CN101747298B - Preparation process of high-purity diketene - Google Patents
Preparation process of high-purity diketene Download PDFInfo
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- CN101747298B CN101747298B CN2010101033381A CN201010103338A CN101747298B CN 101747298 B CN101747298 B CN 101747298B CN 2010101033381 A CN2010101033381 A CN 2010101033381A CN 201010103338 A CN201010103338 A CN 201010103338A CN 101747298 B CN101747298 B CN 101747298B
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Abstract
The invention relates to a preparation process of high-purity diketene. The defects of low ketene purity, low purity and poor safety of diketene products prepared by absorption polymerization of ketene, complex flow, high cost and high content of residual acetic acid in concentration and recovery of dilute acetic acid are overcome. The invention is suitable for the preparation process of high-purity diketene: absorbing and polymerizing ketene dimer under low temperature condition on the basis of generating pure ketene gas by removing impurities from cracked gas by adopting stable acetic acid cracking condition and deep freezing, further purifying the diketene product by adopting a membrane evaporator under low temperature and low pressure condition, introducing a polymerization inhibitor and adding a stabilizer after refining diketene in the ketene absorption polymerization process so as to improve the safety in synthesis and the stability of the product in a storage tank; meanwhile, the temperature of each point of the stripping section is reasonably matched by the dilute acetic acid generated in the process through a sensitive plate technology, the water carrying capacity of butyl acetate is improved, and the concentration of acetic acid in the concentrated residual liquid is greatly reduced.
Description
Technical field
The present invention relates to the preparation technology of ketene, relate in particular to a kind of process for preparing high-purity diketene.
Background technology
Contain two two keys in the molecular structure of ketene dimer; Make it have the nonsaturation of height, chemical property is very active, can with reactions such as generation such as alcohol, amine, halogen, ketone, acid additions, decomposition, nitrated, polymerization; Be important organic intermediate, the multiple product of can deriving.Has application widely at aspects such as medicine, agricultural chemicals, dyestuff, food and feed additive, organic syntheses.
Prior art does not still have open high-purity diketene production technology, is in the technical know-how state.Side reaction is many in the preparation of the ketene that relevant conventional process techniques contains and the purification, product purity is low; The refining middle low and poor stability of product purity of the absorbing polymer of the ketene that contains and thick ketene dimer; The dilute acetic acid that contains is put forward flow process complicacy in the dense recovery, cost is high, the raffinate acetic acid content high.
The high-purity diketene production technology is to generate on the maturation process basis of ketene at acetic acid cracking; Develop the new technology route of a cover low consumption high yield that comes out voluntarily; The product purity of producing in the existing technology is low, the difficult problem of poor stability thereby solve, and satisfies the domestic needs growing to this important organic intermediate.
Summary of the invention
Technical problem to be solved by this invention is to provide production cost low to above-mentioned prior art deficiency, and facility investment is few, and side reaction is few, the process for preparing high-purity diketene that product purity is high.
The present invention solves the problems of the technologies described above the technical scheme that is adopted: process for preparing high-purity diketene, contain the preparation technology of ketene; The absorbing polymer technology that contains ketene; The process for refining that contains ketene dimer; Also contain the dilute acetic acid extracting and concentrating technology.
Described acetic acid cracking and freezing removal of impurities operation are that acetic acid is got into pyrolyzer, cracking production ketene gas under the condition of high temperature, decompression and catalyzer through gasification; Described freezing removal of impurities is to remove foreign gas wherein through low-temperature cooling system from the ketene gas of pyrolyzer outlet, thereby obtains highly purified ketene gas;
Described absorption and polymerization process are that the ketene gas of purifying is introduced the packed absorber bottom, and the reverse spray of the thick ketene dimer that under 5-10 ℃ of condition, gets into the top absorbs, and forms absorption liquid, and absorption liquid gets into polymeric kettle; Generate thick ketene dimer 15-25 ℃ of following polymerization, pump into then and carry out circulated sprinkling in the absorption tower;
Described distillation refining step is for introducing in the film-type evaporator and carry out underpressure distillation adding stablizer in the thick ketene dimer, 50-55 ℃ with the 8-10kPa negative pressure under collect pure ketene dimer cut;
Described dilute acetic acid is put forward dense operation and is collected for the dilute acetic acid that acetic acid cracking and freezing removal of impurities operation, absorbing polymer operation and distillation refining step are produced and carry out rectifying and carry densely, and the dense acetic acid that is produced returns the acetic acid cracking operation.
The catalyzer that described cracking operation is used is made as in the storage tank of selecting for use triethyl phosphate is mixed in 1: 10 ratio with deionized water, is mixed with the triethyl phosphate aqueous solution as catalyzer, introduces the catalyzer header tank with pump then.
