CN101992055B - Method and device of continuously synthesizing tetramethyl ammonium carbonate by multi-reactors in series - Google Patents
Method and device of continuously synthesizing tetramethyl ammonium carbonate by multi-reactors in series Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 30
- WJZPIORVERXPPR-UHFFFAOYSA-L tetramethylazanium;carbonate Chemical compound [O-]C([O-])=O.C[N+](C)(C)C.C[N+](C)(C)C WJZPIORVERXPPR-UHFFFAOYSA-L 0.000 title claims abstract description 27
- 230000002194 synthesizing effect Effects 0.000 title abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims abstract description 139
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 claims abstract description 84
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 57
- 239000002904 solvent Substances 0.000 claims abstract description 36
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000000463 material Substances 0.000 claims abstract description 21
- 239000000376 reactant Substances 0.000 claims abstract description 15
- 239000007788 liquid Substances 0.000 claims abstract description 11
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- 238000004064 recycling Methods 0.000 claims abstract 3
- 239000000203 mixture Substances 0.000 claims description 16
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- 235000007164 Oryza sativa Nutrition 0.000 claims description 5
- 235000009566 rice Nutrition 0.000 claims description 5
- UCVQOIPQDBZRMG-UHFFFAOYSA-N [C].COC(C=1C(C(=O)OC)=CC=CC1)=O Chemical compound [C].COC(C=1C(C(=O)OC)=CC=CC1)=O UCVQOIPQDBZRMG-UHFFFAOYSA-N 0.000 claims description 3
- 239000012492 regenerant Substances 0.000 claims description 2
- 240000007594 Oryza sativa Species 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 23
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 239000007810 chemical reaction solvent Substances 0.000 abstract 1
- 230000008020 evaporation Effects 0.000 abstract 1
- 238000001704 evaporation Methods 0.000 abstract 1
- 238000010574 gas phase reaction Methods 0.000 abstract 1
- 239000011541 reaction mixture Substances 0.000 abstract 1
- QEMXHQIAXOOASZ-UHFFFAOYSA-N tetramethylammonium Chemical compound C[N+](C)(C)C QEMXHQIAXOOASZ-UHFFFAOYSA-N 0.000 description 22
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Substances [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 12
- HADKRTWCOYPCPH-UHFFFAOYSA-M trimethylphenylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C1=CC=CC=C1 HADKRTWCOYPCPH-UHFFFAOYSA-M 0.000 description 12
- 238000004458 analytical method Methods 0.000 description 10
- 238000005516 engineering process Methods 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- -1 tetramethyl oxyammonia Chemical compound 0.000 description 6
- VFHDWENBWYCAIB-UHFFFAOYSA-M hydrogen carbonate;tetramethylazanium Chemical compound OC([O-])=O.C[N+](C)(C)C VFHDWENBWYCAIB-UHFFFAOYSA-M 0.000 description 5
- 241000209094 Oryza Species 0.000 description 4
- 238000005868 electrolysis reaction Methods 0.000 description 4
- 238000007701 flash-distillation Methods 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- 239000002918 waste heat Substances 0.000 description 4
- 241000370738 Chlorion Species 0.000 description 3
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- OKIZCWYLBDKLSU-UHFFFAOYSA-M N,N,N-Trimethylmethanaminium chloride Chemical compound [Cl-].C[N+](C)(C)C OKIZCWYLBDKLSU-UHFFFAOYSA-M 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 235000019253 formic acid Nutrition 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- 125000001453 quaternary ammonium group Chemical group 0.000 description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 2
- 230000036632 reaction speed Effects 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 150000003512 tertiary amines Chemical class 0.000 description 2
- WWIYWFVQZQOECA-UHFFFAOYSA-M tetramethylazanium;formate Chemical compound [O-]C=O.C[N+](C)(C)C WWIYWFVQZQOECA-UHFFFAOYSA-M 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000001099 ammonium carbonate Substances 0.000 description 1
- 235000012501 ammonium carbonate Nutrition 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- OMYOBDYSDXYBAL-UHFFFAOYSA-N carbonic acid;diethyl carbonate Chemical compound OC(O)=O.CCOC(=O)OCC OMYOBDYSDXYBAL-UHFFFAOYSA-N 0.000 description 1
- XDEFSTVHLNXBTJ-UHFFFAOYSA-N carbonic acid;dimethyl carbonate Chemical compound OC(O)=O.COC(=O)OC XDEFSTVHLNXBTJ-UHFFFAOYSA-N 0.000 description 1
