CN104710471A - Production method of phosphotriester - Google Patents
Production method of phosphotriester Download PDFInfo
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- CN104710471A CN104710471A CN201510113475.6A CN201510113475A CN104710471A CN 104710471 A CN104710471 A CN 104710471A CN 201510113475 A CN201510113475 A CN 201510113475A CN 104710471 A CN104710471 A CN 104710471A
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 23
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 126
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 70
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 claims abstract description 58
- 238000006243 chemical reaction Methods 0.000 claims abstract description 54
- 238000000034 method Methods 0.000 claims abstract description 54
- 238000005406 washing Methods 0.000 claims abstract description 48
- 238000005886 esterification reaction Methods 0.000 claims abstract description 41
- 230000032050 esterification Effects 0.000 claims abstract description 37
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000003513 alkali Substances 0.000 claims abstract description 24
- 238000011084 recovery Methods 0.000 claims abstract description 24
- 239000006227 byproduct Substances 0.000 claims abstract description 18
- 239000000047 product Substances 0.000 claims abstract description 15
- 238000001914 filtration Methods 0.000 claims abstract description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 49
- 239000000463 material Substances 0.000 claims description 47
- 150000002148 esters Chemical class 0.000 claims description 37
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 27
- 238000010521 absorption reaction Methods 0.000 claims description 27
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 claims description 26
- 238000006386 neutralization reaction Methods 0.000 claims description 20
- 238000010438 heat treatment Methods 0.000 claims description 19
- 239000007788 liquid Substances 0.000 claims description 17
- 230000035484 reaction time Effects 0.000 claims description 16
- 239000011780 sodium chloride Substances 0.000 claims description 16
- 125000006226 butoxyethyl group Chemical group 0.000 claims description 15
- 239000002351 wastewater Substances 0.000 claims description 14
- 238000001816 cooling Methods 0.000 claims description 12
- 238000012805 post-processing Methods 0.000 claims description 11
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 10
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 10
- 150000001447 alkali salts Chemical class 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- 238000006297 dehydration reaction Methods 0.000 claims description 9
- 230000018044 dehydration Effects 0.000 claims description 8
- 238000009833 condensation Methods 0.000 claims description 7
- 230000005494 condensation Effects 0.000 claims description 7
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 5
- 238000004458 analytical method Methods 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 5
- 235000017550 sodium carbonate Nutrition 0.000 claims description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 5
- 239000003054 catalyst Substances 0.000 claims description 4
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims description 4
- 238000005070 sampling Methods 0.000 claims description 4
- 238000013019 agitation Methods 0.000 claims description 3
- 235000019628 coolness Nutrition 0.000 claims description 3
- 125000004122 cyclic group Chemical group 0.000 claims description 3
- 238000002309 gasification Methods 0.000 claims description 3
- DKAGJZJALZXOOV-UHFFFAOYSA-N hydrate;hydrochloride Chemical compound O.Cl DKAGJZJALZXOOV-UHFFFAOYSA-N 0.000 claims description 3
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical group Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 3
- 238000009834 vaporization Methods 0.000 claims description 3
- 230000008016 vaporization Effects 0.000 claims description 3
- 238000004065 wastewater treatment Methods 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 150000001805 chlorine compounds Chemical class 0.000 claims description 2
- 229910001510 metal chloride Inorganic materials 0.000 claims description 2
- 238000006276 transfer reaction Methods 0.000 claims description 2
- 238000005516 engineering process Methods 0.000 abstract description 3
- 238000003912 environmental pollution Methods 0.000 abstract description 2
- 239000012535 impurity Substances 0.000 abstract description 2
- 238000007086 side reaction Methods 0.000 abstract description 2
- 230000003472 neutralizing effect Effects 0.000 abstract 3
- 239000012267 brine Substances 0.000 abstract 1
- 239000007795 chemical reaction product Substances 0.000 abstract 1
- 238000000926 separation method Methods 0.000 abstract 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 abstract 1
- 235000019441 ethanol Nutrition 0.000 description 7
- 238000003756 stirring Methods 0.000 description 5
- 239000002253 acid Substances 0.000 description 3
- 239000006210 lotion Substances 0.000 description 3
- 125000004183 alkoxy alkyl group Chemical group 0.000 description 2
- 150000007942 carboxylates Chemical class 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- -1 polyethylene Polymers 0.000 description 2
- CJTNLEQLKKYLFO-UHFFFAOYSA-N 1-butoxyethanol Chemical class CCCCOC(C)O CJTNLEQLKKYLFO-UHFFFAOYSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 238000004064 recycling Methods 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
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Abstract
A production method of phosphotriester comprises the steps of allowing phosphorus oxychloride and 2-butoxyethanol to directly carry out esterification reaction, recovering generated HCl gas via an absorbing device into a byproduct hydrochloric acid with a concentration of 31%, desorbing, recovering and reusing 2-butoxyethanol from an esterification reaction product via a dealcoholization procedure, and neutralizing, washing, dehydrating and filtering coarse phosphotriester to obtain a qualified product. The method comprises the following production procedures: the esterification procedure, a dealcoholization procedure, a hydrochloric acid recovery procedure and a post-treatment procedure. The method has the advantages: first, the technology of allowing 2-butoxyethanol and phosphorus oxychloride to directly carry out the esterification reaction is simple, the byproduct HCl is completely recovered, and the environmental pollution is reduced; second, a three-stage programmed temperature rise reaction is employed, and the side reaction is reduced under a high vacuum condition for the esterification reaction, so that a product yield is increased; third, 3% alkali brine is used for neutralizing and water washing to solve the production problem of failure in separation by washing with pure water; and fourth, secondary neutralizing and water washing can reduce impurities in the product and improve product quality.
