 1.3ppm | 8.94 | 0.036 | 1.2ppm | 0.071 | 256 | 36 | |
*Remaining material component is N
2
CH
3I: methyl-iodide; MEAC: methyl acetate; HAC: acetate; MEOH: methyl alcohol; H
2O: water; M+M: methyl acetate+methyl alcohol; H+H: acetate+water.
Table 5
| Embodiment | F1 g/h | P5 kPa | P6 kPa | T 1 ℃ | T 2 ℃ | T 3 ℃ | Analyze material component %wt * | F2 g/h M+M | F3 g/h H+H | ||||||||
| A 1 | A 2 | A 3 | |||||||||||||||
| CH 3I | MEAC | CH 3I | MEAC | MEOH | CH 3I | MEAC | HAC | MEOH | |||||||||
| 33 | 28 | 30 | 27 | 15 | 20 | 20 | 15.4 | 1.31 | 0.37 | 11.59 | 7.32 | 0.31 | 0.67 | 0.67 | 0.016 | 309 | 50 |
| 34 | 28 | 30 | 27 | 15 | 20 | 30 | 26.39 | 2.25 | 0.85 | 11.62 | 7.34 | 0.71 | 0.68 | 0.67 | 0.016 | 309 | 50 |
| 35 | 28 | 30 | 27 | 10 | 20 | 20 | 15.4 | 1.31 | 0.15 | 9.22 | 5.55 | 0.11 | 0.23 | 0.62 | 37ppm | 309 | 50 |
| 36 | 28 | 30 | 27 | 10 | 20 | 30 | 26.39 | 2.25 | 0.32 | 9.23 | 5.56 | 0.23 | 0.24 | 0.62 | 37ppm | 309 | 50 |
*Remaining material component is N
2
CH
3I: methyl-iodide; MEAC: methyl acetate; HAC: acetate; MEOH: methyl alcohol; H
2O: water; M+M: methyl acetate+methyl alcohol; H+H: acetate+water.
M+M: methyl acetate 30%wt, methyl alcohol 70%wt.
H+H: acetate 40%wt, methyl alcohol 60%wt.
Claims (8)
1. a carbonylation is produced the recovery method of tail gas light constituent in acetate/aceticanhydride, prepare in the technology of acetate/aceticanhydride at carbonylation: contain the 8th family's metal catalyst, methyl-iodide, inorganic iodide, methyl acetate, the reaction solution of water and acetate/aceticanhydride exists down, in reactor, carry out carbonylation with carbon monoxide and prepare acetate/aceticanhydride with the reactive derivative of methyl alcohol or methyl alcohol, simultaneously, reaction solution is advanced the flasher flash distillation, from the flash distillation volatile matter, pass through to extract acetate/aceticanhydride at rectifying tower, it is characterized in that, reclaim light constituent in the low-pressure tail gas of in acetate/aceticanhydride process is extracted in rectifying, emitting and reclaim in the process of light constituent at the high pressure exhaust gas of the emptying of reactor, adopt the method for secondary solution absorption, tail gas is carried out absorption cleaning twice, described light constituent is methyl-iodide and ethyl acetate, first step absorbent solution is methyl acetate, any of methyl alcohol and acetate or two or more mixture, second stage absorbent solution are the mixture of any or two kinds of acetate and water.
2. carbonylation according to claim 1 is produced the recovery method of tail gas light constituent in acetate/aceticanhydride, it is characterized in that, secondary is absorbed as in-line secondary and absorbs, and high pressure exhaust gas and low-pressure tail gas enter the second stage after absorbing by the first step.
3. carbonylation according to claim 2 is produced the recovery method of tail gas light constituent in acetate/aceticanhydride, it is characterized in that first step absorption temperature is 15 ℃～20 ℃, and second stage absorption temperature is 15 ℃～25 ℃.
4. carbonylation according to claim 2 is produced the recovery method of tail gas light constituent in acetate/aceticanhydride, it is characterized in that, it can be a low pressure absorption tower that the first step absorbs, and also can be that a low pressure absorption tower and high-pressure absorber are formed.
5. carbonylation according to claim 4 is produced the recovery method of tail gas light constituent in acetate/aceticanhydride, it is characterized in that, the first step absorbs when having only a low pressure absorption tower, and absorption tower pressure is approaching with rectifying zone low-pressure tail gas emptying pressure.
6. carbonylation according to claim 4 is produced the recovery method of tail gas light constituent in acetate/aceticanhydride, it is characterized in that, when first step absorption is made up of low pressure absorption tower and high-pressure absorber, low pressure absorption tower pressure is approaching with rectifying zone low-pressure tail gas emptying pressure, and high-pressure absorber pressure is approaching with the high pressure exhaust gas pressure of reactor emptying.
7. carbonylation according to claim 1 is produced the recovery method of tail gas light constituent in acetate/aceticanhydride, it is characterized in that first step absorbent solution is methyl alcohol.
8. carbonylation according to claim 1 is produced the recovery method of tail gas light constituent in acetate/aceticanhydride, it is characterized in that, second stage absorbent solution is with the mixture of acetate or acetate and water.
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| US10537847B2 (en) | 2014-06-17 | 2020-01-21 | Bp Chemicals Limited | Method and apparatus for treating offgases in a acetic acid production unit |
| US20210122694A1 (en) * | 2018-07-02 | 2021-04-29 | Daicel Corporation | Method for producing acetic acid |
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