- 238000010523 cascade reaction Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 150000001924 cycloalkanes Chemical class 0.000 description 1
- 230000003467 diminishing effect Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000000411 inducer Substances 0.000 description 1
- 150000007529 inorganic bases Chemical class 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- DAZMQARMQFEKQY-UHFFFAOYSA-L oxalate;tetramethylazanium Chemical compound C[N+](C)(C)C.C[N+](C)(C)C.[O-]C(=O)C([O-])=O DAZMQARMQFEKQY-UHFFFAOYSA-L 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
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- 239000011877 solvent mixture Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
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- 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
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/582—Recycling of unreacted starting or intermediate materials
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method and a device of continuously synthesizing tetramethyl ammonium carbonate by multi-reactors in series. Liquid-phase reaction materials in each reactor are connected in series through a pipeline. Gas-phase reaction materials are connected in parallel to keep the pressure between reactors balanced. The reaction materials flow into a next stage reactor from a previousstage reactor through the difference of liquid level in the reactors. The two stage reactors have a difference of liquid level of 0.5-1.0 m. The tetramethyl ammonium carbonate is prepared by continuously adding raw materials including dimethyl carbonate, trimethylamine and solvent methanol to a first stage tank reactor in a mole ratio of 1:0.8:3-1:1.5:8, leading a reaction mixture to continuouslyflow out from the last stage tank reactor, recycling a reaction solvent and an unconverted reactant by flash evaporation, then re-adding to the first stage tank reactor for recycling, and finally removing the solvent and the unconverted reactant. The operation pressure of the invention is the lowest, the reaction is stable, and continuous operation and automatic control are realized. Simultaneously, the reaction materials are heated to a reaction temperature by reaction heat, so the energy is saved and the production cost is reduced.
Description
Technical field
The present invention relates to method and device that a kind of continuous many still series connection prepare the tetramethyl ammonium carbonate salts.
Background technology
The tetramethyl oxyammonia claims tetramethylphosphonihydroxide hydroxide base amine (TMAH) again, it is the strongest a kind of organic base, be decomposed into methyl alcohol and trimethylamine in the time of 130 ℃, because TMAH has strong basicity, add not residual any material after the thermal decomposition simultaneously, particularly do not stay conductive ionic substance, therefore, it extensively is used in the manufacture process of LCD, LED and semiconductor chip as developer.It also has purposes very widely at other industrial circle, and for example: it can be used as the catalyst of organosilicon series product in synthetic, can be used for industries such as polyester polymerization, weaving, plastic products, leather.
TMAH made by two steps, and the first step is the synthetic of tetramethyl ammonium; Second step was that the method by electrolysis with ion-exchange film is converted into hydroxide with this ammonium salt.The material that can be used as tetramethyl ammonium has multiple, as tetramethyl ammonium chloride, tetramethyl ammonium formate, tetramethyl ammonium oxalate and tetramethyl ammonium carbonate.
Synthetic TMAH is by trimethylamine (TMA) and the synthetic tetramethyl ammonium chloride of monochloro methane the earliest, then by electrolytic preparation, owing to inevitably have chlorion in the product, chlorion can corrode the aluminium connecting line of integrated circuit, influence the quality of chip, in order to solve the etching problem to the aluminium connecting line, replace chloromethanes to synthesize with the more weak methyl formate of corrosivity and do not have the TMAH of chlorion solution, but when electrolysis tetramethyl ammonium formate, a spot of formic acid can enter cathode chamber by the anode chamber by amberplex, makes to contain a spot of formic acid among the TMAH.In order to prepare the higher TMAH of purity, the method for synthesizing TMAH with the tetramethyl ammonium carbonate salts has appearred.
