CN101704839B - Preparation process of high-purity triisobutyl phosphate - Google Patents
Preparation process of high-purity triisobutyl phosphate Download PDFInfo
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- CN101704839B CN101704839B CN2009102467332A CN200910246733A CN101704839B CN 101704839 B CN101704839 B CN 101704839B CN 2009102467332 A CN2009102467332 A CN 2009102467332A CN 200910246733 A CN200910246733 A CN 200910246733A CN 101704839 B CN101704839 B CN 101704839B
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- esterification
- dealcoholysis
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- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- HRKAMJBPFPHCSD-UHFFFAOYSA-N Tri-isobutylphosphate Chemical compound CC(C)COP(=O)(OCC(C)C)OCC(C)C HRKAMJBPFPHCSD-UHFFFAOYSA-N 0.000 title claims abstract description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 90
- 238000006243 chemical reaction Methods 0.000 claims abstract description 53
- 238000005886 esterification reaction Methods 0.000 claims abstract description 43
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000000463 material Substances 0.000 claims abstract description 40
- 230000032050 esterification Effects 0.000 claims abstract description 39
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims abstract description 39
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims abstract description 36
- 239000007789 gas Substances 0.000 claims abstract description 34
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims abstract description 32
- 238000010521 absorption reaction Methods 0.000 claims abstract description 30
- 238000004821 distillation Methods 0.000 claims abstract description 19
- 230000007613 environmental effect Effects 0.000 claims abstract description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 84
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 43
- 238000000034 method Methods 0.000 claims description 32
- 150000002148 esters Chemical class 0.000 claims description 31
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 31
- 230000008569 process Effects 0.000 claims description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- 229910019213 POCl3 Inorganic materials 0.000 claims description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 15
- 239000002253 acid Substances 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 14
- HWJPHQNEWARZLH-UHFFFAOYSA-N 1,1,2,2,3,3,4,4,5,5-decafluoro-6,6-bis(trifluoromethyl)cyclohexane Chemical compound FC(F)(F)C1(C(F)(F)F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C1(F)F HWJPHQNEWARZLH-UHFFFAOYSA-N 0.000 claims description 12
- 239000003513 alkali Substances 0.000 claims description 12
- 238000009835 boiling Methods 0.000 claims description 12
- 238000005516 engineering process Methods 0.000 claims description 12
- 238000001577 simple distillation Methods 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 12
- 238000001704 evaporation Methods 0.000 claims description 10
- 230000008020 evaporation Effects 0.000 claims description 10
- 239000002351 wastewater Substances 0.000 claims description 10
- 238000011084 recovery Methods 0.000 claims description 9
- 241000282326 Felis catus Species 0.000 claims description 5
- 239000012295 chemical reaction liquid Substances 0.000 claims description 5
- 150000003014 phosphoric acid esters Chemical class 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- 238000010992 reflux Methods 0.000 claims description 5
- 238000007086 side reaction Methods 0.000 claims description 5
- 238000010792 warming Methods 0.000 claims description 5
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical group O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims description 4
- 150000004713 phosphodiesters Chemical class 0.000 claims description 4
- -1 phosphoric acid diester Chemical class 0.000 claims description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 239000012267 brine Substances 0.000 claims description 2
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 claims description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 2
- 239000002912 waste gas Substances 0.000 claims description 2
- 239000000047 product Substances 0.000 abstract description 22
- 238000004064 recycling Methods 0.000 abstract description 3
- 230000009467 reduction Effects 0.000 abstract description 3
- 239000002699 waste material Substances 0.000 abstract description 3
- 239000007795 chemical reaction product Substances 0.000 abstract description 2
- 238000004134 energy conservation Methods 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 36
- 238000003756 stirring Methods 0.000 description 8
- 239000000498 cooling water Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 238000009834 vaporization Methods 0.000 description 6