Acetic acid cracking and freezing removal of impurities operation are operated according to following technology:
(1) the acetic acid cracking reaction adopts high temperature catalyst that triethyl phosphate, primary ammonium phosphate are arranged, and the present invention adopts triethyl phosphate.Will from dilute acetic acid carry that dense operation obtains＞80% acetic acid;＞80% acetic acid dense with carrying and 99% Glacial acetic acid min. 99.5 are mixed with 91%～95% acetum; This acetum of 91%～95% is through gasification; The triethyl phosphate of acetic acid steam and quality percentage composition about 8～12% is carried out Pintsch process in the cracking tube that 100: 2～100: 4 ratio gets under 730 ℃～750 ℃, 10～15kPa negative pressure simultaneously, and acetic acid is the mixed pyrolysis gas that contains ketene, water and side reaction product by thermo-cracking;
(2) for stoping the reversed reaction and the polymerization of ketene in the mixed pyrolysis gas; Mixed pyrolysis gas is cooled to rapidly below-20 ℃ through cooler package before the pump with 0.3～0.5% the liquefied ammonia that adds by the acetic acid charging capacity; And pass through four sections cooling condensation processes step by step with the water in the mixed pyrolysis gas; Other side reaction gas, and uncracked acetic acid becomes phlegma and gets into the phlegma receiver of each section, obtains pure ethylene ketone gas; Each section phlegma is delivered to dilute acetic acid and is put forward dense operation;
(3) pure ethylene ketone gas is through liquid ring vacuum pump delivery operation; Be cooled to rapidly below-30 ℃ through pump aftercooler group by vacuum pump; And isolate piecemeal by liquid behind the pump of generations such as liquid-ring vacuum pump compression through four sections cooling condensation processes and to obtain pure ketene gas, send into ketene absorbing polymer operation again; Liquid forms dilute acetic acid and delivers to dilute acetic acid and put forward dense operation behind the pump after hydrolysis.
Described ketene absorbing polymer is operated according to following technology:
(1) pure ethylene ketone gas is got into the thick ketene dimer liquid spraying that ceramic ripple type whole plate packed absorber bottom and cat head introducing are housed and carries out 5～10 ℃ of counter current contact under the condition down;
(2) go out absorption liquid and stablizer from tower bottom flow and get into polymeric kettle simultaneously in 0.01%～0.1% ratio, generate thick ketene dimer 15-25 ℃ of following polymerization, the thick ketene dimer solution after polyreaction returns the absorption tower, absorbs circularly and polymerization process;
The reaction end gas of (3) overflowing from cat head enters total waste pipe after washing; Water lotion is that dilute acetic acid is delivered to dilute acetic acid and put forward dense operation.
Described ketene polymerization, ketene dimer distillation refining step use stablizer; Stablizer is selected from sulphur, alcohols, phenols, borate, vitriol, preferred terepthaloyl moietie, Ucar 35, Virahol, dihydroxy-benzene; The monomethyl ether of Resorcinol, more preferably terepthaloyl moietie, Ucar 35, dihydroxy-benzene.
The process for refining of described ketene dimer includes:
(1) the thick ketene dimer liquid that polymeric kettle is produced gets into refining step: 50-55 ℃ with the 8-10kPa condition of negative pressure under, thick ketene dimer liquid is introduced from the thin-film evaporator top, thick ketene dimer is along the dirty formation film of wall and by continuous still battery;
The low-boiling point gas of (2) discharging from the vaporizer top is pure ketene dimer product through the cooled phlegma of shell and tube cooler; For guaranteeing the stable of dipolymer, avoid forming trimer, this product needs the stablizer of adding 0.1%～1% after getting into the product storage tank;
Said shell and tube cooler is the shell and tube cooler of-5～-10 ℃ of terepthaloyl moietie cryogens.
(3) from the effusive high boiling point raffinate of base of evaporator, get into residual liquid tank, the formation dilute acetic acid is delivered to dilute acetic acid and is put forward dense operation after hydrolysis.
Described dilute acetic acid extracting and concentrating technology includes:
(1) will be collected in the dilute acetic acid holding tank from the dilute acetic acid of cooler package operation before the acetic acid cracking operation pump and pump aftercooler group operation, ketene absorbing polymer operation washing bath and the generation of ketene dimer refining step hydrolytic tank;
(2) dilute acetic acid from the dilute acetic acid holding tank pumps into the middle part of dilute acetic acid rectifying tower through flow measurement device; Disposable adding acetic acid is as bed material during beginning; Reboiler begins heating then, adds N-BUTYL ACETATE from cat head when treating that tower top temperature reaches 85-95 ℃, simultaneously with 2m
3/ h～5m
3The speed of/h adds dilute acetic acid to rectifying tower;
(3) when gas in the tower and phegma carry out heat exchange; Adopt the sensitive plate control techniques; Make the desired temperature (107～110 ℃) at the 5th column plate place of stripping section carry out chain adjusting with reboiler heating steam vapour amount; Thereby reach the band outlet capacity that gas-liquid phase equilibrium has improved N-BUTYL ACETATE, the azeotrope of N-BUTYL ACETATE and water steams from cat head, steams thing and after condenser condenses, gets into ester water stratification device; N-BUTYL ACETATE returns rectifying tower cat head dehydration cycle after the layering, and waste water is discharged to treatment tank after treatment; Reboiler round-robin acetate concentration analyze qualified after, discharging continuously again behind condensing surface, concentrated acid storage tank, is turned back to the acetic acid configured slot of cracking operation by pump after the decolouring of concentrated acid bleaching tower;
(4) superpolymer at the bottom of the bleaching tower still becomes dilute acetic acid through washing, turns back to the charging of rectifying tower dilute acetic acid through the dilute acetic acid basin
Device.
