CN102441288B - Reactive distillation unpowered circulation technology and device - Google Patents
Reactive distillation unpowered circulation technology and device Download PDFInfo
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- CN102441288B CN102441288B CN201110293116.5A CN201110293116A CN102441288B CN 102441288 B CN102441288 B CN 102441288B CN 201110293116 A CN201110293116 A CN 201110293116A CN 102441288 B CN102441288 B CN 102441288B
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- reboiler
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- rectifying column
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- 238000000066 reactive distillation Methods 0.000 title claims abstract description 18
- 238000005516 engineering process Methods 0.000 title claims abstract description 11
- 239000000463 material Substances 0.000 claims abstract description 33
- 238000006243 chemical reaction Methods 0.000 claims abstract description 27
- 238000005381 potential energy Methods 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims description 25
- 238000010438 heat treatment Methods 0.000 claims description 11
- 239000000470 constituent Substances 0.000 claims description 7
- 230000000694 effects Effects 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 6
- 238000002309 gasification Methods 0.000 claims description 2
- 230000007547 defect Effects 0.000 abstract description 4
- 239000000203 mixture Substances 0.000 abstract description 4
- 238000000926 separation method Methods 0.000 abstract description 3
- 239000007792 gaseous phase Substances 0.000 abstract 2
- 230000005484 gravity Effects 0.000 abstract 1
- 239000007788 liquid Substances 0.000 description 9
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 7
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 230000032050 esterification Effects 0.000 description 4
- 238000005886 esterification reaction Methods 0.000 description 4
- 239000011552 falling film Substances 0.000 description 4
- 230000007062 hydrolysis Effects 0.000 description 4
- 238000006460 hydrolysis reaction Methods 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- NUMQCACRALPSHD-UHFFFAOYSA-N tert-butyl ethyl ether Chemical compound CCOC(C)(C)C NUMQCACRALPSHD-UHFFFAOYSA-N 0.000 description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- BKOOMYPCSUNDGP-UHFFFAOYSA-N 2-methylbut-2-ene Chemical compound CC=C(C)C BKOOMYPCSUNDGP-UHFFFAOYSA-N 0.000 description 2
- MSXVEPNJUHWQHW-UHFFFAOYSA-N 2-methylbutan-2-ol Chemical class CCC(C)(C)O MSXVEPNJUHWQHW-UHFFFAOYSA-N 0.000 description 2
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000006266 etherification reaction Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000003466 welding Methods 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- -1 alkyl methyl ether Chemical group 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 150000002118 epoxides Chemical class 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 210000000952 spleen Anatomy 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
Landscapes
- Vaporization, Distillation, Condensation, Sublimation, And Cold Traps (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention belongs to the technical field of reactive distillation, in particular relates to a reactive distillation unpowered circulation technology and device. The technical scheme is as follows: gaseous-phase condensate in a rectifying tower tray falls into a downflow weir from a tower plate; under the action of potential difference, self gravity and siphon force, materials in a forced convection tube and a natural convection tube on the bottom of the tower kettle of the rectifying tower are mixed; then the mixture enters a reboiler; after the mixture reaches reaction temperature after being heated by the reboiler, mixed liquor enters the tower kettle of the rectifying tower; and after the mixed liquor reacts, gaseous phase rises to the rectifying tower connected with the upper end of the tower kettle of the rectifying tower so as to realize unpowered circulation. Reaction and separation are centralized in one tower, the purpose of unpowered circulation is achieved by the thermodynamic principle, the siphoning and the potential energy difference, and defects existing at present can be effectively solved.
Description
Technical field
The invention belongs to the technical field of reactive distillation, be specifically related to the unpowered circulation technology of a kind of reactive distillation and device.
Background technology
Tradition reactive distillation process is, material enters reactor reaction, sent into again the falling-film reboiler at reactor top by evaporimeter circulating pump, from falling-film reboiler out heated liquid object get back to reactor, in reactor, there is balanced reaction, liquid in reactor is constantly delivered to falling-film reboiler from Polycondensation Reactor and Esterification Reactor extraction by evaporimeter circulating pump and is heated, and the phase materials of working off one's feeling vent one's spleen enters rectifying column from reactor top; Gaseous state material from reactor enters rectifying column from bottom, at the bottom of unreacted material accumulates in rectifying tower, sends reactor back to by reactor circulating pump; A whole set of technique needs two power-equipments to realize solution circulation.This process chart is shown in accompanying drawing 1.
