CN102430247B - Treatment method for separation system tar in carbonylation synthetizingsis for acetic anhydride through carbonylation - Google Patents
Treatment method for separation system tar in carbonylation synthetizingsis for acetic anhydride through carbonylation Download PDFInfo
- Publication number
- CN102430247B CN102430247B CN201110262736.2A CN201110262736A CN102430247B CN 102430247 B CN102430247 B CN 102430247B CN 201110262736 A CN201110262736 A CN 201110262736A CN 102430247 B CN102430247 B CN 102430247B
- Authority
- CN
- China
- Prior art keywords
- tar
- evaporimeter
- aceticanhydride
- acetic anhydride
- carbonylation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 title claims abstract description 83
- 238000000034 method Methods 0.000 title claims abstract description 19
- 238000000926 separation method Methods 0.000 title claims abstract description 9
- 230000006315 carbonylation Effects 0.000 title abstract 5
- 238000005810 carbonylation reaction Methods 0.000 title abstract 5
- 239000000463 material Substances 0.000 claims abstract description 29
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 12
- 239000003112 inhibitor Substances 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000010438 heat treatment Methods 0.000 claims abstract description 8
- 238000003756 stirring Methods 0.000 claims abstract description 6
- 238000011084 recovery Methods 0.000 claims abstract description 5
- BHVICADLOSIXKE-UHFFFAOYSA-N oxaldehydoyl 2-oxoacetate Chemical compound O=CC(=O)OC(=O)C=O BHVICADLOSIXKE-UHFFFAOYSA-N 0.000 claims description 14
- 238000001704 evaporation Methods 0.000 claims description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 3
- 239000005864 Sulphur Substances 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical class C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 claims description 3
- 230000008020 evaporation Effects 0.000 claims description 3
- 229910001220 stainless steel Inorganic materials 0.000 claims description 2
- 239000010935 stainless steel Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 abstract description 4
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 239000011269 tar Substances 0.000 description 43
- 238000004519 manufacturing process Methods 0.000 description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 5
- 238000009835 boiling Methods 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 3
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Natural products OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 2
- 150000004075 acetic anhydrides Chemical class 0.000 description 2
- 239000011285 coke tar Substances 0.000 description 2
- -1 oxalic acid ethylidene ester Chemical class 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 150000001336 alkenes Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 150000002561 ketenes Chemical group 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000002075 main ingredient Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a treatment method for separation system tar in synthetizingcarbonylation synthesis for acetic anhydride through carbonylation, which comprises the following steps of: separation, recovery and incineration, wherein the step of separation comprises the following steps of: taking outdelivering a tar material at the bottom of a acetic anhydride tower delivering the tar material into an evaporator (3); adding water and a polymerization inhibitor into the evaporator (3); and after uniformly stirring, heating the mixture to 120 to 140 DEG C. By the method, the problem that the separation system tar is generated in the generation process of carbonylation synthetizingsynthesis thefor acetic anhydride through the carbonylation is better solved, the operation stability of a system can be kept, a large number of useful materials are recovered, the efficiency is improved, and the pollution is reduced.
Description
One, technical field
The present invention relates to the recycling of tar in oxo-acetic anhydride production, specifically the burnt oil treatment process of piece-rate system in a kind of oxo-acetic anhydride.