Description
Technical field
The present invention relates to fine chemical product production technical field, especially relate to a kind of tricresyl phosphate fat production method.
Background technology tricresyl phosphate (butoxyethyl group) ester is mainly used in soluble cotton, cellulose acetate, Vinyl Acetate Copolymer, polyvinyl chloride, polyethylene, polyvinyl alcohol, butyral and elastomeric fine plasticizer, and has flame retardant resistance.
The patent US3020303 of FMC Corp. and EP0091426 describes the production technique of tricresyl phosphate (alkoxyalkyl) ester, production technique adopts alkoxyalkyl alcohol and alkalimetal oxide to react, and react through dehydration reaction generation alkali alcoholate and phosphorus oxychloride, generate the product of tricresyl phosphate (alkoxyalkyl) ester.Complex manufacturing, by-product HCl gas and alkali reaction generate a large amount of salt, and product purity is low, and chromaticness is poor, and waste water is many, seriously polluted.
Summary of the invention
For solving the problems of the technologies described above, the present invention adopts following technical scheme:
A kind of tricresyl phosphate fat production method, it is characterized in that, technique is as follows:
Esterification:
Step one: phosphorus oxychloride drips and low-temp reaction; To dripping the butoxy ethanol dropping into fresh butoxy ethanol and recovery in still, drop into catalyzer by a certain percentage, drip phosphorus oxychloride under vacuum, drip material pump in still play circulation and cool through external water cooler 5 DEG C of cold water, control to drip temperature of charge 10-20 DEG C in still, continue after dripping phosphorus oxychloride to carry out low-temp reaction, temperature of reaction 15 ~ 25 DEG C, 4 ~ 6 hours reaction times at dropping still.
Step 2: middle temperature reaction; The material pump dripped in still after low-temp reaction is pumped in middle temperature reactor, circulation played by middle temperature material in reactor recycle pump, and through external heat exchanger 50 DEG C of hot water heatings, warm reactor temperature of charge 30 ~ 40 DEG C in control, 4 ~ 6 hours circulating reaction time.
Step 3: back flow reaction; The material pump of temperature reaction in process in middle temperature reactor is pumped into back flow reaction still, material pump in back flow reaction still beat circulation and through external heat exchanger 90 DEG C of hot water heatings, control back flow reaction still temperature of charge 70 ~ 80 DEG C, heat exchanger exit produces a small amount of butoxy ethanol gas and is back to back flow reaction still through condenser with after 5 DEG C of cold water condensations, 8 ~ 10 hours reaction times, esterification material pump after esterification completes is continuously pumped into dealcoholysis operation, and esterification produces HCl gas and enters HCl recovery operation.
Dealcoholysis operation: esterification material contains the boiling-point difference that HCl gas and excessive butoxy ethanol utilize alcohol and ester, adopts heating means to deviate from butoxy ethanol for esterification step recovery; Esterification material pump pumps into dealcoholize column top, after dealcoholize column steam heating, alcohol vaporization becomes gas, shift out from top and apply mechanically for esterification with flowing into recovery alcohol scale tank after 5 DEG C of cold water condensations through condenser, after the HCl gas that uncondensable HCl gas and esterification produce merges, remove HCl recovery process.Tricresyl phosphate (butoxyethyl group) ester goes postprocessing working procedures after flowing out bottom dealcoholize column and entering the metering of thick ester scale tank; At the bottom of control dealcoholize column between thick ester drop temperature 135 ~ 145 DEG C.