The tetramethyl ammonium carbonate salts is the intermediate of the synthetic TMAH of electrolysis, it is to react in methyl alcohol (MEOH) solvent by trimethylamine and dimethyl carbonate (DMC) to generate tetramethyl-ammonium carbonic acid mono-methyl, under the situation of uniform temperature and water existence, tetramethyl-ammonium carbonic acid mono-methyl generation hydrolysis generates tetramethyl ammonium hydrogen carbonate and methyl alcohol, have the part tetramethyl ammonium hydrogen carbonate to add thermal decomposition simultaneously and generate the tetramethyl ammonium carbonate, the mixture of tetramethyl ammonium hydrogen carbonate and tetramethyl ammonium carbonate generates TMAH by electrolysis with ion-exchange film then.Its reaction equation is as follows:
Disclose the synthetic method of quaternary ammonium carbonate as far back as nineteen fifty-three US 2635100, this patent is by the method for chain tertiary amine and linear carbonate such as dimethyl carbonate or diethyl carbonate carbonate synthesis quaternary ammonium salt.US5438034 has disclosed the preparation process of another kind of carbonic acid quaternary ammonium salt, at first allows the reaction of quaternary ammonium chloride and inorganic base generate organic quaternary ammonium base, prepares the carbonic acid quaternary ammonium salt with carbon dioxide reaction then.US2004/0162343A1 discloses the method for carbonic acid mono-methyl quaternary ammonium salt, by tank reactor intermittently, by the method for tertiary amine and polycarbonate or alkane carbonic acid fat or cycloalkane carbonic acid fat prepared in reaction carbonic acid quaternary ammonium salt.Shumpei Shimizu etc. has proposed to pass through the method for electrolytic preparation TMAH then with trimethylamine and dimethyl carbonate carbonate synthesis quaternary ammonium salt in the clear 61-170588 of patent and US 4634509.All be to adopt tank reactor intermittently to carry out in the synthetic patent of carbonic acid quaternary ammonium salt, and its scale all is the preparative-scale in laboratory, the mode that shifts out of the continuity of course of reaction and reaction heat is not considered.
Patent CN101314572A discloses the method that a kind of tubular reactor prepares tetramethyl ammonium hydrogen carbonate continuously, with material carbon dimethyl phthalate, trimethylamine and solvent mixture preheating, carries out condensation reaction by tubular reactor then and makes tetramethyl ammonium hydrogen carbonate.
From above patent as can be seen, it is tank reactor or tubular reactor all has its shortcoming intermittently, intermittent reaction production efficiency is low, complicated operation, reaction between trimethylamine and the dimethyl carbonate is a strong exothermic reaction, carrying out along with reaction, concentration of reactants constantly changes, reaction rate is also along with change, so the heat that reaction system is emitted is also in continuous variation, in order to guarantee the temperature-resistant of reaction system, need constantly to adjust the consumption of cooling water, this causes reaction temperature to fluctuate in a big way again, has brought many troubles to practical operation, owing to the fluctuation of reaction condition, also influenced the stability of intermittent reaction process product quality and yield.