The principle of described cracking operation and reaction formula:
Main reaction:
Side reaction: 2CH
3COOH → CH
2=CO+CH
4+ H
2O+CO
2
2CH
2＝CO→CH
4+C+2CO
The principle of described absorption and polymerization process and reaction formula:
Main reaction:
Side reaction: CH
2=CO+H
2O → CH
3COOH
CH
2＝CO+CH
3COOH→(CH
3CO)
2O
Described dilute acetic acid is carried the principle and the reaction formula of dense operation:
The ketene that acetic acid cracking generated absorbs the dilute acetic acid that obtains through condensation of freezing removal of impurities operation and water, and the unabsorbed ketene gas of absorbing polymer operation, and water captures and absorbs the dilute acetic acid that generates in the water absorption tower:
CH
2＝CO+H
2O→CH
3COOH
With the reuse of N-BUTYL ACETATE component distillation.
Described four sections cooling condensation processes promptly refer to splitting gas through four cooling condensation processes, and one section cooling condensation device is made up of a water cooler and a storage tank, then representes cracked gas through a water cooler, and its phlegma is collected in the storage tank.Wherein, the structure of water cooler is the sleeve structure except that first section, and other several sections are generally shell and tube cooler.Four sections cooling condensation processes are promptly represented to be made up of quadruplet cooling condensation device, and the cracked gas just temperature when cracking tube exports is 780～800 ℃, and whenever through a section apparatus, temperature descends, and through four-stage device, its temperature will reach-20 ℃ step by step.Splitting gas dependence oil ring vacuum pump is bled and is power; And the malleation of four sections cooling condensation processes dependence oil ring vacuum pumps behind the pump is carried, but the cracked gas of suction vacuum pump compresses intensification because pump is interior, thereby need carry out the cooling condensation process again.Each cooling condensation process promptly is the removal of impurities process.
Compare with conventional art, the invention has the advantages that: the one, adopt vertical pyrolyzer with the Sweet natural gas heating, system is stable, ketene purity high, running cost is low; The 2nd, rationally select good ketene dimer stablizer terepthaloyl moietie for use, its advantage is that add-on is few, and steady time is long, and stability does not subtract when high temperature, and low price is prone to mix with ketene dimer; The 3rd, adopt the sensitive plate control techniques, temperature in the rational Match dilute acetic acid rectifying tower makes that acetate concentration reduces greatly in the raffinate.
Stablizer is actual, and what rise is inhibition, in the product prepn process, is stopper, and in the product storage process, can plays stabilization.
Remarkable innovative point of the present invention has:
1. adopt novel acetic acid cracking device: with the vertical pyrolyzer of Sweet natural gas heating, to improve the economy that ketene is produced; Adopt novel oil ring vacuum pump, make the reactive site vacustat, to improve the acetic acid transformation efficiency; Implement the deep refrigeration removal of impurities, make ketene output temperature reach-25～-30 ℃, with purity to 94%～95% of raising ketene, thus the purity of assurance the finished product.
2. strengthen the processing condition of ketene absorbing polymer and ketene dimer rectification operation: the absorbing polymer operation adopts the low temperature process condition, to improve the solubleness of ketene in thick ketene dimer; The whole plate filling-material structure of novel ceramic ripple type is adopted on the absorption tower, is the transformation efficiency of ketene dimer to improve ketene gas dimerization in thick ketene dimer liquid; The terepthaloyl moietie stablizer is adopted in screening in ketene absorbing polymer and ketene dimer storage, and the height that had both suppressed ketene dimer gathers, and has improved security in service again.Thereby the purity that makes ketene dimer reaches >=and 98%.
3. optimize dilute acetic acid and put forward dense recovery technology: adopt the sensitive plate control techniques; Each point temperature between reboiler and stripping section is carried out rational Match and chain adjusting; Increase the band outlet capacity of N-BUTYL ACETATE; Not only make acetate concentration rise to 80%～90%, and in the raffinate acetate concentration be reduced to≤0.1%.Put forward dense flow process thereby simplified, reduce power source consumption.
Description of drawings
Fig. 1 is embodiment of the invention process flow sheet top (an acetic acid cracking operation);
Fig. 2 is embodiment of the invention process flow sheet middle part (ketene dimer synthesis procedure);
Fig. 3 is embodiment of the invention process flow sheet bottom (dilute acetic acid is put forward dense operation).