HCl recovery operation: the HCl gas that esterification and dealcoholysis operation produce need through concentrated hydrochloric acid absorption tower, dilute hydrochloric acid absorption tower, weak hydrochloric acid absorption tower, water wash column and soda-wash tower Pyatyi gas absorption, HCl gas reclaims completely, tail gas is extracted out by vacuum pump set and is entered air through vapor pipe, and Pyatyi absorbs and all adopts continuous compulsory circulative cooling absorption technique flow process; Circulation groove internal recycle liquid pump pumps into water cooler cooling, and water cooler adopts 5 DEG C of cold water coolings, and controlled circulation absorption liquid temperature is at 10 ~ 20 DEG C.By-product hydrochloric acid water drops in proportion from water washing cycles groove, weak hydrochloric acid in water washing cycles groove utilizes liquid level difference automatically to flow into weak hydrochloric acid circulation groove, the dilute hydrochloric acid of weak hydrochloric acid circulation groove utilizes liquid level difference automatically to flow into dilute hydrochloric acid circulation groove, and salt acid-utilising liquid level difference denseer in dilute hydrochloric acid circulation groove flows into concentrated hydrochloric acid circulation groove automatically.Concentration of hydrochloric acid in concentrated hydrochloric acid circulation groove controls more than 31%, and major part is used for cyclic absorption HCl gas, and a part goes by-product hydrochloric acid storage tank to sell as by-product hydrochloric acid simultaneously; Alkali lye circulation groove has two, another alkali lye circulation groove is switched to when an alkali lye circulation pH value reaches 7, discharge of wastewater in alkali lye circulation groove is reconfigured the NaOH alkali lye of 5% concentration as subsequent use after going wastewater treatment, wastewater discharge is the NaCl waste water that absorption 400 ton of 31% by-product hydrochloric acid produces that 1m3 contains about 7% simultaneously.
Postprocessing working procedures: it is twice neutralization &washing and dehydration, filtration four steps that postprocessing working procedures comprises, the density of tricresyl phosphate (butoxyethyl group) ester is 1020kg/m3, very close with water, after adopting pure water washing, material is not stratified, and the alkali salt water of 3% concentration need be adopted to carry out neutralization &washing.
First time washing alkali salt water configuration concentration: NaOH content 2%, NaCl content 1%, raw phosphoric acid three (butoxyethyl group) ester neutralization &washing alkali weight saline is 0.5 ~ 0.8 times of thick ester weight, and 70 ~ 80 DEG C are stirred standing 3 hours branch vibration layers after 2 hours, then carry out second time washing; Second time washing alkali salt water configuration concentration: Na2CO3 content 0.5%, NaCl content 2.5%, all the other wash identical with first time, and neutralization &washing carries out in atmospheric conditions.
The material washed through Two-step neutralization is carried out processed, dehydration terminal temperature 130 DEG C, vacuum-0.098MPa, keep the temperature 2 as a child qualified rear cooling material to 70 DEG C of sampling analysis under agitation, qualified tricresyl phosphate (butoxyethyl group) ester pump is pumped, after being filtered, is delivered to finished product scale tank.
In the step one of described technique (1), catalyzer comprises as Louis's metal chloride series, preferred catalyst is titanium tetrachloride, aluminum trichloride (anhydrous), Vanadium Pentoxide in FLAKES, butyl (tetra) titanate, and catalyst levels is phosphorus oxychloride with the molar mass ratio of phosphorus oxychloride consumption: catalyzer=1:0.003-0.06.
Phosphorus oxychloride in the step one of described technique (1): the preferred 1:0.05 of catalyzer.
Feed ratio 1:3 ~ 4:3 ~ the 4mol/mol of the butoxy ethanol of phosphorus oxychloride and fresh butoxy ethanol and recovery in the step one of described technique (1).
Drip temperature of charge preferably 15 DEG C in still in the step one of described technique (1), the rate of addition of phosphorus oxychloride is 100 ~ 30kg/h.
Low-temp reaction temperature preferably 20 DEG C in the step one of described technique (1), preferably 5 hours low-temp reaction time, vacuum tightness-0.096Mpa, middle temperature reactor temperature of charge preferably 35 DEG C, vacuum tightness-0.096Mpa, preferably 6 hours warm reactor Matter Transfer reaction times.