For tubular reactor, because the boiling point of raw material trimethylamine, dimethyl carbonate and reaction dissolvent differs greatly, under reaction temperature, can form biphase gas and liquid flow in the tubular reactor, for two kinds of raw materials of trimethylamine and dimethyl carbonate are fully mixed, will in tubular reactor, pack into static mixer and filling Raschig ring ceramic packing, so just increased the complexity of reactor, the DESIGN OF REACTOR difficulty is increased, loading the Raschig ring ceramic packing has simultaneously also increased the probability of introducing foreign ion in the sintetics, is unfavorable for the electronic grade product TMAH that reaches qualified.The synthetic reaction of trimethylamine and dimethyl carbonate is a strong exothermic reaction simultaneously, very responsive to reaction temperature, inducer at tubular reactor, the material concentration height, reaction speed is fast, liberated heat is big, shift out if reaction temperature is untimely, reaction temperature can further improve, reaction speed further increases, make that at last the temperature of reaction system is uncontrollable, so shifting out of reaction heat be the key that reacting balance carries out, the problem that also exists reaction temperature how to control to adiabatic tubular reactor; For isothermal tube reactor, reactor concentration of reactants in the axial direction constantly reduces, and reaction rate is corresponding reducing also, and liberated heat is also diminishing, and steadily shifting out also of reaction heat has difficulties.
Summary of the invention
The invention provides the connect method of the synthetic tetramethyl ammonium carbonate salts of continuous tank reactor of a kind of many stills, this method has overcome many weak points of batch reactor and tubular reactor, the reaction condition gentleness, course of reaction is steady, is easy to control, can realize serialization production and automation control, be convenient to large-scale production, the reactor simplicity of design, product yield height and steady quality, specific energy consumption is low.
Technical scheme of the present invention is as follows:
A kind of many stills tandem reactor prepares the device of tetramethyl-ammonium carbonate continuously, comprise at least two reactors, liquid phase reacting material in each still connects by the pipeline polyphone, gas phase is connected in parallel, be connected in parallel by gas phase and make between the reactor pressure keep balance, by the liquid level difference in the reactor, make reaction mass flow into the next stage reactor voluntarily from upper level, the liquid level difference of two-stage reaction still differs 0.5-1.0 rice.
Many stills cascade reaction still of the present invention is the series connection of two-stage reaction still or the series connection of third-order reaction still.
A kind of many stills tandem reactor prepared the method for tetramethyl-ammonium carbonate continuously: with material carbon dimethyl phthalate, trimethylamine and solvent methanol 1: 0.8 in molar ratio: 3-1: 1.5: 8 ratio adds first order reactor continuously, dimethyl carbonate and trimethylamine react in solvent, in continuous feed, reaction mass flows into the next stage reactor continuously automatically, the mixture that the afterbody reactor comes out enters flash tank and reclaims solvent and unconverted reactant, squeezes into the utilization of first order reactor cycles again after regenerant and the new solvent of replenishing.
The pressure of many stills tandem reactor is at 0.4-2.5MPa, and reaction temperature is 90-200 ℃.The temperature of each stage reactor is identical or different, but the pressure of each stage reactor is identical.
Describe the present invention below in detail:
The method of the continuously synthetic tetramethyl ammonium carbonate salts of a kind of many still series connection, the technical process of corresponding three stills series connection as shown in Figure 1, comprise: with the raw material trimethylamine, dimethyl carbonate and solvent are with mol ratio 1: 0.8: 3-1: 1.5: 8 respectively by measuring pump P1, P2, squeeze among the tank reactor R-1 with P3, after stopping certain hour therein, under the effect of liquid level difference among the inflow reactor R-2, and then from R-2, flow among the R-3, the pressure that reaches the reactant mixture utilization reaction of requirement conversion ratio itself enters among the flash tank V-1, in V-1, utilize the pressure of mixture and the waste heat of mixed material to carry out flash distillation, solvent and a small amount of unconverted trimethylamine and dimethyl carbonate become gas phase, coagulate the back by the cold E-1 of condenser and flow among the solvent recovery jar V-2, recovered solvent is returned in the reactor again as the solvent utilization by pump P-3 with the new solvent that replenishes.