- 230000008016 vaporization Effects 0.000 description 6
- 238000010025 steaming Methods 0.000 description 5
- 239000006227 byproduct Substances 0.000 description 4
- 238000009833 condensation Methods 0.000 description 4
- 230000005494 condensation Effects 0.000 description 4
- 150000003016 phosphoric acids Chemical class 0.000 description 4
- 239000002910 solid waste Substances 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 238000006386 neutralization reaction Methods 0.000 description 3
- 238000007639 printing Methods 0.000 description 3
- 238000007670 refining Methods 0.000 description 3
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 230000004907 flux Effects 0.000 description 2
- 239000013505 freshwater Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 241001550224 Apha Species 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 239000004902 Softening Agent Substances 0.000 description 1
- 238000005267 amalgamation Methods 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 229910001510 metal chloride Inorganic materials 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000000526 short-path distillation Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a preparation process of high-purity triisobutyl phosphate, which comprises the following steps of carrying out esterification reaction on phosphorus oxychloride and excessive isobutanol, recovering hydrogen chloride gas generated in the reaction by using an absorption device, dealcoholizing the esterification reaction product, removing the excessive isobutanol, recovering and recycling the excessive isobutanol, carrying out coarse distillation and fine distillation on the dealcoholized material, and finally obtaining a qualified product, wherein the production process comprises the following steps: esterification, dealcoholization, hydrochloric acid absorption, crude distillation and fine distillation. The preparation process has the advantages of high product yield, energy conservation, consumption reduction, high product purity, less three-waste discharge, environmental protection and the like. The purity of the triisobutyl phosphate prepared was 99.9%.
Description
Technical field
The present invention relates to the fine chemical technology field, is a kind of preparation technology who produces high purity triisobutyl phosphate.
Background technology
High purity triisobutyl phosphate is mainly as the solvent of paint, printing ink, tackiness agent, textile auxiliary agent, permeate agent, colour additive, softening agent, skimmer etc.
Existing three iso-butyl ester of phosphoric acid preparation technology is made up of esterification-dealcoholization and acid removal-neutralization and hydrochloric acid absorption-distillation.Esterification step: reaction ratio POCl3: the isopropylcarbinol mol ratio equals 1: 5～and 1: 9,15～60 ℃ of temperature of reaction, dripping the POCl3 time is that 1～6 hour reaction process is a single step reaction, product yield about 78%; The dealcoholization and acid removal operation: reacted material is changed in the dealcoholysis still, and more than the dealcoholysis vacuum tightness maintenance-0.06MPa, 1～8 hour time, the dealcoholysis outlet temperature can not exceed 10 ℃ of isopropylcarbinol boiling points less than 118.1 ℃, and obtaining thick ester content is 91～92.5%; In and washing step: put into and still through the material after the dealcoholysis; Add alkaline matter while stirring and carry out neutralization reaction; In with pH value 6～8 being and terminal point, add 30～100 ℃ of hot washes then, the amount that adds entry is quality of material or volume 0.5～1.5 times; Branch vibration layer after static 0.2～2 hour obtains thick ester product.This process is chemical neutralization reaction, large quantity of exhaust gas, discharge of wastewater; Distillation process: distill in the material suction still kettle after will neutralizing, purify, process content and be about 99% three iso-butyl ester of phosphoric acid product with thin film evaporation and short-path distillation.Its weak point is: the product earning rate of existing processes preparation is low, and product contains small amount of impurities, influences product purity, and the caustic wash process material loss is big, three waste discharge exceeds standard not environmental protection.
Summary of the invention
Technical problem to be solved by this invention is, existing technology is carried out substantive technological improvement, provides that a kind of product yield is high, product purity is high, and three wastes discharge amount is few, the high purity triisobutyl phosphate preparation technology of environmental protection, energy-conservation, consumption reduction.