Back flow reaction still temperature of charge preferably 75 DEG C in the step one of described technique (1), preferably 9 hours reaction times, vacuum tightness-0.096MPa.
Thick ester drop temperature preferably 140 DEG C at the bottom of dealcoholize column is controlled, vacuum tightness-0.098Mpa in described technique (2).
Controlled circulation absorption liquid temperature preferably 15 DEG C in described technique (3).
0.6 times of the preferred thick ester weight of raw phosphoric acid three (butoxyethyl group) ester neutralization &washing alkali weight saline in described technique (4).
Advantage of the present invention is: the first, and the technique that direct butoxy ethanol carries out esterification in phosphorus oxychloride is simple, and by-product HCl all recycles, and reduces environmental pollution; The second, adopt three rank temperature-programmed reaction and esterification carries out minimizing side reaction in high vacuum conditions, product yield is improved; 3rd, adopt the alkali salt water of 3% to carry out neutralization &washing and make originally to wash the production difficult problem that cannot be separated with pure water and solved; 4th, wash the impurity that can reduce in product with Two-step neutralization, product quality is improved.
Embodiment
A kind of tricresyl phosphate fat production method, it is characterized in that, technique is as follows:
Esterification:
Step one: phosphorus oxychloride drips and low-temp reaction; To dripping the butoxy ethanol dropping into fresh butoxy ethanol and recovery in still, drop into catalyzer by a certain percentage, drip phosphorus oxychloride under vacuum, drip material pump in still play circulation and cool through external water cooler 5 DEG C of cold water, control to drip temperature of charge 10-20 DEG C in still, continue after dripping phosphorus oxychloride to carry out low-temp reaction, temperature of reaction 15 ~ 25 DEG C, 4 ~ 6 hours reaction times at dropping still.
Step 2: middle temperature reaction; The material pump dripped in still after low-temp reaction is pumped in middle temperature reactor, circulation played by middle temperature material in reactor recycle pump, and through external heat exchanger 50 DEG C of hot water heatings, warm reactor temperature of charge 30 ~ 40 DEG C in control, 4 ~ 6 hours circulating reaction time.
Step 3: back flow reaction; The material pump of temperature reaction in process in middle temperature reactor is pumped into back flow reaction still, material pump in back flow reaction still beat circulation and through external heat exchanger 90 DEG C of hot water heatings, control back flow reaction still temperature of charge 70 ~ 80 DEG C, heat exchanger exit produces a small amount of butoxy ethanol gas and is back to back flow reaction still through condenser with after 5 DEG C of cold water condensations, 8 ~ 10 hours reaction times, esterification material pump after esterification completes is continuously pumped into dealcoholysis operation, and esterification produces HCl gas and enters HCl recovery operation.
Dealcoholysis operation: esterification material contains the boiling-point difference that HCl gas and excessive butoxy ethanol utilize alcohol and ester, adopts heating means to deviate from butoxy ethanol for esterification step recovery; Esterification material pump pumps into dealcoholize column top, after dealcoholize column steam heating, alcohol vaporization becomes gas, shift out from top and apply mechanically for esterification with flowing into recovery alcohol scale tank after 5 DEG C of cold water condensations through condenser, after the HCl gas that uncondensable HCl gas and esterification produce merges, remove HCl recovery process.Tricresyl phosphate (butoxyethyl group) ester goes postprocessing working procedures after flowing out bottom dealcoholize column and entering the metering of thick ester scale tank; At the bottom of control dealcoholize column between thick ester drop temperature 135 ~ 145 DEG C.