This technology also can adopt the mode of two stills series connection, the technical process of corresponding two stills series connection as shown in Figure 2, comprise: with the raw material trimethylamine, dimethyl carbonate and solvent are with mol ratio 1: 0.8: 3-1: 1.5: 8 respectively by measuring pump P1, squeeze among the tank reactor R-1 with P2, after stopping certain hour therein, under the effect of liquid level difference among the inflow reactor R-2, the pressure that reaches the reactant mixture utilization reaction of requirement conversion ratio itself enters among the flash tank V-1, in V-1, utilize the pressure of mixture and the waste heat of mixed material to carry out flash distillation, solvent and a small amount of unconverted trimethylamine and dimethyl carbonate become gas phase, by flowing into after the condenser E1 condensation among the solvent recovery jar V-2, recovered solvent is returned in the reactor again as the solvent utilization by pump P-3 with the new solvent that replenishes.
For reactant mixture is not flow to into another reactor by a reactor voluntarily by pump, between each reactor balance pipe is housed, the setting height(from bottom) of reactor is reduced to R-3 successively by R-1, and its potential difference differs 0.5-1.0 rice.
The pressure of reactor depends primarily on the mole fraction of trimethylamine in reaction temperature and the reactant mixture, and reactive mode can adopt the temperature of each stage reactor identical, also can adopt the different mode of temperature of each stage reactor to react.If adopt the identical mode of reactor reaction temperature at different levels, first order reactor reaction-ure conversion-age is minimum, trimethylamine content is the highest, therefore reaction pressure is the highest, and the afterbody reaction-ure conversion-age is the highest, and the content of trimethylamine is minimum, the pressure of reactor is minimum, its shortcoming is that the trimethylamine that dissolves in the final reacting mixture is many, has increased the load that raw material reclaims.If adopt the different reactive mode of reactor reaction temperature at different levels, concentration of reactants height in the first order reactor, reaction rate is corresponding also high, the control reaction temperature is a little low, the pressure of reaction is also just low, and reaction rate is slow, and reaction heat is few, reaction can be carried out more stably, to the afterbody reactor, concentration of reactants is very low, and the height of reaction temperature control a bit, can improve the conversion ratio of reaction rate and reactant, make unconverted raw material fully react, the dividing potential drop of trimethylamine is very fast with the increase rising of temperature simultaneously, with the increase of temperature, the trimethylamine that dissolves in the mixture reduces, and has reduced the load of trimethylamine post processing.
Method of the present invention can be implemented under the following conditions
Reaction temperature: at 90-200 ℃; Reaction pressure: 0.4-2.5MPa; Raw material proportioning: dimethyl carbonate: trimethylamine: methyl alcohol is: 1: 0.8: 3-1: 1.5: 8, and reactor potential difference 0.5-1.0 rice.
The continuous tank reactor of plural serial stage, because strong agitation, material moment mixes fully in the material that enters reactor and the still, temperature everywhere in the still, parameters such as concentration are identical, equal outlet temperature and concentration, the concentration of first order reaction kettle for reaction thing reaches effectively and reduces, reaction rate reduces, and the reaction heat of emitting in the unit interval is few, just can effectively shift out reaction heat by general equipment, simplified production technology, reaction mass adds reactor continuously, and material is discharged reactor, continued operation continuously in the still, there is not in the intermittently operated problem non-cutting time, can be used for large-scale production.After raw material adds immediately with still in material evenly mix, there is not thermal accumlation and causes hot-spot, because the material capacity is big in the still, when to a certain degree fluctuation took place feed conditions, still internal reaction condition did not have significant change, good stability, handling safety, can realize automatic control, simple to operate, save manpower.
This technology has also reduced the energy consumption in the course of reaction, for intermittent reaction and pipe reaction, in order to reach the temperature that reaction requires, begins and will raw material and solvent heating be shifted out reaction heat after the reaction beginning again.And the present invention can utilize reaction heat itself to heat reaction mass, therefore can play energy-saving effect.
The technology of Fig. 1 and Fig. 2 has embodied advantage of the present invention; but the invention is not restricted to the technology of Fig. 1 and Fig. 2 indication; those skilled in the art can design the various modifications and changes in the technical scope of theory of the present invention; should be noted that these modifications and change also drop in protection scope of the present invention.