The synthetic rectification process of above-mentioned tradition is realized solution circulation and is mainly relied on evaporimeter circulating pump and reactor circulating pump two to overlap power-equipment.According to 180,000 tons of calculating of device load, the required flow of evaporimeter circulating pump should be greater than 650Nm3/h, reactor circulating pump minimum discharge is 60Nm3/h, therefore minimum 140KW and the 15KW of being respectively of required two cover power-equipment power, by annual normal operation 8000 hours, every degree electricity is by 0.56 yuan of calculating, and required power consumption is 1,240,000 kwh, and the electricity charge are 69.44 ten thousand yuan.In a word, the defect of existence is: energy consumption is large, and unit scale is larger, and seal point is more, equipment complexity, and maintenance cost is high, and operation easier is larger.
Summary of the invention
Object of the present invention is exactly to provide the unpowered circulation technology of a kind of reactive distillation and device for the defect of above-mentioned existence, reaction and separation processes is concentrated in a tower, by thermodynamic principles, siphonage and potential energy difference, reach the object of unpowered circulation, effectively solve the defect existing at present.
Reactive distillation of the present invention is unpowered circulation technology, its technical scheme is as follows: the gaseous condensate in rectifying column tower tray falls into downflow weir from column plate, under the effect of potential difference, self gravitation and siphon power, by entering in reboiler after the mixing of materials in forced convertion pipe and tower bottom of rectifying tower bottom natural convection tube, reach after reaction temperature through reboiler heating, mixed liquor is sent into tower bottom of rectifying tower, after reaction, gas phase rises in the rectifying column tower tray connecting in tower bottom of rectifying tower upper end, thereby realizes unpowered circulation.
Its detailed step of technique of the present invention is: under rectifying column tower tray backflow effect, in gasification materiel, in the overwhelming majority, component and heavy constituent material are condensed, fall into the rectifying tower downflow weir of trying to get to the heart of a matter, a mixed liquor part in downflow weir flows in reboiler under potential difference and rainbow suction by forced convertion pipe, and another part overflows across downflow weir and falls into from the upper side in tower bottom of rectifying tower; Under the effect of siphon power and self gravitation, rectifying column tower tray gaseous condensate enters in reboiler by the mixing of materials in forced convertion pipe and tower bottom of rectifying tower bottom natural convection tube, in reboiler, material is heated from bottom to top to be moved, after reaching reaction temperature, material enters tower bottom of rectifying tower from reboiler top, react, and owing to moving on material, produce siphon power; In tower bottom of rectifying tower, mixed liquor material reacts, after reaction, wherein most light components are vaporized and rise in rectifying column tower tray with a small amount of middle component and heavy constituent, whole flow process relies on siphon power and self the height potential energy that Steam Heating produces to carry out Matter Transfer completely, without any power-equipment, thereby realize unpowered circulation.
Reactive distillation of the present invention is unpowered EGR, comprises tower bottom of rectifying tower, rectifying column tower tray, reboiler, it is characterized in that: the upper end of this tower bottom of rectifying tower connects rectifying column tower tray, and the bottom of described rectifying column tower tray arranges downflow weir; This downflow weir connects forced convertion pipe, and described forced convertion pipe is connected reboiler after merging with the free convection pipe being stretched out by tower bottom of rectifying tower bottom; Described reboiler height is lower than downflow weir, and this reboiler upper end outlet is connected with end entrance on tower bottom of rectifying tower.
Described downflow weir ring rectifying tower tray bottom one week, in order to collect the heavy constituent material being condensed in rectifying column tower tray, a condensate liquid part of collecting is entered in reboiler and is heated by forced convertion pipe, a part flows in tower bottom of rectifying tower by overflowing across downflow weir, after mixing, enters reboiler with raw material again; The rear material part of heating enters top rectifying column tower tray with gas form and carries out rectification and purification, and part loops back tower bottom of rectifying tower.
Described reboiler is 2, is symmetrical arranged.