HCl recovery operation: the HCl gas that esterification and dealcoholysis operation produce need through concentrated hydrochloric acid absorption tower, dilute hydrochloric acid absorption tower, weak hydrochloric acid absorption tower, water wash column and soda-wash tower Pyatyi gas absorption, HCl gas reclaims completely, tail gas is extracted out by vacuum pump set and is entered air through vapor pipe, and Pyatyi absorbs and all adopts continuous compulsory circulative cooling absorption technique flow process; Circulation groove internal recycle liquid pump pumps into water cooler cooling, and water cooler adopts 5 DEG C of cold water coolings, and controlled circulation absorption liquid temperature is at 10 ~ 20 DEG C.By-product hydrochloric acid water drops in proportion from water washing cycles groove, weak hydrochloric acid in water washing cycles groove utilizes liquid level difference automatically to flow into weak hydrochloric acid circulation groove, the dilute hydrochloric acid of weak hydrochloric acid circulation groove utilizes liquid level difference automatically to flow into dilute hydrochloric acid circulation groove, and salt acid-utilising liquid level difference denseer in dilute hydrochloric acid circulation groove flows into concentrated hydrochloric acid circulation groove automatically.Concentration of hydrochloric acid in concentrated hydrochloric acid circulation groove controls more than 31%, and major part is used for cyclic absorption HCl gas, and a part goes by-product hydrochloric acid storage tank to sell as by-product hydrochloric acid simultaneously; Alkali lye circulation groove has two, another alkali lye circulation groove is switched to when an alkali lye circulation pH value reaches 7, discharge of wastewater in alkali lye circulation groove is reconfigured the NaOH alkali lye of 5% concentration as subsequent use after going wastewater treatment, wastewater discharge is the NaCl waste water that absorption 400 ton of 31% by-product hydrochloric acid produces that 1m3 contains about 7% simultaneously.
Postprocessing working procedures: it is twice neutralization &washing and dehydration, filtration four steps that postprocessing working procedures comprises, the density of tricresyl phosphate (butoxyethyl group) ester is 1020kg/m3, very close with water, after adopting pure water washing, material is not stratified, and the alkali salt water of 3% concentration need be adopted to carry out neutralization &washing.
First time washing alkali salt water configuration concentration: NaOH content 2%, NaCl content 1%, raw phosphoric acid three (butoxyethyl group) ester neutralization &washing alkali weight saline is 0.5 ~ 0.8 times of thick ester weight, and 70 ~ 80 DEG C are stirred standing 3 hours branch vibration layers after 2 hours, then carry out second time washing; Second time washing alkali salt water configuration concentration: Na2CO3 content 0.5%, NaCl content 2.5%, all the other wash identical with first time, and neutralization &washing carries out in atmospheric conditions.
The material washed through Two-step neutralization is carried out processed, dehydration terminal temperature 130 DEG C, vacuum-0.098MPa, keep the temperature 2 as a child qualified rear cooling material to 70 DEG C of sampling analysis under agitation, qualified tricresyl phosphate (butoxyethyl group) ester pump is pumped, after being filtered, is delivered to finished product scale tank.
Embodiment one:
(1) esterification step
The butoxy ethanol 380kg of butoxy ethanol 480kg and recovery is put in 1000L dropping still, drop into catalyzer titanium tetrachloride 500ml, open absorption by Hydrochloric Acid system and vacuum pump set, open when vacuum reaches-0.096MPa and drip still recycle pump, drip water cooler cold water by when material is cooled to 15 DEG C in dropping still, start to drip 200kg phosphorus oxychloride, keep dropping temperature between 15 ~ 20 DEG C, phosphorus oxychloride rate of addition is 50 ~ 100kg/h, after dripping phosphorus oxychloride, material continues circulating reaction, control low-temp reaction 15 ~ 20 DEG C of 4 hours times of temperature, low-temp reaction terminates rear pump and reaction mass is pumped into warm reactor in 1000L.Circulation played by material pump in middle temperature reactor, and material is with 50 DEG C of hot water through interchanger computer heating control temperature of charge 35 ± 2 DEG C, and middle temperature reaction reaction in 5 hours terminates, and with pump, material is pumped into 1000L back flow reaction still.In back flow reaction still, circulation played by material pump, with 90 DEG C of hot water through interchanger heated material, controls back flow reaction temperature 75 ± 2 DEG C, 8 hours reaction times.Drip phosphorus oxychloride, low-temp reaction, the reaction of middle temperature, back flow reaction vacuum tightness >-0.096MPa, after back flow reaction terminates, with back flow reaction recycle pump, material is pumped into esterification material and proceed to 3000L carboxylate week turn trough.
(2) dealcoholysis operation
Carboxylate week, the material volume pump of turn trough to pump on dealcoholize column not by the flow of 300L/h, and dealcoholize column steam heating, control blanking temperature 135 ± 2 DEG C bottom dealcoholize column, the thick ester of outlet at bottom flows into thick ester scale tank.Control dealcoholysis vacuum >=-0.098MPa, dealcoholize column discharge butoxy ethanol suitable for reading and HCl gas enter condenser with 5 DEG C of cold water condensation butoxy ethanols and are back to recovery butoxy ethanol groove and apply mechanically as esterification.