Description of drawings
The principle process schematic diagram of the synthetic tetramethyl ammonium carbonate salts of Fig. 1 three stills series connection.
The principle process schematic diagram of the synthetic tetramethyl ammonium carbonate salts of Fig. 2 two stills series connection.
The specific embodiment
Adopt three still tandem arrangements shown in Figure 1 to implement the inventive method, with the raw material trimethylamine, dimethyl carbonate and solvent are with mol ratio 1: 0.8: 3-1: 2: 8 respectively by measuring pump P1, P2, squeeze among the tank reactor R-1 with P3, after stopping certain hour therein, under the effect of liquid level difference among the inflow reactor R-2, and then from R-2, flow among the R-3, the pressure that reaches the reactant mixture utilization reaction of requirement conversion ratio itself enters among the flash tank V-1, in V-1, utilize the pressure of mixture and the waste heat of mixed material to carry out flash distillation, solvent and a small amount of unconverted trimethylamine and dimethyl carbonate become gas phase, by flowing into after the condenser condenses among the solvent recovery jar V-2, recovered solvent is returned in the reactor again as the solvent utilization by pump P-3 with the new solvent that replenishes.
Under the constant situation of production capacity, increase the volume of each grade tank reactor, prolong the time of staying of reaction mass in each stage reactor, reduce reactor progression, can reach the reaction effect identical with the series connection of three stills, two still tandem arrangements shown in Figure 2 are implemented the inventive method, and its technological process is that method of the present invention can be implemented under the following conditions: reaction temperature: at 90-200 ℃; Reaction pressure: 0.4-2.5MPa; Raw material proportioning: dimethyl carbonate: trimethylamine: methyl alcohol is: 1: 0.8: 3-1: 1.5: 8, and reactor potential difference 0.5-1.0 rice.
With the raw material trimethylamine, dimethyl carbonate and solvent are respectively by measuring pump P1, P2, squeeze among the tank reactor R-1 with P3, after stopping certain hour therein, under the effect of liquid level difference among the inflow reactor R-2, the pressure that reaches the reactant mixture utilization reaction of requirement conversion ratio itself enters among the flash tank V-1, in V-1, utilize the pressure of mixture and the waste heat of mixed material to carry out flash distillation, solvent and a small amount of unconverted trimethylamine and dimethyl carbonate become gas phase, by flowing into after the condenser E1 condensation among the solvent recovery jar V-2, recovered solvent is returned in the reactor again as the solvent utilization by pump P-3 with the new solvent that replenishes.Compare with three still tandem arrangements, except reactor reduced one, other technological process was identical with three still serial flows.
Followingly be described more specifically the present invention according to embodiment and comparative example:
By three grades of synthetic tetramethyl-ammonium carbonate of series connection tank reactor, the raw material proportioning is DMC: TMA: MEOH=1: 1: 6, the reaction temperature of first order reaction still is 100 ℃, the reaction temperature of second order reaction still is 110 ℃, and the reaction temperature of third-order reaction still is 120 ℃, and reaction pressure is 0.7MPa, the potential difference of each stage reactor is 0.5 meter, reaction mass is 2 hours at the mean residence time of each grade, the content of sample analysis tetramethylammonium ion, and the yield that gets the tetramethylammonium ion is 94.5%.
By three grades of synthetic tetramethyl-ammonium carbonate of series connection tank reactor, the raw material proportioning is DMC: TMA: MEOH=1: 0.8: 3, the reaction temperature of each order reaction still all is all 90 ℃ mutually, reaction pressure is 0.4MPa, the potential difference of each stage reactor is 1.0 meters, reaction mass is 2 hours at the mean residence time of each grade, the content of sample analysis tetramethylammonium ion, and the yield that gets the tetramethylammonium ion is 70.0%.