Embodiment
Embodiment describes in further detail the present invention below in conjunction with accompanying drawing.
Embodiment 1
To shown in Figure 3, process for preparing high-purity diketene comprises that acetic acid cracking operation, ketene dimer synthesis procedure, dilute acetic acid put forward dense operation like Fig. 1.
The acetic acid cracking operation includes:
Will from dilute acetic acid carry that dense operation obtains＞80% acetic acid and 99% Glacial acetic acid min. 99.5 be mixed with 92% acetum; This acetum is got into 740 ℃ cracking tube simultaneously and under the 12kPa negative pressure, carries out Pintsch process by 0.3% of unit time acetic acid charging capacity with the triethyl phosphate solution catalyst that configures through being gasificated as acetic acid steam, and acetic acid is the mixed pyrolysis gas that contains ketene, water and side reaction product by thermo-cracking; For stoping ketene reversed reaction and polymerization; Feed in real time 0.3% the liquefied ammonia of pressing the acetic acid charging capacity in the mixed pyrolysis gas; Be cooled to rapidly below-20 ℃ through cooler package before the pump simultaneously then, and pass through four sections cooling condensation processes step by step with the water in the mixed pyrolysis gas, other side reaction gas; And uncracked acetic acid becomes phlegma and gets into the phlegma receiver of each section, obtains pure ethylene ketone gas; Each section phlegma is delivered to dilute acetic acid and is put forward dense operation; Purified ketene gas is through the liquid ring vacuum pump delivery; Be cooled to rapidly below-30 ℃ through pump aftercooler group by vacuum pump; And isolate piecemeal through four sections cooling condensation processes that to obtain purity by liquid behind the pump of generations such as liquid-ring vacuum pump compression be 94～95% ketene, send into ketene absorbing polymer operation; Liquid forms dilute acetic acid and delivers to dilute acetic acid and put forward dense operation behind the pump after hydrolysis.
The ketene dimer synthesis procedure includes:
Pure ethylene ketone gas is got into
The thick ketene dimer liquid spraying introduced of packed absorber bottom and cat head and carry out 8 ℃ of counter current contact under the condition down; Gather and improve processing safety and go out the 5m that absorption liquid and terepthaloyl moietie stablizer get in 0.05% ratio simultaneously for suppressing the ketene dimer height from tower bottom flow
3Polymeric kettle generates thick ketene dimer 20 ℃ of following polymerizations, and the thick ketene dimer solution after polyreaction returns the absorption tower, absorbs circularly and polymerization process; From the reaction end gas that cat head is overflowed, after washing, discharge and get into total waste pipe; Water lotion is that dilute acetic acid is delivered to dilute acetic acid and put forward dense operation; When the thick ketene dimer composition in the polymeric kettle when analysis reaches 90%, the absorption program that stops to circulate, the thick ketene dimer liquid that polymeric kettle is produced gets into the distillation refining step.
53 ℃ with the 9kPa condition of negative pressure under; Thick ketene dimer liquid is introduced with the thin-film evaporator top of flow from
of 700kg/h, and thick ketene dimer is along the dirty formation film of wall and by continuous still battery; The low-boiling point gas of discharging from the vaporizer top is pure ketene dimer product through cooled phlegma, and its purity is 98%; From the effusive high boiling point raffinate of base of evaporator, get into residual liquid tank, the formation dilute acetic acid is delivered to dilute acetic acid and is put forward dense operation after hydrolysis.For guaranteeing the stable of dipolymer, avoid forming trimer, this product adds 0.5% ethylene glycol solution after getting into the product storage tank.
Dilute acetic acid is put forward dense operation and is included:
To be collected in the dilute acetic acid holding tank from the dilute acetic acid of cooler package operation before the acetic acid cracking operation pump and pump aftercooler group operation, ketene absorbing polymer operation washing bath and the generation of ketene dimer refining step hydrolytic tank; Dilute acetic acid from the dilute acetic acid holding tank pumps into through flow measurement device
The middle part of dilute acetic acid rectifying tower, during beginning disposable adding acetic acid as bed material, shell and tube reboiler (F=50m then
2) begin heating, add N-BUTYL ACETATE from cat head when treating that tower top temperature reaches 90 ℃, simultaneously with 3m
3The speed of/h adds dilute acetic acid to rectifying tower; When gas in the tower and phegma carry out heat exchange; Adopt the sensitive plate control techniques, each point temperature between reboiler and stripping section is carried out rational Match and chain adjusting, thereby reach the band outlet capacity that gas-liquid phase equilibrium has improved N-BUTYL ACETATE; The azeotrope of N-BUTYL ACETATE and water steams from cat head; Steam thing and after condenser condenses, get into ester water stratification device, N-BUTYL ACETATE returns rectifying tower cat head dehydration cycle after the layering, and waste water is discharged to treatment tank after treatment; N-BUTYL ACETATE replenishes by 3% rate of loss; After the analysis of reboiler round-robin acetate concentration was 85%, continuously discharging again behind condensing surface, dense acetic acid storage tank, was turned back to the acetic acid configured slot of cracking operation by pump after dense acetic acid bleaching tower decolouring; The superpolymer that contains 0.1% acetic acid at the bottom of the bleaching tower still becomes dilute acetic acid through washing, turns back to rectifying tower dilute acetic acid feeding unit through the dilute acetic acid basin.