(3) HCl recovery operation
The HCl gas Pyatyi packing tower series connection pump circulation recycling that esterification and dealcoholysis operation produce, packing tower size Φ 400*5000, HCl gas enters after vacuum pump set vacuumizes after absorbing process through concentrated acid tower, diluted acid tower, dilture acid tower, water wash column, soda-wash tower and enters air.By-product hydrochloric acid absorbs water and adds from water cycle groove, and add-on controls by phosphorus oxychloride charging capacity, and ratio is phosphorus oxychloride: water=1:1.58, and by-product hydrochloric acid concentration is 31%.
(4) postprocessing working procedures
Postprocessing working procedures comprises Two-step neutralization washing, dehydration and filters four steps, the heating of washing kettle 2000L jacketed and stirring heating still.
Water lotion formula: 500kg water+10kg sheet alkali (NaOH)+5kg salt (NaCl) for the first time.The thick ester pump of thick ester scale tank is dropped into washing kettle, charging capacity is 1000kg, add the water lotion configured, by steam heating, intensification limit, limit is stirred to 75 DEG C and keeps temperature 70 ~ 80 DEG C, continuously stirring after 2 hours leave standstill 3 little time-divisions remove bottom aqueous layer, waste water puts into waste water collection tank, washing carry out at ambient pressure.
Once after washing, material carries out secondary washing, intermediate water lotion prescription again: 500kg water+12.5kg salt (NaCl)+2.5kg soda ash (Na2CO3).The secondary configured washing is also dropped into washing kettle, heats up and be stirred to 70 ~ 80 DEG C, continuously stirring is washed after 2 hours and is left standstill 3 hours, and divide and remove bottom aqueous layer, waste water puts into waste water collection tank, and 3000L washing material scale tank put into by the material after secondary washing.
Dehydration procedure: 2000kg washing material is dropped into 2000L dehydrating kettle, dehydrating kettle jacketed and stirring, when dehydrating kettle vacuum pump set vacuumizes and reaches-0.098MPa, by steam heating, intensification limit, limit is stirred, stop when temperature of charge reaches 130 DEG C in still heating up, stir insulation 2 hours, be cooled to 60 DEG C of sampling analysis qualified after go to filter.
Filter progress: the qualified finished product pump of analysis is pumped in dehydrating kettle, send into finished product scale tank, as sale of finished goods after deep bed filter filters.
The above; be only the specific embodiment of the present invention, but protection scope of the present invention is not limited thereto, is anyly familiar with those skilled in the art in the technical scope that the present invention discloses; change can be expected easily or replace, all should be encompassed within protection scope of the present invention.Therefore, protection scope of the present invention should be as the criterion with the protection domain of described claim.
Claims (10)
1. a tricresyl phosphate fat production method, is characterized in that, technique is as follows:
(1) esterification:
Step one: phosphorus oxychloride drips and low-temp reaction; To dripping the butoxy ethanol dropping into fresh butoxy ethanol and recovery in still, drop into catalyzer by a certain percentage, drip phosphorus oxychloride under vacuum, drip material pump in still play circulation and cool through external water cooler 5 DEG C of cold water, control to drip temperature of charge 10-20 DEG C in still, continue after dripping phosphorus oxychloride to carry out low-temp reaction, temperature of reaction 15 ~ 25 DEG C, 4 ~ 6 hours reaction times at dropping still;
Step 2: middle temperature reaction; The material pump dripped in still after low-temp reaction is pumped in middle temperature reactor, circulation played by middle temperature material in reactor recycle pump, and through external heat exchanger 50 DEG C of hot water heatings, warm reactor temperature of charge 30 ~ 40 DEG C in control, 4 ~ 6 hours circulating reaction time;
Step 3: back flow reaction; The material pump of temperature reaction in process in middle temperature reactor is pumped into back flow reaction still, material pump in back flow reaction still beat circulation and through external heat exchanger 90 DEG C of hot water heatings, control back flow reaction still temperature of charge 70 ~ 80 DEG C, heat exchanger exit produces a small amount of butoxy ethanol gas and is back to back flow reaction still through condenser with after 5 DEG C of cold water condensations, 8 ~ 10 hours reaction times, esterification material pump after esterification completes is continuously pumped into dealcoholysis operation, and esterification produces HCl gas and enters HCl recovery operation;