The technical scheme that solves its technical problem employing is: a kind of high purity triisobutyl phosphate preparation technology; This technology is that POCl3 and excessive isopropylcarbinol are carried out esterification; The hydrogen chloride gas that produces in the reaction reclaims through absorption unit; Esterification reaction product is deviate from excessive isopropylcarbinol recovery set usefulness through dealcoholysis, and the material after the dealcoholysis is smart distillation behind simple distillation; Finally obtain specification product, production process comprises: esterification step, dealcoholysis operation, hydrochloric acid absorb operation, simple distillation operation and smart distillation process.
(1) esterification step: the first step adds fresh isopropylcarbinol, behind certain feed ratio adding catalyzer in dripping still; By vacuum POCl3 is sucked the dropping still; Dripping the POCl3 time is 7 hours, and the feed ratio of POCl3 and isopropylcarbinol is 1: 3～1: 4mol/mol, and material is played circulation; Through condensing surface-10 ℃ chilled brine cooling, it is 10～14 ℃ thereby the control esterification and low temperature is reflected at the temperature of reaction that drips in the still; Second step, behind the low-temp reaction, warm reaction kettle during reaction mass pumped into, process temperature control curve is: be warming up to 20 ℃, isothermal reaction control 5 hours; The 3rd step: after middle temperature is accomplished, by the reaction liquid pump material is pumped into temperature rise heat exchanger and heat up, temperature of reaction is at 35 ℃; And constantly circulating reaction is accomplished up to esterification; Reaction times is 5 hours, and system pressure is a normal pressure, and esterification is continuously pumped into the dealcoholysis system by esterification material pump after accomplishing;
(2) dealcoholysis operation: utilize hydrogenchloride, alcohol and the thick ester boiling-point difference of three iso-butyl ester of phosphoric acid big; Adopt heating method, the esterification material is controlled at 110～115 ℃ through washing pure tower, dealcoholize column through the heating dealcoholysis with the dealcoholysis column bottom temperature; Make and the alcohol excess of the reaction do not participated in to deviate from reuse in the thick ester of raw phosphoric acid three isobutylates; And react the hydrogenchloride that is dissolved in material that generates and all tell, make raw phosphoric acid three isobutylates, side reaction takes place in temperature-rise period for avoiding alcohol, hydrogenchloride and three iso-butyl ester of phosphoric acid; The dealcoholysis process is the high negative pressure state, and vacuum tightness is-0.098Mpa;
(3) hydrochloric acid absorbs operation: with HCL gas under low-temperature condition in water the high characteristics of solubleness; After the HCL gas that produces in esterification and the dealcoholysis operation was total to the absorption of Pyatyi absorption tower via a concentrated hydrochloric acid absorption tower, two Hydrogen chloride absorption towers, a soda-wash tower and a water wash column, HCL was absorbed fully in the gas, and the water vapour of waste gas is extracted out by the vacuum unit with the HCL gas of trace; Drain into atmosphere through aiutage; Concentrated hydrochloric acid is reclaimed on the concentrated hydrochloric acid absorption tower, and the Hydrogen chloride part of two Hydrogen chloride absorption towers, a soda-wash tower and a water wash column formation recycles, and a part gets into the concentrated hydrochloric acid absorption tower; The HCL recovery is 99.85%; In operating process, regularly measure simultaneously the pH value of alkali lye circulation groove, guarantee pH value＞7, when pH value≤7, switch to another alkali lye circulation groove; Again carry out environmental protection treatment and recycle, whole process has only a small amount of discharge of wastewater up to standard;
(4) simple distillation operation: thick ester material sucks the thick tower that steams with vacuum continuously through under meter; Heating steams three iso-butyl ester of phosphoric acid; The control blanking temperature is at 160～180 ℃; Thick ester vacuum and main vacuum are consistent, and gas is condensed into raw phosphoric acid three isobutylates through thick evaporation condenser and flows into thick ester groove, and high boiling acid phosphoric acid ester flows into crude steam kettle and continues to steam three iso-butyl ester of phosphoric acid;
(5) smart distillation process: the small amounts of phosphoric acid diester that contains in the material, different according to three iso-butyl ester of phosphoric acid with the phosphodiester boiling point, with the principle of rectifying three iso-butyl ester of phosphoric acid is separated from cat head; High boiling phosphodiester is stayed at the bottom of the still, because of the SULPHOSUCCINIC ACID ESTER boiling point is high, so native system adopts rectification under vacuum; In the operating process: vacuum tightness is-0.098Mpa, adopts foreshot after the intensification earlier, and temperature in the kettle is controlled at 110 ℃; When temperature in the kettle reaches 120 ℃～125 ℃; Quantity of reflux reaches 400kg/h, adopts foreshot entirely, analyzes to go out finished product after qualified.150～168 ℃ of terminal point still temperature controls.