Embodiment 2
Acetic acid cracking and freezing removal of impurities operation are operated according to following technology, and all the other are with embodiment 1:
(1) acetic acid cracking reaction employing high temperature catalyst is a triethyl phosphate.Will from dilute acetic acid carry that dense operation obtains＞80% acetic acid;＞80% acetic acid dense with carrying and 99% Glacial acetic acid min. 99.5 are mixed with 91% acetum; This acetum of 91% is through gasification; The triethyl phosphate of acetic acid steam and quality percentage composition about 8 is carried out Pintsch process in the cracking tube that 100: 2 ratio gets under 730 ℃, 10kPa negative pressure simultaneously, and acetic acid is the mixed pyrolysis gas that contains ketene, water and side reaction product by thermo-cracking;
(2) for stoping the reversed reaction and the polymerization of ketene in the mixed pyrolysis gas; Mixed pyrolysis gas is cooled to rapidly below-20 ℃ through cooler package before the pump with 0.3% the liquefied ammonia that adds by the acetic acid charging capacity; And pass through four sections cooling condensation processes step by step with the water in the mixed pyrolysis gas; Other side reaction gas, and uncracked acetic acid becomes phlegma and gets into the phlegma receiver of each section, obtains pure ethylene ketone gas; Each section phlegma is delivered to dilute acetic acid and is put forward dense operation;
(3) pure ethylene ketone gas is through liquid ring vacuum pump delivery operation; Be cooled to rapidly below-30 ℃ through pump aftercooler group by vacuum pump; And isolate piecemeal by liquid behind the pump of generations such as liquid-ring vacuum pump compression through four sections cooling condensation processes and to obtain pure ketene gas, send into ketene absorbing polymer operation again; Liquid forms dilute acetic acid and delivers to dilute acetic acid and put forward dense operation behind the pump after hydrolysis.
Embodiment 3
Acetic acid cracking and freezing removal of impurities operation are operated according to following technology, and all the other are with embodiment 1:
(1) acetic acid cracking reaction employing high temperature catalyst is a primary ammonium phosphate; Will from dilute acetic acid carry that dense operation obtains＞80% acetic acid;＞80% acetic acid dense with carrying and 99% Glacial acetic acid min. 99.5 are mixed with 95% acetum; This acetum of 95% is through gasification; The primary ammonium phosphate of acetic acid steam and quality percentage composition about 12% is carried out Pintsch process in the cracking tube that 100: 4 ratio gets under 750 ℃, 15kPa negative pressure simultaneously, and acetic acid is the mixed pyrolysis gas that contains ketene, water and side reaction product by thermo-cracking;
(2) mixed pyrolysis gas is cooled to rapidly below-20 ℃ through cooler package before the pump; And pass through four sections cooling condensation processes step by step with the water in the mixed pyrolysis gas; Other side reaction gas, and uncracked acetic acid becomes phlegma and gets into the phlegma receiver of each section, obtains pure ethylene ketone gas; Each section phlegma is delivered to dilute acetic acid and is put forward dense operation;
(3) pure ethylene ketone gas is through liquid ring vacuum pump delivery operation; Be cooled to rapidly below-30 ℃ through pump aftercooler group by vacuum pump; And isolate piecemeal by liquid behind the pump of generations such as liquid-ring vacuum pump compression through four sections cooling condensation processes and to obtain pure ketene gas, send into ketene absorbing polymer operation again; Liquid forms dilute acetic acid and delivers to dilute acetic acid and put forward dense operation behind the pump after hydrolysis.
Embodiment 4
Described ketene absorbing polymer is operated according to following technology, and all the other are with embodiment 1:
(1) pure ethylene ketone gas is got into the thick ketene dimer liquid spraying that ceramic ripple type whole plate packed absorber bottom and cat head introducing are housed and carries out 5 ℃ of counter current contact under the condition down;
(2) go out absorption liquid and terepthaloyl moietie from tower bottom flow and get into polymeric kettle simultaneously in 0.01% ratio, generate thick ketene dimer 15 ℃ of following polymerizations, the thick ketene dimer solution after polyreaction returns the absorption tower, absorbs circularly and polymerization process;
The reaction end gas of (3) overflowing from cat head enters total waste pipe after washing; Water lotion is that dilute acetic acid is delivered to dilute acetic acid and put forward dense operation.