Two, background technology
The technology that methyl acetate, CO be raw material oxo-acetic anhydride of take is by America and Europe, to be invented the eighties in last century, and forms large-scale production.China, in earlier 2000s, has broken through oxo-acetic anhydride technology, and has several covering devices in succession to put into production.Owing to not allowed water to exist in the production system of aceticanhydride, very easily produce tar.The Main Ingredients and Appearance of tar is high-boiling components, polymer etc.Tar is constantly accumulation in production system, is seriously restricting production scale and production efficiency.The tar that oxo-acetic anhydride produces in synthesis reaction vessel, is referred to as reaction system tar, is comprising a large amount of catalyst in this tar, when reaction system tar-concentration reaches one regularly, synthetic reaction cannot be carried out, and must constantly take out aborning tar, and keeping system is produced stable.In the reactant liquor of aceticanhydride, containing mixtures such as acetic acid, aceticanhydride, the methyl acetate not reacting, CO, need to pass through separated rectifying.In separation process, especially in aceticanhydride is refining, because the boiling point higher of aceticanhydride is 138 ℃, in aceticanhydride tower reactor and reboiler, will produce high-boiling components is tar---be referred to as piece-rate system tar.The different output stages of reaction system tar and piece-rate system tar are seen Fig. 1.These two kinds of tar are all difficult to process, and become and are restricting the bottleneck that aceticanhydride is produced.Due to the existence of tar, system material viscosity is increased, heat and mass weak effect.In research and practice, when piece-rate system tar content reaches 15%, still temperature is along with tar content increases and rises, every increase one percentage point, still temperature rises 1 ℃, when piece-rate system tar content reaches 20%, still temperature can rise rapidly, along with still temperature rises, the speed that generates tar is accelerated, form vicious circle, finally cause reboiler tubulation to stop up and cannot move, be forced to the block clearing of stopping.At present, way both domestic and external is that the aceticanhydride solution containing tar 15% is constantly taken out from tower reactor, incinerates, and makes like this aceticanhydride cost increase, and meanwhile, burns and causes environmental pollution.
Three, summary of the invention
The present invention is for fear of the existing weak point of above-mentioned prior art, the burnt oil treatment process of piece-rate system in a kind of oxo-acetic anhydride is provided, thereby reaches the object that reclaims useful materials a large amount of in piece-rate system tar, raises the efficiency, reduces pollution.
Technical solution problem of the present invention adopts following technical scheme:
The burnt oil treatment process of piece-rate system in oxo-acetic anhydride of the present invention, comprise separation, recovery and burning, difference with the prior art is: described separation is that the tar material at the bottom of aceticanhydride tower reactor is taken out and sent in evaporimeter (3), in evaporimeter (3), add water and polymerization inhibitor, after stirring, be heated to 120-140 ℃;
Described recovery is by the cooling rear recovery of the aceticanhydride evaporating;
Described burning is that the quality of coke tar concentration of material in evaporimeter stops heating while being 90%, and normal temperature, curing, finally burning disposal are discharged and be cooled to interior the material of evaporimeter (3);
The addition of water is the 3-10% of tar quality of material;
The addition of polymerization inhibitor is the 0.2-1.0% of tar quality of material.
In oxo-acetic anhydride of the present invention, the feature of the burnt oil treatment process of piece-rate system is also: the addition of water is 10% of tar quality of material.
In oxo-acetic anhydride of the present invention, the feature of the burnt oil treatment process of piece-rate system is also: described polymerization inhibitor is sulphur fork diphenylamines.
In oxo-acetic anhydride of the present invention, the feature of the burnt oil treatment process of piece-rate system is also: the addition of polymerization inhibitor is 1.0% of tar quality of material.
In oxo-acetic anhydride of the present invention, the feature of the burnt oil treatment process of piece-rate system is also: mixing speed is 80-120 rev/min.
The composition of tar is mainly the high-boiling components such as oxalic acid ethylidene ester.Along with tar material is from continuous extraction at the bottom of aceticanhydride tower reactor, keep tar content in aceticanhydride tower reactor to be less than 15%, tower reactor temperature is controlled in 120 ± 2 ℃, guaranteed that aceticanhydride tower can permanently effective operation.
Aceticanhydride issues raw decomposition reaction at higher temperature, and product composition is very complicated, and primary product is ketenes, acetic acid diacetyl ester, methyl acetate, CO, CO
2and ethane etc., particularly there is alkene to exist, be easy to polymerization.The present invention, by destroying the existence of free radical, the method for reduction monomer reactivity, adds H simultaneously
2o reduces the concentration of free radical, reduces interactional probability, effectively prevents that Yin Gaowen produces tar in evaporation process.Polymerization inhibitor is finally discharged with tar.
Compared with the prior art, beneficial effect of the present invention is embodied in:
1, in aceticanhydride tower, the quality of coke tar concentration of material is to 15% time, and extraction continuously, remains on below 15% tar-concentration in tower reactor, thereby keeps the stable operation of tower.