By three grades of synthetic tetramethyl-ammonium carbonate of series connection tank reactor, the raw material proportioning is DMC: TMA: MEOH=1: 1.5: 8, the reaction temperature of each order reaction still all is all 200 ℃ mutually, reaction pressure is 2.5MPa, the potential difference of each stage reactor is 0.5 meter, reaction mass is 2 hours at the mean residence time of each grade, the content of sample analysis tetramethylammonium ion, and the yield that gets the tetramethylammonium ion is 88.5%.
Embodiment 4
By three grades of synthetic tetramethyl-ammonium carbonate of series connection tank reactor, the raw material proportioning is DMC: TMA: MEOH=1: 1.2: 6, the reaction temperature of first order reaction still is 110 ℃, the reaction temperature of second order reaction still is 120 ℃, and the reaction temperature of third-order reaction still is 130 ℃, and reaction pressure is 1.0MPa, the potential difference of each stage reactor is 0.6 meter, reaction mass is 2 hours at the mean residence time of each grade, the content of sample analysis tetramethylammonium ion, and the yield that gets the tetramethylammonium ion is 95.6%.
Embodiment 5
By three grades of synthetic tetramethyl-ammonium carbonate of series connection tank reactor, the raw material proportioning is DMC: TMA: MEOH=1: 1.2: 4, the reaction temperature of each order reaction still all is all 120 ℃ mutually, reaction pressure is 0.8MPa, the potential difference of each stage reactor is 0.8 meter, reaction mass is 2 hours at the mean residence time of each grade, the content of sample analysis tetramethylammonium ion, and the yield that gets the tetramethylammonium ion is 93.6%.
Embodiment 6
By the synthetic tetramethyl-ammonium carbonate of two-stage series connection tank reactor, the raw material proportioning is DMC: TMA: MEOH=1: 0.8: 3, the reaction temperature of each order reaction still all is all 90 ℃ mutually, reaction pressure is 0.4MPa, the potential difference of reactor is 1.0 meters, reaction mass is 3 hours at the mean residence time of each grade, the content of sample analysis tetramethylammonium ion, and the yield that gets the tetramethylammonium ion is 75.6%.
Embodiment 7
By the synthetic tetramethyl-ammonium carbonate of two-stage series connection tank reactor, the raw material proportioning is DMC: TMA: MEOH=1: 1.5: 8, the reaction temperature of each order reaction still all is all 200 ℃ mutually, reaction pressure is 2.0MPa, the potential difference of reactor is 0.5 meter, reaction mass is 3 hours at the mean residence time of each grade, the content of sample analysis tetramethylammonium ion, and the yield that gets the tetramethylammonium ion is 90.2%.
Embodiment 8
By the synthetic tetramethyl-ammonium carbonate of two-stage series connection tank reactor, the raw material proportioning is DMC: TMA: MEOH=1: 1.2: 4, the reaction temperature of first order reactor is 115 ℃, the reaction temperature of second level reactor is 120 ℃, reaction pressure is 0.9MPa, and the potential difference of reactor is 0.7 meter, and reaction mass is 3 hours at the mean residence time of each grade, the content of sample analysis tetramethylammonium ion, the yield that gets the tetramethylammonium ion is 96.1%
Embodiment 9
By the synthetic tetramethyl-ammonium carbonate of two-stage series connection tank reactor, the raw material proportioning is DMC: TMA: MEOH=1: 1.1: 6, the reaction temperature of each order reaction still all is all 115 ℃ mutually, reaction pressure is 0.8MPa, the potential difference of reactor is 0.5 meter, reaction mass is 3 hours at the mean residence time of each grade, the content of sample analysis tetramethylammonium ion, and the yield that gets the tetramethylammonium ion is 92.2%.
Comparative Examples 1
Adopt batch reactor, the raw material proportioning is DMC: TMA: MEOH=1: 1.2: 4, reaction temperature was 110 ℃, and reaction pressure is 1.0MPa, successive reaction 6 hours, and the content of sample analysis tetramethylammonium ion, the yield that gets the tetramethylammonium ion is 90.6%
Continuous many still series connection that the present invention proposes prepare method and the device of tetramethyl ammonium carbonate salts, be described by on-the-spot preferred embodiment, person skilled obviously can be changed or suitably change and combination method as herein described in not breaking away from content of the present invention, spirit and scope, realizes the technology of the present invention.Special needs to be pointed out is, the replacement that all are similar and change apparent to those skilled in the artly, they are regarded as being included in spirit of the present invention, scope and the content.