The present invention is raw materials used to be easy to get, and POCl3 is by Jilin petrochemical industry amalgamation plant produced; Isopropylcarbinol is produced by Siping City ethanol Ltd, is the commercially available prod.
The main chemical reactions equation of high purity triisobutyl phosphate preparation technology of the present invention
Main reaction:
Side reaction:
The molecular formula of the three iso-butyl ester of phosphoric acid of high purity triisobutyl phosphate preparation technology preparation of the present invention: C
12H
27O
4P
Proterties: colourless transparent liquid is slightly soluble in water
Purposes: mainly as the solvent of paint, printing ink, tackiness agent, skimmer, dyeing and printing auxiliary, additive, skimmer etc.
The quality index table
| Sequence number | Index name | Index |
| 1 | Outward appearance | Colourless transparent liquid |
| 2 | Content, % >= | 99.9 |
| 3 | Moisture content (H 2O)％≤ | 0.2 |
| 4 | Colourity APHA<= | 30 |
| 5 | Acidity mgKOH/g<= | 0.1 |
| 6 | Density (20 ℃), g/ml | 0.960-0.970 |
| 7 | Refractive index n D 25 | 1.4190-1.4210 |
Said catalyzer is a custom catalysts, like Lewis acid metal chloride series, Vanadium Pentoxide in FLAKES, titanium tetrachloride, aluminum trichloride (anhydrous), tetrabutyl titanate etc.; The molar mass of catalyst levels and POCl3 consumption is such as following: POCl3: catalyzer=1: 0.12～1: 0.15.
The invention has the advantages that: the first, through adding excessive alcohol, and to make the esterification control process be three-step reaction, the POCl3 of participating in reaction reacted completely under the effect of catalyzer, thereby improve product yield; The second, the dealcoholysis operation utilizes hydrogenchloride, alcohol and the thick ester boiling-point difference of three iso-butyl ester of phosphoric acid big, adopts heating method, makes the alcohol excess of the reaction do not participated in to deviate from recovery set usefulness in the thick ester of raw phosphoric acid three isobutylates, and is energy-saving and cost-reducing; The 3rd, with HCL gas under low-temperature condition in water the high characteristics of solubleness, after the HCL gas that produces in esterification and the dealcoholysis operation absorbed with the Pyatyi absorption tower, the HCL recovery reached 99.85%, whole process has only a small amount of discharge of wastewater up to standard, environmental emission reduction; The 4th, rectification working process divides simple distillation and smart distillation process, reaches refining purpose, and making high purity triisobutyl phosphate purity is 99.9%, and product yield surpasses 95% (in theoretical yield).
Embodiment
Embodiment one
1, esterification step: by the catalyzer feed ratio 12kg catalyzer is together joined in the 1000L reaction kettle with the 300kg isopropylcarbinol and to mix; Stir and make interior-10 ℃ of chilled brines of reacting kettle jacketing play circulation and cool off,, begin to drip the 100kg POCl3 when the material in reactor temperature is 10 ℃; Keeping temperature of reaction is 10 ℃; Stirring velocity is 60rpm, 7 hours dropping time, drips POCl3 and finishes; Reaction mass is pumped into warm reaction kettle among the 1000L, and process temperature control curve is: be warming up to 20 ℃, isothermal reaction control 5 hours; In after temperature accomplishes, by the reaction liquid pump material is pumped into temperature rise heat exchanger and heats up, temperature of reaction is at 35 ℃, and constantly circulating reaction is accomplished up to esterification, the reaction times is 5 hours, system pressure is a normal pressure.