Embodiment 5
Described ketene absorbing polymer is operated according to following technology, and all the other are with embodiment 1:
(1) pure ethylene ketone gas is got into the thick ketene dimer liquid spraying that ceramic ripple type whole plate packed absorber bottom and cat head introducing are housed and carries out 10 ℃ of counter current contact under the condition down;
(2) go out absorption liquid and terepthaloyl moietie from tower bottom flow and get into polymeric kettle simultaneously in 0.1% ratio, generate thick ketene dimer 25 ℃ of following polymerizations, the thick ketene dimer solution after polyreaction returns the absorption tower, absorbs circularly and polymerization process;
The reaction end gas of (3) overflowing from cat head enters total waste pipe after washing; Water lotion is that dilute acetic acid is delivered to dilute acetic acid and put forward dense operation.
Embodiment 6-13
Catalyzer and quality percentage composition thereof in the acetic acid cracking reaction are selected from following table; Stablizer and consumption thereof are selected from following table, and all the other are with embodiment 1.
Embodiment 14
The process for refining of described ketene dimer includes, and all the other are with embodiment 1:
(1) the thick ketene dimer liquid that polymeric kettle is produced gets into refining step: 50 ℃ with the 8kPa condition of negative pressure under, thick ketene dimer liquid is introduced from the thin-film evaporator top, thick ketene dimer is along the dirty formation film of wall and by continuous still battery;
The low-boiling point gas of (2) discharging from the vaporizer top is pure ketene dimer product through the cooled phlegma of shell and tube cooler of-5 ℃ of terepthaloyl moietie cryogens; For guaranteeing the stable of dipolymer, avoid forming trimer, this product needs the ethylene glycol solution of adding 0.1% after getting into the product storage tank;
(3) from the effusive high boiling point raffinate of base of evaporator, get into residual liquid tank, the formation dilute acetic acid is delivered to dilute acetic acid and is put forward dense operation after hydrolysis.
Embodiment 15
The process for refining of described ketene dimer includes, and all the other are with embodiment 1:
(1) the thick ketene dimer liquid that polymeric kettle is produced gets into refining step: 55 ℃ with the 10kPa condition of negative pressure under, thick ketene dimer liquid is introduced from the thin-film evaporator top, thick ketene dimer is along the dirty formation film of wall and by continuous still battery;
The low-boiling point gas of (2) discharging from the vaporizer top is pure ketene dimer product through the cooled phlegma of shell and tube cooler of-10 ℃ of terepthaloyl moietie cryogens; For guaranteeing the stable of dipolymer, avoid forming trimer, this product needs the ethylene glycol solution of adding 1% after getting into the product storage tank;
(3) from the effusive high boiling point raffinate of base of evaporator, get into residual liquid tank, the formation dilute acetic acid is delivered to dilute acetic acid and is put forward dense operation after hydrolysis.
Embodiment 16
Described dilute acetic acid extracting and concentrating technology includes, and all the other are with embodiment 1:
(1) will be collected in the dilute acetic acid holding tank from the dilute acetic acid of cooler package operation before the acetic acid cracking operation pump and pump aftercooler group operation, ketene absorbing polymer operation washing bath and the generation of ketene dimer refining step hydrolytic tank;
(2) dilute acetic acid from the dilute acetic acid holding tank pumps into the middle part of dilute acetic acid rectifying tower through flow measurement device; Disposable adding acetic acid is as bed material during beginning; Reboiler begins heating then, adds N-BUTYL ACETATE from cat head when treating that tower top temperature reaches 85 ℃, simultaneously with 2m
3The speed of/h adds dilute acetic acid to rectifying tower;
(3) when gas in the tower and phegma carry out heat exchange; Adopt the sensitive plate control techniques; Make the desired temperature (107～110 ℃) at the 5th column plate place of stripping section carry out chain adjusting with reboiler heating steam vapour amount; Thereby reach the band outlet capacity that gas-liquid phase equilibrium has improved N-BUTYL ACETATE, the azeotrope of N-BUTYL ACETATE and water steams from cat head, steams thing and after condenser condenses, gets into ester water stratification device; N-BUTYL ACETATE returns rectifying tower cat head dehydration cycle after the layering, and waste water is discharged to treatment tank after treatment; Reboiler round-robin acetate concentration analyze qualified after, discharging continuously again behind condensing surface, concentrated acid storage tank, is turned back to the acetic acid configured slot of cracking operation by pump after the decolouring of concentrated acid bleaching tower;
(4) superpolymer at the bottom of the bleaching tower still becomes dilute acetic acid through washing, turns back to rectifying tower dilute acetic acid feeding unit through the dilute acetic acid basin.