(2) dealcoholysis operation: esterification material contains the boiling-point difference that HCl gas and excessive butoxy ethanol utilize alcohol and ester, adopts heating means to deviate from butoxy ethanol for esterification step recovery; Esterification material pump pumps into dealcoholize column top, after dealcoholize column steam heating, alcohol vaporization becomes gas, shift out from top and apply mechanically for esterification with flowing into recovery alcohol scale tank after 5 DEG C of cold water condensations through condenser, after the HCl gas that uncondensable HCl gas and esterification produce merges, remove HCl recovery process;
Tricresyl phosphate (butoxyethyl group) ester goes postprocessing working procedures after flowing out bottom dealcoholize column and entering the metering of thick ester scale tank; At the bottom of control dealcoholize column between thick ester drop temperature 135 ~ 145 DEG C;
(3) HCl recovery operation: the HCl gas that esterification and dealcoholysis operation produce need through concentrated hydrochloric acid absorption tower, dilute hydrochloric acid absorption tower, weak hydrochloric acid absorption tower, water wash column and soda-wash tower Pyatyi gas absorption, HCl gas reclaims completely, tail gas is extracted out by vacuum pump set and is entered air through vapor pipe, and Pyatyi absorbs and all adopts continuous compulsory circulative cooling absorption technique flow process; Circulation groove internal recycle liquid pump pumps into water cooler cooling, and water cooler adopts 5 DEG C of cold water coolings, and controlled circulation absorption liquid temperature is at 10 ~ 20 DEG C;
By-product hydrochloric acid water drops in proportion from water washing cycles groove, weak hydrochloric acid in water washing cycles groove utilizes liquid level difference automatically to flow into weak hydrochloric acid circulation groove, the dilute hydrochloric acid of weak hydrochloric acid circulation groove utilizes liquid level difference automatically to flow into dilute hydrochloric acid circulation groove, and salt acid-utilising liquid level difference denseer in dilute hydrochloric acid circulation groove flows into concentrated hydrochloric acid circulation groove automatically;
Concentration of hydrochloric acid in concentrated hydrochloric acid circulation groove controls more than 31%, and major part is used for cyclic absorption HCl gas, and a part goes by-product hydrochloric acid storage tank to sell as by-product hydrochloric acid simultaneously; Alkali lye circulation groove has two, another alkali lye circulation groove is switched to when an alkali lye circulation pH value reaches 7, discharge of wastewater in alkali lye circulation groove is reconfigured the NaOH alkali lye of 5% concentration as subsequent use after going wastewater treatment, wastewater discharge is the NaCl waste water that absorption 400 ton of 31% by-product hydrochloric acid produces that 1m3 contains about 7% simultaneously;
(4) postprocessing working procedures: it is twice neutralization &washing and dehydration, filtration four steps that postprocessing working procedures comprises, the density of tricresyl phosphate (butoxyethyl group) ester is 1020kg/m3, very close with water, after adopting pure water washing, material is not stratified, and the alkali salt water of 3% concentration need be adopted to carry out neutralization &washing;
First time washing alkali salt water configuration concentration: NaOH content 2%, NaCl content 1%, raw phosphoric acid three (butoxyethyl group) ester neutralization &washing alkali weight saline is 0.5 ~ 0.8 times of thick ester weight, and 70 ~ 80 DEG C are stirred standing 3 hours branch vibration layers after 2 hours, then carry out second time washing; Second time washing alkali salt water configuration concentration: Na2CO3 content 0.5%, NaCl content 2.5%, all the other wash identical with first time, and neutralization &washing carries out in atmospheric conditions;
The material washed through Two-step neutralization is carried out processed, dehydration terminal temperature 130 DEG C, vacuum-0.098MPa, keep the temperature 2 as a child qualified rear cooling material to 70 DEG C of sampling analysis under agitation, qualified tricresyl phosphate (butoxyethyl group) ester pump is pumped, after being filtered, is delivered to finished product scale tank.
2. a kind of tricresyl phosphate fat production method according to claim 1, it is characterized in that: in the step one of described technique (1), catalyzer comprises as Louis's metal chloride series, preferred catalyst is titanium tetrachloride, aluminum trichloride (anhydrous), Vanadium Pentoxide in FLAKES, butyl (tetra) titanate, and catalyst levels is phosphorus oxychloride with the molar mass ratio of phosphorus oxychloride consumption: catalyzer=1:0.003-0.06.
3. a kind of tricresyl phosphate fat production method according to claim 2, is characterized in that: phosphorus oxychloride in the step one of described technique (1): the preferred 1:0.05 of catalyzer.