2, dealcoholysis operation: after esterification is accomplished, open earlier and wash pure tower and dealcoholize column heating system, thick ester is squeezed into 20m with pump
3To wash in the pure tower, this process carries out dealcoholysis to low-boiling-point substance and separates-when material after washing treats that the dealcoholysis column bottom temperature reaches 110 ℃, be continuously pumped into 20m by esterification material pump
3Dealcoholize column heats vaporization, and the centering thing that boils separates, and from cat head extraction isopropylcarbinol, HCL, the gas after vaporization gets into dealcoholize column, obtains thick ester from tower is low, and thick ester content is 98.5%, analyzes qualified back entering simple distillation operation; Make the alcohol excess 148.5kg that the reaction do not participated in get back to the recovery alcohol jar of 1000L after the dealcoholysis, return esterification step and recycle.Material after the dealcoholysis is got into the thick ester scale tank of 1000L by dealcoholize column.For fear of side reaction takes place, the dealcoholysis process is the high negative pressure reaction, and vacuum tightness is-0.098MPa.
3, hydrochloric acid absorbs operation: the HCL gas that produces in esterification and the dealcoholysis operation absorbs with the Pyatyi absorption tower; One of them concentrated hydrochloric acid absorption tower, two Hydrogen chloride absorption towers, a soda-wash tower, a water wash column; At first open lye pump outlet valve, alkali lye reverse flow valve, start NaOH solution circulating pump, open the pump discharge valve; Regulate flux of alkaline liquor, be controlled at 6m
3/ h internal circulating load is opened the soda-wash tower cooling water valve, and controlled temperature is 20 ℃; Secondly open washing pump discharge valve, washing reverse flow valve, start the washing recycle pump, open the pump discharge valve, regulate the cleaning water flow, be controlled at 6m
3/ h internal circulating load is opened the water wash column cooling water valve, and controlled temperature is 20 ℃; Open Hydrogen chloride pump discharge valve, Hydrogen chloride reverse flow valve once more, start diluted HCl solution circulating pump, regulate Hydrogen chloride under meter flow.Open the pump discharge valve, regulate the Hydrogen chloride flow, be controlled at 6m
3/ h internal circulating load is opened Hydrogen chloride absorption tower cooling water valve, and controlled temperature is 20 ℃; The 4th step was opened the Hydrogen chloride under meter terminal valve on concentrated hydrochloric acid absorption tower, advanced the Hydrogen chloride amount and regulated according to concentrated acid HCl content, guaranteed that concentrated hydrochloric acid HCl content is 31%.The HCL recovery is 99.85%, in operating process, regularly measures the pH value of alkali lye circulation groove simultaneously, guarantees that pH value is 7, and the entering system replenishes fresh water and recycles.When pH value≤7, switch to another alkali lye circulation groove, readjust the NaOH strength of solution, the alkali lye circulation groove is absorbed water carry out environmental protection treatment, handle recycling after qualified, whole process has only a small amount of discharge of wastewater up to standard.
4, simple distillation operation: thick ester material sucks the thick tower that steams with vacuum continuously through under meter, and heating steams three iso-butyl ester of phosphoric acid.The control blanking temperature is at 160 ℃, and thick ester vacuum and main vacuum are consistent, and gas is condensed into raw phosphoric acid three isobutylates through thick evaporation condenser and flows into thick ester groove, and high boiling acid phosphoric acid ester flows into crude steam kettle and continues to steam three iso-butyl ester of phosphoric acid.