Claims (2)
1. still tandem reactor more than a kind prepares the method for tetramethyl-ammonium carbonate continuously: this reactor comprises at least two reactors, it is characterized in that the liquid phase reacting material in each still is connected in series by pipeline, gas phase is connected in parallel, be connected in parallel by gas phase and make between the reactor pressure keep balance, by the liquid level difference in the reactor, make reaction mass flow into the next stage reactor voluntarily from upper level, the liquid level difference of two-stage reaction still differs 0.5-1.0 rice; With material carbon dimethyl phthalate, trimethylamine and solvent methanol in molar ratio the ratio of 1:1:6,1:0.8:3,1:1.5:8,1:1.2:6,1:1.2:4 or 1:1.1:6 add first order reactor continuously, dimethyl carbonate and trimethylamine react in solvent, in continuous feed, reaction mass flows into the next stage reactor continuously automatically, the mixture that the afterbody reactor comes out enters flash tank and reclaims solvent and unconverted reactant, and it is recycling to squeeze into first order reactor again after regenerant and the new solvent of replenishing; The pressure of many stills tandem reactor is at 0.4-2.5MPa, and reaction temperature is 90-200 ℃; The temperature of each order reaction still is identical or different, but the pressure of each order reaction still is identical.
2. the method for claim 1 is characterized in that many stills tandem reactor is the series connection of two-stage reaction still or the series connection of third-order reaction still.
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| CN103157425B (en) * | 2011-12-13 | 2015-01-07 | 中国科学院大连化学物理研究所 | Continuous production device for catalytic reaction by adopting phase transfer catalyst |
| CN106905176B (en) * | 2017-02-13 | 2019-07-09 | 湘潭大学 | Continuous hydrolysis prepares the method and self-oscillation reactor of imido oxalic acid |
| CN107417539B (en) * | 2017-05-16 | 2019-09-03 | 天津大学 | A kind of method of tank reactor series connection tubular reactor synthesis tetramethyl ammonium hydrogen carbonate |
| CN108440306B (en) * | 2018-05-24 | 2023-11-03 | 柏川新材料科技(宁波)有限公司 | Green production equipment and method of tetramethyl ammonium carbonate |
| CN109369418A (en) * | 2018-10-10 | 2019-02-22 | 河南师范大学 | A kind of continuous synthesis technology and synthesizer of energy saving and environment friendly alkyl benzene amine class I liquid I antioxidant |
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| CN114181158A (en) * | 2021-12-29 | 2022-03-15 | 江西禾益化工股份有限公司 | Device and method for producing bupirimate in continuous kettle manner |
| CN114573458A (en) * | 2022-03-07 | 2022-06-03 | 沧州信联化工有限公司 | Method for synthesizing tetramethylammonium bicarbonate by using microchannel reactor and tubular reactor connected in series |
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| US4776929A (en) * | 1986-11-25 | 1988-10-11 | Mitsubishi Gas Chemical Company, Inc. | Process for production of quaternary ammonium hydroxides |
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| US4776929A (en) * | 1986-11-25 | 1988-10-11 | Mitsubishi Gas Chemical Company, Inc. | Process for production of quaternary ammonium hydroxides |
| CN1464873A (en) * | 2001-07-09 | 2003-12-31 | 伦萨公司 | In situ process for preparing quaternary ammonium bicarbonates and quaternary ammonium carbonates |
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| CN101314572A (en) * | 2008-07-08 | 2008-12-03 | 杭州格林达化学有限公司 | Method for preparing tetramethyl ammonium hydrogen carbonate with condensation reaction of pipe type reactor |
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