4. a kind of tricresyl phosphate fat production method according to claim 1, is characterized in that: the feed ratio 1:3 ~ 4:3 ~ 4mol/mol of the butoxy ethanol of phosphorus oxychloride and fresh butoxy ethanol and recovery in the step one of described technique (1).
5. a kind of tricresyl phosphate fat production method according to claim 1, is characterized in that: drip temperature of charge preferably 15 DEG C in still in the step one of described technique (1), the rate of addition of phosphorus oxychloride is 100 ~ 30kg/h.
6. a kind of tricresyl phosphate fat production method according to claim 1, it is characterized in that: low-temp reaction temperature preferably 20 DEG C in the step one of described technique (1), preferably 5 hours low-temp reaction time, vacuum tightness-0.096Mpa, middle temperature reactor temperature of charge preferably 35 DEG C, vacuum tightness-0.096Mpa, preferably 6 hours warm reactor Matter Transfer reaction times.
7. a kind of tricresyl phosphate fat production method according to claim 1, is characterized in that: back flow reaction still temperature of charge preferably 75 DEG C in the step one of described technique (1), preferably 9 hours reaction times, vacuum tightness-0.096MPa.
8. a kind of tricresyl phosphate fat production method according to claim 1, is characterized in that: control thick ester drop temperature preferably 140 DEG C at the bottom of dealcoholize column in described technique (2), vacuum tightness-0.098Mpa.
9. a kind of tricresyl phosphate fat production method according to claim 1, is characterized in that: controlled circulation absorption liquid temperature preferably 15 DEG C in described technique (3).
10. a kind of tricresyl phosphate fat production method according to claim 1, is characterized in that: 0.6 times of the preferred thick ester weight of raw phosphoric acid three (butoxyethyl group) ester neutralization &washing alkali weight saline in described technique (4).
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106008592A (en) * | 2016-06-01 | 2016-10-12 | 浙江万盛股份有限公司 | Industrial synthesis method of tris(butoxyethyl)phosphate and device thereof |
| CN109516623A (en) * | 2018-11-16 | 2019-03-26 | 浙江万盛股份有限公司 | A kind of method of comprehensive utilization of tri butylethyl phosphate waste water |
| CN109679139A (en) * | 2018-12-21 | 2019-04-26 | 天津利海石化有限公司 | A kind of low acid value cold-resistant plasticizer and preparation method thereof |
| CN109796627A (en) * | 2018-12-21 | 2019-05-24 | 天津利海石化有限公司 | A kind of stable type phosphate plasticizer and preparation method thereof |
| CN111925390A (en) * | 2020-09-14 | 2020-11-13 | 太仓康源化建医药有限公司 | Preparation method of tris (butoxyethyl) phosphate |
| CN112745346A (en) * | 2019-10-30 | 2021-05-04 | 邓华萍 | Phosphate preparation equipment and preparation method thereof |
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| CN1884286A (en) * | 2006-06-30 | 2006-12-27 | 周聚潞 | Process for preparing high-purity butoxy ethyl phosphate |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1884286A (en) * | 2006-06-30 | 2006-12-27 | 周聚潞 | Process for preparing high-purity butoxy ethyl phosphate |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106008592A (en) * | 2016-06-01 | 2016-10-12 | 浙江万盛股份有限公司 | Industrial synthesis method of tris(butoxyethyl)phosphate and device thereof |
| CN109516623A (en) * | 2018-11-16 | 2019-03-26 | 浙江万盛股份有限公司 | A kind of method of comprehensive utilization of tri butylethyl phosphate waste water |
| CN109516623B (en) * | 2018-11-16 | 2021-06-01 | 浙江万盛股份有限公司 | Comprehensive utilization method of tributoxyethyl phosphate wastewater |
| CN109679139A (en) * | 2018-12-21 | 2019-04-26 | 天津利海石化有限公司 | A kind of low acid value cold-resistant plasticizer and preparation method thereof |
| CN109796627A (en) * | 2018-12-21 | 2019-05-24 | 天津利海石化有限公司 | A kind of stable type phosphate plasticizer and preparation method thereof |
| CN112745346A (en) * | 2019-10-30 | 2021-05-04 | 邓华萍 | Phosphate preparation equipment and preparation method thereof |
| CN111925390A (en) * | 2020-09-14 | 2020-11-13 | 太仓康源化建医药有限公司 | Preparation method of tris (butoxyethyl) phosphate |
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