5, smart distillation process: slightly steam in the smart steaming of the material suction still; The warp essence is steamed the still heating and is steamed the three iso-butyl ester of phosphoric acid gas, flows into preceding part groove through the refining low-boiling-point substance foreshot that separates of essence steaming tower, and vacuum degree control is-0.098Mpa; Adopt foreshot after the intensification earlier; Temperature in the kettle is controlled at 110 ℃, and when temperature in the kettle reached 120 ℃, quantity of reflux reached 400kg/h.Adopt foreshot entirely, analyze and go out finished product after qualified.150 ℃ of terminal point still temperature controls; Make with extra care out the three iso-butyl ester of phosphoric acid gas through the qualified three iso-butyl ester of phosphoric acid 170.33kg of smart evaporation condenser condensation output, reclaim pure 148.5kg, by-product concentration is 31% hydrochloric acid 234.16kg; Exhaust gas emission 0.0107kg, 0.015 ton of waste water.Product yield is 96.96%, analytical results: colourity 4APHA, purity 99.98%, acid number 0.0045mgKOH/g, moisture content 0.018%.Solid waste 15.18kg at the bottom of the still of smart distillation back, after water cleaned, the evaporate to dryness weathering formed phosphoric acid salt.
Embodiment two
1, esterification step: by the catalyzer feed ratio 19.5kg catalyzer is together joined in the 1000L reaction kettle with the 450kg isopropylcarbinol and to mix; Stir and make interior-10 ℃ of chilled brines of reacting kettle jacketing play circulation and cool off,, begin to drip the 150kg POCl3 when the material in reactor temperature is 12 ℃; Keeping temperature of reaction is 12 ℃; Stirring velocity is 60rpm, 10 hours dropping time, drips POCl3 and finishes; Reaction mass is pumped into warm reaction kettle among the 1000L, and process temperature control curve is: be warming up to 20 ℃, isothermal reaction control 5 hours; After middle temperature is accomplished, by the reaction liquid pump material is pumped into temperature rise heat exchanger and heat up, temperature of reaction is at 35 ℃, and continuous circulating reaction is accomplished up to esterification.Reaction times is 5 hours, and system pressure is a normal pressure.
2, dealcoholysis operation: after esterification is accomplished, open earlier and wash pure tower and dealcoholize column heating system, thick ester is squeezed into 20m with pump
3To wash in the pure tower, this process carries out dealcoholysis to low-boiling-point substance and separates-when material after washing treats that the dealcoholysis column bottom temperature reaches 113 ℃, be continuously pumped into 20m by esterification material pump
3Dealcoholize column heats vaporization, and the centering thing that boils separates, and from cat head extraction isopropylcarbinol, HCL, the gas after vaporization gets into dealcoholize column, obtains thick ester from tower is low, and thick ester content is 98.9%, analyzes qualified back entering simple distillation operation; Make the alcohol excess 231.2kg that the reaction do not participated in get back to the recovery alcohol jar of 1000L after the dealcoholysis, return esterification step and recycle, the material after the dealcoholysis is got into the thick ester scale tank of 1000L by dealcoholize column.For fear of side reaction takes place, the dealcoholysis process is the high negative pressure reaction, and vacuum tightness is-0.098MPa.
3, hydrochloric acid absorbs operation: the HCL gas that produces in esterification and the dealcoholysis operation absorbs with the Pyatyi absorption tower; One of them concentrated hydrochloric acid absorption tower, two Hydrogen chloride absorption towers, a soda-wash tower, a water wash column; At first open lye pump outlet valve, alkali lye reverse flow valve, start NaOH solution circulating pump, open the pump discharge valve; Regulate flux of alkaline liquor, be controlled at 6m
3/ h internal circulating load is opened the soda-wash tower cooling water valve, and controlled temperature is 20 ℃; Secondly open washing pump discharge valve, washing reverse flow valve, start the washing recycle pump, open the pump discharge valve, regulate the cleaning water flow, be controlled at 6m
3/ h internal circulating load is opened the water wash column cooling water valve, and controlled temperature is 20 ℃; Open Hydrogen chloride pump discharge valve, Hydrogen chloride reverse flow valve once more, start diluted HCl solution circulating pump, regulate Hydrogen chloride under meter flow.Open the pump discharge valve, regulate the Hydrogen chloride flow, be controlled at 6m
3/ h internal circulating load is opened Hydrogen chloride absorption tower cooling water valve, and controlled temperature is 20 ℃; The 4th step was opened the Hydrogen chloride under meter terminal valve on concentrated hydrochloric acid absorption tower; Advancing the Hydrogen chloride amount regulates according to concentrated acid HCl content; Guarantee concentrated acid HCl content 31%, the HCL recovery is 99.91%, in operating process, regularly measures the pH value of alkali lye circulation groove simultaneously; Guarantee that pH value is 7, the entering system replenishes fresh water and recycles.When pH value≤7, switch to another alkali lye circulation groove, readjust the NaOH strength of solution, the alkali lye circulation groove is absorbed water carry out environmental protection treatment, handle recycling after qualified, whole process has only a small amount of discharge of wastewater up to standard.