Embodiment 17
Described dilute acetic acid extracting and concentrating technology includes, and all the other are with embodiment 1:
(1) will be collected in the dilute acetic acid holding tank from the dilute acetic acid of cooler package operation before the acetic acid cracking operation pump and pump aftercooler group operation, ketene absorbing polymer operation washing bath and the generation of ketene dimer refining step hydrolytic tank;
(2) dilute acetic acid from the dilute acetic acid holding tank pumps into the middle part of dilute acetic acid rectifying tower through flow measurement device; Disposable adding acetic acid is as bed material during beginning; Reboiler begins heating then, adds N-BUTYL ACETATE from cat head when treating that tower top temperature reaches 95 ℃, simultaneously with 5m
3The speed of/h adds dilute acetic acid to rectifying tower;
(3) when gas in the tower and phegma carry out heat exchange; Adopt the sensitive plate control techniques; Make the desired temperature (107～110 ℃) at the 5th column plate place of stripping section carry out chain adjusting with reboiler heating steam vapour amount; Thereby reach the band outlet capacity that gas-liquid phase equilibrium has improved N-BUTYL ACETATE, the azeotrope of N-BUTYL ACETATE and water steams from cat head, steams thing and after condenser condenses, gets into ester water stratification device; N-BUTYL ACETATE returns rectifying tower cat head dehydration cycle after the layering, and waste water is discharged to treatment tank after treatment; Reboiler round-robin acetate concentration analyze qualified after, discharging continuously again behind condensing surface, concentrated acid storage tank, is turned back to the acetic acid configured slot of cracking operation by pump after the decolouring of concentrated acid bleaching tower;
(4) superpolymer at the bottom of the bleaching tower still becomes dilute acetic acid through washing, turns back to rectifying tower dilute acetic acid feeding unit through the dilute acetic acid basin.
Though the present invention is through illustrating and describe with reference to preferred embodiment,, those skilled in the art should understand, and in the scope of claims, can do the various variation on form and the details.
Claims (4)
1. high-purity diketene preparation method is characterized in that: comprise a: acetic acid cracking and freezing removal of impurities operation, b: absorption and polymerization process, c: distillation refining step, d: dilute acetic acid is put forward dense operation;
Said a: acetic acid cracking and freezing removal of impurities operation are operated according to following method:
A1) catalyzer is adopted in the acetic acid cracking reaction; Dense with carrying>80% acetic acid and 99% Glacial acetic acid min. 99.5 be mixed with 91%～95% acetum; This acetum of 91%～95% is through gasification; The catalyzer of acetic acid steam and quality percentage composition 8 ~ 12% is carried out Pintsch process in the cracking tube that the ratio of 100:2～100:4 gets under 730 ℃～750 ℃, 10 ~ 15kPa negative pressure simultaneously, and acetic acid is the mixed pyrolysis gas that contains ketene, water and side reaction product by thermo-cracking;
A2) mixed pyrolysis gas is cooled to rapidly below-20 ℃ through cooler package before the pump with 0.3～0.5% the liquefied ammonia that adds by the acetic acid charging capacity; And pass through four sections cooling condensation processes step by step with the water in the mixed pyrolysis gas; Other side reaction gas; And uncracked acetic acid condensation, become phlegma and get into the phlegma receiver of each section, obtain pure ethylene ketone gas; Each section phlegma is delivered to dilute acetic acid and is put forward dense operation;
A3) pure ethylene ketone gas is through liquid ring vacuum pump delivery operation; Be cooled to rapidly below-30 ℃ through pump aftercooler group by vacuum pump; And liquid obtains pure ketene gas after isolating the pump that is produced by liquid-ring vacuum pump compression piecemeal through four sections cooling condensation processes, sends into ketene absorbing polymer operation again; Liquid forms dilute acetic acid and delivers to dilute acetic acid and put forward dense operation behind the pump after hydrolysis;
Said catalyzer is selected from triethyl phosphate solution, ammonium dihydrogen phosphate;
Described b: absorbing polymer is operated according to following method:
B1) pure ethylene ketone gas is got into the bottom, absorption tower and carry out 5 ~ 10 ℃ of counter current contact under the condition down with the thick ketene dimer liquid spraying of cat head introducing;
B2) go out absorption liquid and stablizer from tower bottom flow and get into polymeric kettle simultaneously in 0.01%～0.1% ratio, generate thick ketene dimer in 25 ℃ of following polymerizations of 15-, the thick ketene dimer solution after polyreaction returns the absorption tower, absorbs circularly and polymerization process;
The reaction end gas of b3) overflowing from cat head enters total waste pipe after washing; Water lotion is that dilute acetic acid is delivered to dilute acetic acid and put forward dense operation;
Described distillation refining step includes:
C1) the thick ketene dimer liquid that polymeric kettle is produced gets into refining step: 50-55 ℃ with the 8-10kPa condition of negative pressure under, thick ketene dimer liquid is introduced from the thin-film evaporator top, thick ketene dimer is along the dirty formation film of wall and by continuous still battery;
The low-boiling point gas of C2) discharging from the vaporizer top is pure ketene dimer product through the cooled phlegma of shell and tube cooler; For guaranteeing the stable of dipolymer, avoid forming trimer, this product needs the stablizer of adding 0.1%～1% after getting into the product storage tank;
C3) from the effusive high boiling point raffinate of base of evaporator, get into residual liquid tank, the formation dilute acetic acid is delivered to dilute acetic acid and is put forward dense operation after hydrolysis;
Said stablizer is selected from terepthaloyl moietie, Ucar 35, Virahol, dihydroxy-benzene, the monomethyl ether of Resorcinol.