Described tower bottom of rectifying tower adopts the mode of welding to be connected with rectifying column tower tray, and rectifying column tower tray is directly welded on tower bottom of rectifying tower.
Technique of the present invention and equipment are mainly used in reactant and produce thing the chemical reaction that is all liquid phase, as esterification, hydrolysis and etherification reaction.
Esterification wherein, to generate esters product by alcohol and acid reaction, in this course of reaction, contain multiple azeotropic mixtures, conventional distillation separation process is comparatively complicated, if adopt reactive distillation invention, can replace the rectification process that tradition is complicated, and the product purity of producing can reach more than 99.8%.
Be applied to hydrolysis, as the hydrolysis of epoxides (being hydrolyzed into 1,2-epoxy prapanol by 1,2-expoxy propane), the hydrolysis of alkene (be hydrolyzed into 2-methyl-2-butanols by 2-methyl-2-butene, be hydrolyzed into 2-methyl-2-butanols etc. by isobutene).
Be applied to etherification reaction, be successively applied in the Chemical Manufacture such as tertiary alkyl methyl ether, ethyl tert-butyl ether (ETBE).
This process has the outer loop of reactionless device and cooling compared with traditional process, makes full use of reaction liberated heat, has the high and product purity high of reaction-ure conversion-age.
What meet following application conditions all can apply technique of the present invention and device:
(1) chemical reaction must carry out in liquid phase;
(2), under operating system pressure, the bubble point temperature of the reaction temperature of main reaction and object product approaches, so that product can shift out timely from reaction system;
(3) main reaction can not be strong endothermic reaction, otherwise the mass-and heat-transfer of distillation operation can be affected, and column plate separative efficiency is reduced;
(4) the main reaction time compared with the rectifying time, and the main reaction time can not be long, otherwise the separating power of rectifying column tower tray can not be fully used.
Beneficial effect of the present invention is: technology utilization thermodynamic principles of the present invention, principle of hydrodynamics etc., adjustment by device structure is used the form of free convection, forced convertion to carry out the mass-and heat-transfer of heating material and rectifying section material in tower bottom of rectifying tower, reach the object without device power cycle, reduce the use of power-equipment, can save power consumption; By the increase of forced convertion pipe, improve the circulation of having strengthened solution in tower, reduced on the one hand because gaseous component rises condensate liquid is declined and produces the impact of resistance, strengthened on the other hand the siphonage of solution in reboiler, the thermal balance and the material that are beneficial in device distribute.In addition, because technique of the present invention is taking reactive distillation process as basis, therefore this technique has several large advantage of reactive distillation process simultaneously: first due to the merging of tower bottom of rectifying tower and rectifying column tower tray, significantly reduced the manufacturing cost of equipment and saved space, place; And the merging of tower bottom of rectifying tower and rectifying column tower tray, reaction heat is used directly to distillation operation process, thus can reduce the thermic load of tower reactor, and the required heat of tower bottom of rectifying tower significantly will be lacked, reduce the whole steam consumption of system; Reaction and rectifying are carried out in same tower, can reduce heating times and condensation, cooling number of times, can save more energy.In a word, reactive distillation of the present invention is unpowered circulation technology and device, has realized unpowered circulation, and the performance of enterprises is played a positive role, and plays good effect for society saves the energy, has obtained outstanding substantive distinguishing features and significant progressive.
Brief description of the drawings
Fig. 1 is the structural representation of the prior art of background technology record;
Fig. 2 is apparatus structure schematic diagram of the present invention;
Fig. 3 is process flow diagram of the present invention, and has comprised the common process flow process after rectifying column;
Fig. 4 is the process chart that butyl acetate is produced;
Wherein, 1 is falling-film reboiler, and 2 is tower bottom of rectifying tower, and 3 is rectifying column tower tray, 4 is reactor circulating pump, and 5 is evaporimeter circulating pump, and 6 is downflow weir, 7 is forced convertion pipe, and 8 is free convection pipe, and 9 is reboiler, 10 is end entrance on tower bottom of rectifying tower, and 11 is rectifying column cooler, and 12 is collecting tank, 13 is rectifying column reflux pump, and 14 is quantizer, and 15 is rectifying column fractional distilling tube, 16 is feed preheater, and 17 is reactor, and 18 is rectifying column.