4, simple distillation operation: thick ester material sucks the thick tower that steams with vacuum continuously through under meter, and heating steams three iso-butyl ester of phosphoric acid.The control blanking temperature is at 170 ℃, and thick ester vacuum and main vacuum are consistent, and gas is condensed into raw phosphoric acid three isobutylates through thick evaporation condenser and flows into thick ester groove.High boiling acid phosphoric acid ester flows into crude steam kettle and continues to steam three iso-butyl ester of phosphoric acid.
5, smart distillation process: slightly steam in the smart steaming of the material suction still; The warp essence is steamed the still heating and is steamed the three iso-butyl ester of phosphoric acid gas, flows into preceding part groove through the refining low-boiling-point substance foreshot that separates of essence steaming tower, and vacuum degree control is-0.098Mpa; Adopt foreshot after the intensification earlier; Temperature in the kettle is controlled at 110 ℃, and when temperature in the kettle reached 123 ℃, quantity of reflux reached 420kg/h.Adopt foreshot entirely, analyze and go out finished product after qualified.160 ℃ of terminal point still temperature controls.Make with extra care out the three iso-butyl ester of phosphoric acid gas through the qualified three iso-butyl ester of phosphoric acid 259.2kg of smart evaporation condenser condensation output, reclaim pure 231.2kg, by-product concentration is 31% hydrochloric acid 353.2kg, exhaust gas emission 0.01508kg, 0.0215 ton of waste water.Product yield is 98.3%, analytical results: colourity 5APHA, purity 99.92%, acid number 0.0048mgKOH/g, moisture content 0.019%.Solid waste 22.45kg at the bottom of the still of smart distillation back, after water cleaned, the evaporate to dryness weathering formed phosphoric acid salt.
Embodiment three
Earlier catalyzer is added to be added drop-wise to then in the POCl3 when difference of embodiment three and embodiment two is esterification and carry out esterification in the isopropylcarbinol material.Practical implementation is earlier isopropylcarbinol 450kg to be put in the 1000L reaction kettle, when the material in reactor temperature is 10 ℃, begins to drip the 150kg POCl3 that contains the 19.5kg catalyzer; Keeping temperature of reaction is 14 ℃; Stirring velocity is 60rpm, 10 hours dropping time, drips POCl3 and finishes; Reaction mass is pumped into warm reaction kettle among the 1000L, and process temperature control curve is: be warming up to 20 ℃, isothermal reaction control 5 hours; After middle temperature is accomplished, by the reaction liquid pump material is pumped into temperature rise heat exchanger and heat up, temperature of reaction is at 35 ℃, and continuous circulating reaction is accomplished up to esterification.Reaction times is 5 hours, and system pressure is a normal pressure; The dealcoholysis operation: low-boiling-point substance is carried out dealcoholysis to be separated-when material after washing treats that the dealcoholysis column bottom temperature reaches 115 ℃, be continuously pumped into 50m by esterification material pump
3Dealcoholize column heats vaporization, and the centering thing that boils separates, and from cat head extraction isopropylcarbinol, HCL, the gas after vaporization gets into dealcoholize column, and low to obtain thick ester content be 98.9% from tower, analyzes qualified back entering simple distillation operation; Vacuum tightness-0.098MPa, the dealcoholysis inlet amount is 400L/h; Hydrochloric acid absorbs operation: the HCL gas that produces in esterification and the dealcoholysis operation absorbs with the Pyatyi absorption tower and is controlled at 10m