2. a kind of high-purity diketene preparation method according to claim 1; It is characterized in that; Described catalyzer is made as: in the storage tank of selecting for use, triethyl phosphate is mixed in the ratio of 1:10 with deionized water; Be mixed with the triethyl phosphate aqueous solution as catalyzer, introduce the catalyzer header tank with pump then.
3. a kind of high-purity diketene preparation method according to claim 1 is characterized in that stablizer is selected from terepthaloyl moietie, Ucar 35, dihydroxy-benzene.
4. a kind of high-purity diketene preparation method according to claim 1; It is characterized in that; Described dilute acetic acid is put forward dense operation and is collected for the dilute acetic acid that acetic acid cracking and freezing removal of impurities operation, absorbing polymer operation and distillation refining step are produced and carry out rectifying and carry densely, and the dense acetic acid that is produced returns the acetic acid cracking operation;
Described dilute acetic acid concentrating method step includes:
D1) dilute acetic acid is collected in the dilute acetic acid holding tank;
D2) dilute acetic acid from the dilute acetic acid holding tank pumps into the middle part of dilute acetic acid rectifying tower through flow measurement device; Disposable adding acetic acid is as bed material during beginning; Reboiler begins heating then, adds N-BUTYL ACETATE from cat head when treating that tower top temperature reaches 85-95 ℃, simultaneously with 2m
3/ h ~ 5m
3The speed of/h adds dilute acetic acid to rectifying tower;
D3) when gas in the tower and phegma carry out heat exchange; Adopt the sensitive plate control techniques; Make the desired temperature and the reboiler heating steam vapour amount at the 5th column plate place of stripping section carry out chain adjusting, said desired temperature between 107～110 ℃, thereby reach the band outlet capacity that gas-liquid phase equilibrium has improved N-BUTYL ACETATE; The azeotrope of N-BUTYL ACETATE and water steams from cat head; Steam thing and after condenser condenses, get into ester water stratification device, N-BUTYL ACETATE returns rectifying tower cat head dehydration cycle after the layering, and waste water is discharged to treatment tank after treatment; Reboiler round-robin acetate concentration analyze qualified after, discharging continuously again behind condensing surface, concentrated acid storage tank, is turned back to the acetic acid configured slot of cracking operation by pump after the decolouring of concentrated acid bleaching tower;
D4) superpolymer at the bottom of the bleaching tower still becomes dilute acetic acid through washing, turns back to rectifying tower dilute acetic acid feeding unit through the dilute acetic acid basin.
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| CN101817736A (en) * | 2010-04-30 | 2010-09-01 | 苏州浩波科技股份有限公司 | Thermal cracking process of acetic acid |
| CN103588734B (en) * | 2013-11-01 | 2015-03-11 | 安徽金禾实业股份有限公司 | Recovery method and recovery device of butyl ester and acetone in ketene dimer production |
| CN103787883B (en) * | 2014-02-18 | 2016-03-02 | 山东汇海医药化工有限公司 | A kind of preparation method of 4-chloroacetyl acetacetic ester |
| CN104059033B (en) * | 2014-06-19 | 2016-01-27 | 南京师范大学 | Method for separating dust-containing diketene and acetic anhydride mixed liquid by flash vacuum extraction and rectification |
| CN104262299B (en) * | 2014-09-04 | 2016-04-27 | 苏州浩波科技股份有限公司 | A kind of ketene dimer production technique of high-efficiency environment friendly |
| CN104402670A (en) * | 2014-09-27 | 2015-03-11 | 安徽金禾实业股份有限公司 | Clean production method of diketene |
| CN104592172B (en) * | 2015-01-08 | 2016-11-23 | 青岛科技大学 | Ketene dimer preparation facilities and preparation method |
| CN106749112B (en) * | 2016-12-08 | 2019-07-30 | 南通醋酸化工股份有限公司 | A kind of ketene dimer continuous rectificating technique |
| CN108854460B (en) * | 2018-05-04 | 2021-04-13 | 青岛海湾精细化工有限公司 | Tail gas recovery system in diketene production |
| CN110170280B (en) * | 2019-05-14 | 2022-09-02 | 浙江恒逸石化研究院有限公司 | High-temperature cracking reactor, high-temperature cracking reaction system and preparation method of ketene compounds |
| CN114105748B (en) * | 2020-08-28 | 2024-06-25 | 万华化学集团股份有限公司 | Preparation method, ketene compound prepared by preparation method and application of ketene compound |
| CN114853606B (en) * | 2022-06-18 | 2023-09-29 | 衢州伟荣药化股份有限公司 | Preparation method of isopropenyl acetate |
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