2, in aceticanhydride tower, the tar material of extraction, contain a large amount of aceticanhydrides, reclaimed and can reduce to greatest extent loss of material.
3, the present invention adds water and polymerization inhibitor in evaporimeter, effectively stops the further polymerization of high-boiling components, although evaporator operation temperature is up to 140 ℃, but there are water and polymerization inhibitor to exist, in evaporimeter, tar content can not increase, and after aceticanhydride is distilled out of in evaporimeter, tar-concentration reaches 90% left and right.
4, the present invention solves the problem that oxo-acetic anhydride produces piece-rate system tar in producing preferably, can keeping system stable operation, reclaimed again a large amount of useful materials simultaneously, and raise the efficiency, reduce and pollute.
Four, accompanying drawing explanation
Fig. 1 is the source schematic diagram of reaction system tar and piece-rate system tar.
Fig. 2 is the process chart of piece-rate system tar of the present invention.
1 storage trough wherein, 2 delivery pumps, 3 evaporimeters, 4 paddles, 5 coolers, 6 condensate tanks, 7 dense tar are subject to basin, 8 valves.
Five, the specific embodiment
Below in conjunction with accompanying drawing, the invention will be further described.
At the bottom of aceticanhydride tower reactor, take out tar material storing in storage trough 1, with delivery pump 2, the tar material in storage trough 1 is sent in evaporimeter 3, in evaporimeter 3, add the water of tar quality of material 10% and the polymerization inhibitor sulphur of tar quality of material 1% fork diphenylamines simultaneously, after stirring, paddle 4 starts heating, the interior temperature of evaporimeter 3 is controlled to 120-140 ℃, in the evaporation process of heating, constantly stir, in order to avoid being attached to, tar is subject on thermal interface, produce dead angle, the aceticanhydride steam producing is discharged from the top of evaporimeter 3, after subcooler 5 is cooling, enter condensate tank 6, when the mass concentration of tar reaches 90% in the material in evaporimeter 3, stop heating, opening valve 8 is expelled to the uncovered dense tar of stainless steel by the interior material of evaporimeter 3 and is subject in basin 7, to be cooled to normal temperature, burning disposal after solidifying.
Claims (1)
1. the burnt oil treatment process of piece-rate system in oxo-acetic anhydride, comprises separation, recovery and burning, it is characterized in that:
At the bottom of aceticanhydride tower reactor, take out tar material storing in storage trough (1), keep tar content in aceticanhydride tower reactor to be less than 15%, and make the temperature of aceticanhydride tower reactor be controlled at 118-122 ℃, with delivery pump (2), the tar material in storage trough (1) is sent in evaporimeter (3), in evaporimeter (3), add the water of tar quality of material 10% and the polymerization inhibitor sulphur of tar quality of material 1% fork diphenylamines simultaneously, after stirring, paddle (4) starts heating, the interior temperature of evaporimeter (3) is controlled to 120-140 ℃, in the evaporation process of heating, constantly stir, in order to avoid being attached to, tar is subject on thermal interface, produce dead angle, the aceticanhydride steam producing is discharged from the top of evaporimeter (3), after subcooler (5) is cooling, enter condensate tank (6), when the mass concentration of tar reaches 90% in the material in evaporimeter (3), stop heating, opening valve (8) is expelled to the uncovered dense tar of stainless steel by the interior material of evaporimeter (3) and is subject in basin (7), to be cooled to normal temperature, burning disposal after solidifying.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110262736.2A CN102430247B (en) | 2011-09-06 | 2011-09-06 | Treatment method for separation system tar in carbonylation synthetizingsis for acetic anhydride through carbonylation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110262736.2A CN102430247B (en) | 2011-09-06 | 2011-09-06 | Treatment method for separation system tar in carbonylation synthetizingsis for acetic anhydride through carbonylation |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102430247A CN102430247A (en) | 2012-05-02 |