Detailed description of the invention
Below in conjunction with specific embodiments and the drawings, technical scheme of the present invention is described in detail.
Taking butyl acetate production as example.
At rectifying tower system, according to the butanols of reaction equation proportioning and acetic acid process feed preheater 16(E3105), add from the top of tower bottom of rectifying tower (T3101), in tower bottom of rectifying tower 2, there is esterification in the liquid reaction liquid that comprises catalyst and raw material.Final butyl acetate product material is to feed preheater 16(E3105) thermal source is provided, by mixed material heating, to save energy.
Under the effect of potential difference, self gravitation and siphon power, the material in tower bottom of rectifying tower 2 bottom natural convection tubes and the condensate liquid in downflow weir 6 enter reboiler 9 after mixing.In heated process, the density of mixed material decreases, and reaches after reaction temperature, and material enters tower bottom of rectifying tower 2 from reboiler 9 tops, reacts.In this process, because material moves, produce siphon power, circulation is continued.The mixed material that goes out reboiler 9 after heating flashes to gas-liquid two-phase, gas phase enters 3 sections of rectifying column tower trays and carries out rectifying, liquid phase is got back to tower bottom of rectifying tower 2 and is continued reaction, and whole flow process relies on siphon power and self the height potential energy that Steam Heating produces to carry out Matter Transfer completely, without any power-equipment.
The object that reactive distillation tower tray floor is 3 sections is that butyl acetate and water are separated, heavy constituent acetic acid is fallen rectifying tower tray bottom downflow weir 6 from the bottom tower tray of rectifying column tower tray 3, enters respectively tower bottom of rectifying tower 2 and reboiler 9(E3101A, B subsequently by overflow and two kinds of forms of forced convertion) in again participate in reaction.
The azeotropic mixture of butyl acetate and water and part butanols distillate from the tower top of rectifying column tower tray 3.Overhead fraction is at rectifying column fractional distilling tube 15(E3102) in carry out partial condensation, then at rectifying column condenser 11(E3103) in total condensation.
Rectifying column condenser 11(E3103) condensate liquid out enters collecting tank 12(V3102) after, by rectifying column reflux pump 13(P3102A/B) be sent to quantizer 14(S3101) in carry out phase-splitting.Organic phase partial reflux after layering is to rectifying column tower tray 3, and all the other are as finishing column (T3102) charging.Aqueous portion is back to reactive distillation tower tray floor (T3101), and other enters finishing column quantizer (3102).
Quantizer 14(S3101) in organic phase out except butyl acetate, a small amount of butanols and a small amount of water, also comprise all light components that come from feed material or its product.
While producing butyl acetate product without middle component extraction.
Reactive distillation of the present invention is unpowered EGR, comprises tower bottom of rectifying tower 2, rectifying column tower tray 3, reboiler 9, and the upper end of this tower bottom of rectifying tower 2 connects rectifying column tower tray 9, and the bottom of described rectifying column tower tray arranges downflow weir 6; This downflow weir connects forced convertion pipe 7, and described forced convertion pipe 7 is connected reboiler 9 after merging with the free convection pipe 6 being stretched out by tower bottom of rectifying tower bottom; Described reboiler 9 height are lower than downflow weir 6, and this reboiler upper end outlet is connected with end entrance on tower bottom of rectifying tower 10.
Described downflow weir 6 encircles a week, rectifying column tower tray 3 bottom, in order to collect the heavy constituent material being condensed in rectifying column tower tray 3, a condensate liquid part of collecting enters heating in reboiler 9 by forced convertion pipe 7, a part flows in tower bottom of rectifying tower 2 by overflowing across downflow weir 6, after mixing with raw material, enter again reboiler 9, the rear material part of heating enters top rectifying column tower tray 3 with gas form and carries out rectification and purification, and part loops back tower bottom of rectifying tower 2.
Described reboiler 9 is 2, is symmetrical arranged.
Described tower bottom of rectifying tower adopts the mode of welding to be connected with rectifying column tower tray, and rectifying column tower tray is directly welded on tower bottom of rectifying tower.