| CN102430247B true CN102430247B (en) | 2014-09-03 |
Family
ID=45978818
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201110262736.2A Active CN102430247B (en) | 2011-09-06 | 2011-09-06 | Treatment method for separation system tar in carbonylation synthetizingsis for acetic anhydride through carbonylation |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102430247B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106675605A (en) * | 2016-12-01 | 2017-05-17 | 中国石化长城能源化工（宁夏）有限公司 | Novel tar residue treatment method and device |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0665210A1 (en) * | 1993-08-18 | 1995-08-02 | Daicel Chemical Industries, Ltd. | Process for producing acetic anhydride alone or both of acetic anhydride and acetic acid |
| CN2757892Y (en) * | 2004-12-21 | 2006-02-15 | 上海焦化有限公司 | Screen plate extraction tower having centrifugal mixer |
-
2011
- 2011-09-06 CN CN201110262736.2A patent/CN102430247B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0665210A1 (en) * | 1993-08-18 | 1995-08-02 | Daicel Chemical Industries, Ltd. | Process for producing acetic anhydride alone or both of acetic anhydride and acetic acid |
| CN2757892Y (en) * | 2004-12-21 | 2006-02-15 | 上海焦化有限公司 | Screen plate extraction tower having centrifugal mixer |
Non-Patent Citations (2)
| Title |
|---|
| 吴福胜.醋酸甲醋生产醋酸酐的思路与关键技术分析.《安徽建筑工业学院学报(自然科学版)》.2011,第19卷(第4期),第97-100页. |
| 醋酸甲醋生产醋酸酐的思路与关键技术分析;吴福胜;《安徽建筑工业学院学报(自然科学版)》;20110831;第19卷(第4期);第100页第3-11行 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102430247A (en) | 2012-05-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP2821384B1 (en) | Production process for preparing cyclohexanol and cyclohexanone by cyclohexane oxidation | |
| CN104262299B (en) | A kind of ketene dimer production technique of high-efficiency environment friendly | |
| CN103827072A (en) | Method for recovering acetic acid | |
| CN114085135A (en) | Continuous production method suitable for ibuprofen Friedel-crafts reaction | |
| CN103951792A (en) | Method for producing p-benzenoid unsaturated polyester resin | |
| CN102430247B (en) | Treatment method for separation system tar in carbonylation synthetizingsis for acetic anhydride through carbonylation | |
| CN105084656B (en) | Methionine produces the processing method of waste water | |
| CN104557540A (en) | Clean technique for producing acrylate-hydroxy ester by adopting continuous process | |
| CN102020628B (en) | Improved method of preparation process of polylactic acid midbody lactide | |
| CN202022870U (en) | Device for preparing hydroxycarboxylic acid cyclic dipolymer | |
| CN1883729B (en) | Method for processing rectified residue of ketene dimer | |
| CN101723828B (en) | Method for preparing ethyl caproate by continuous esterification | |
| CN110407780A (en) | A kind of refining methd of furfural | |
| WO2013159347A1 (en) | Method for continuously producing high-content high-optical-purity lactate | |
| CN113443983B (en) | Production method of dimethyl sebacate | |
| CN103159613B (en) | The recovery method of recovery system and this equipment of use | |
| CN108164416A (en) | A kind of new process that monomethyl azelate is prepared based on biodiesel | |
| CN107445927A (en) | The technique that a kind of xylose dehydration prepares furfural | |
| CN106467457B (en) | Method for continuously producing 5-chloro-2-pentanone | |
| CN101757956B (en) | Method for recovering rhodium catalyst from catalyst-tar solution | |
| CN202605762U (en) | Distilling apparatus for producing maltol | |
| CN204874355U (en) | Device of preparation lactide | |
| CN105061193B (en) | Method for recycling organic matters in methionine production wastewater treatment | |
| CN106187778B (en) | A method of processing o-Xylene Oxidation in Liquid Phase residue | |
| CN204816455U (en) | A device for making plasticizer DOTP |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right |
Denomination of invention: A method for treating tar in the separation system of carbonylation synthesis of acetic anhydride Granted publication date: 20140903 Pledgee: Industrial and Commercial Bank of China Limited Chaohu sub branch Pledgor: ANHUI WANWEI UPDATED HIGH-TECH MATERIAL INDUSTRY Co.,Ltd. Registration number: Y2024980032535 |
|
| PE01 | Entry into force of the registration of the contract for pledge of patent right |