Claims (1)
1. the unpowered circulation technology of reactive distillation, its detailed step is: under rectifying column tower tray backflow effect, in gasification materiel, in the overwhelming majority, component and heavy constituent material are condensed, fall into the rectifying tower downflow weir of trying to get to the heart of a matter, a mixed liquor part in downflow weir flows in reboiler under potential difference and rainbow suction by forced convertion pipe, and another part overflows across downflow weir and falls into from the upper side in tower bottom of rectifying tower; Under the effect of siphon power and self gravitation, rectifying column tower tray gaseous condensate enters in reboiler by the mixing of materials in forced convertion pipe and tower bottom of rectifying tower bottom natural convection tube, in reboiler, material is heated from bottom to top to be moved, after reaching reaction temperature, material enters tower bottom of rectifying tower from reboiler top, react, and owing to moving on material, produce siphon power; In tower bottom of rectifying tower, mixed liquor material reacts, after reaction, wherein most light components are vaporized and rise in rectifying column tower tray with a small amount of middle component and heavy constituent, whole flow process relies on siphon power and self the height potential energy that Steam Heating produces to carry out Matter Transfer completely, thereby realizes unpowered circulation.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110293116.5A CN102441288B (en) | 2011-09-30 | 2011-09-30 | Reactive distillation unpowered circulation technology and device |
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| CN201110293116.5A CN102441288B (en) | 2011-09-30 | 2011-09-30 | Reactive distillation unpowered circulation technology and device |
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| CN102441288A CN102441288A (en) | 2012-05-09 |
| CN102441288B true CN102441288B (en) | 2014-07-16 |
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| CN109422615B (en) * | 2017-08-29 | 2022-03-11 | 中国石油化工股份有限公司 | Method and device for decoloring crude styrene separated from pyrolysis gasoline |
| CN113350821B (en) * | 2021-05-28 | 2022-12-06 | 鲁西化工集团股份有限公司硅化工分公司 | Device for improving operation effect of rectification system |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101357887A (en) * | 2008-07-31 | 2009-02-04 | 中国石油大学(华东) | Ethyl acetate synthetic process and apparatus thereof |
| CN201558563U (en) * | 2009-10-27 | 2010-08-25 | 中国石油化工股份有限公司 | Novel distillation tower |
| CN202237323U (en) * | 2011-09-30 | 2012-05-30 | 兖矿国泰乙酰化工有限公司 | Unpowered circulating device of reactive distillation |
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2011
- 2011-09-30 CN CN201110293116.5A patent/CN102441288B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101357887A (en) * | 2008-07-31 | 2009-02-04 | 中国石油大学(华东) | Ethyl acetate synthetic process and apparatus thereof |
| CN201558563U (en) * | 2009-10-27 | 2010-08-25 | 中国石油化工股份有限公司 | Novel distillation tower |
| CN202237323U (en) * | 2011-09-30 | 2012-05-30 | 兖矿国泰乙酰化工有限公司 | Unpowered circulating device of reactive distillation |
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Inventor after: Pei Xuecheng Inventor after: Chen Li Inventor after: Ma Tingwei Inventor after: He Peigen Inventor after: Zhang Yujuan Inventor after: Zhang Zhiwei Inventor after: Wang Jinbing Inventor after: Xu Mingzhong Inventor before: Pei Xuecheng Inventor before: Chen Li Inventor before: Ma Tingwei Inventor before: He Peigen Inventor before: Zhang Yujuan Inventor before: Zhang Zhiwei |
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Address after: Zaozhuang City, Shandong province 277527 wood and stone town Tengzhou City Patentee after: Yankuang Lunan Chemical Co., Ltd. Patentee after: Yancon Cathay Coal Chemicals Co., Ltd. Address before: Zaozhuang City, Shandong province 277527 wood and stone town Tengzhou City Patentee before: Yancon Cathay Coal Acetyl Chemicals Co., Ltd. Patentee before: Yancon Cathay Coal Chemicals Co., Ltd. |
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Effective date of registration: 20170503 Address after: Zaozhuang City, Shandong province 277527 Mu Shi Zhen (Tengzhou Lunan high tech chemical park) Patentee after: Yankuang Lunan Chemical Co., Ltd. Address before: Zaozhuang City, Shandong province 277527 wood and stone town Tengzhou City Co-patentee before: Yancon Cathay Coal Chemicals Co., Ltd. Patentee before: Yankuang Lunan Chemical Co., Ltd. |
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