3/ h internal circulating load is opened the tower cooler water valve, and controlled temperature is 20 ℃; Open the Hydrogen chloride under meter terminal valve on concentrated hydrochloric acid absorption tower, advance the Hydrogen chloride amount and regulate, guarantee that concentrated hydrochloric acid HCl content is 31% according to concentrated hydrochloric acid HCl content; The simple distillation operation: the control blanking temperature is at 175 ℃, and thick ester vacuum and main vacuum are consistent, and gas is condensed into raw phosphoric acid three isobutylates through thick evaporation condenser and flows into thick ester groove.High boiling acid phosphoric acid ester flows into crude steam kettle and continues to steam three iso-butyl ester of phosphoric acid; Smart distillation process: vacuum tightness-0.098Mpa adopts foreshot earlier after the intensification, temperature in the kettle is controlled at 110 ℃, and when temperature in the kettle reached 125 ℃, quantity of reflux reached 400kg/h.Adopt foreshot entirely, analyze and go out finished product after qualified.168 ℃ of terminal point still temperature controls.Make with extra care out the three iso-butyl ester of phosphoric acid gas through the qualified three iso-butyl ester of phosphoric acid 260.5kg of smart evaporation condenser condensation output, reclaim pure 235.4kg, by-product concentration is 31% hydrochloric acid 351kg, exhaust gas emission 0.01408kg, 0.0208 ton of waste water.Product yield is 98.8%, analytical results: colourity 4APHA, purity 99.94%, acid number 0.0043mgKOH/g, moisture content 0.018%.Solid waste 22.13kg at the bottom of the still of smart distillation back, after water cleaned, the evaporate to dryness weathering formed phosphoric acid salt.
Embodiment four
Adopt vacuum when the difference of embodiment four and embodiment three is esterification, in the esterification reaction process, stirring heating keeps the vacuum tightness-0.094MPa of system, and keeping temperature of reaction is 14 ℃, and stirring velocity is 60rpm, 10 hours dropping time; 115 ℃ of dealcoholize column outlet temperatures, vacuum tightness-0.098MPa; The smart terminal point still temperature of steaming must not control above 168 ℃.Make with extra care out the three iso-butyl ester of phosphoric acid gas through the qualified three iso-butyl ester of phosphoric acid 260.8kg of smart evaporation condenser condensation output, reclaim pure 230.2kg, by-product concentration is 31% hydrochloric acid 350.7kg, exhaust gas emission 0.01415kg, 0.0223 ton of waste water.Product yield is 98.9%, analytical results: colourity 5APHA, purity 99.96%, acid number 0.0038mgKOH/g, moisture content 0.018%.Solid waste 22.06kg at the bottom of the still of smart distillation back, after water cleaned, the evaporate to dryness weathering formed phosphoric acid salt.
Claims (1)
1. high purity triisobutyl phosphate preparation technology, it comprises that esterification step, dealcoholysis operation, hydrochloric acid absorb operation, simple distillation and smart distillation process, is characterized in that:
(1) esterification step: the first step adds fresh isopropylcarbinol, behind certain feed ratio adding catalyzer in dripping still; By vacuum POCl3 is sucked the dropping still; Dripping the POCl3 time is 7 hours, and the feed ratio of POCl3 and isopropylcarbinol is 1: 3～1: 4mol/mol, and material is played circulation; Through condensing surface-10 ℃ chilled brine cooling, it is 10～14 ℃ thereby the control esterification and low temperature is reflected at the temperature of reaction that drips in the still; Second step, behind the low-temp reaction, warm reaction kettle during reaction mass pumped into, process temperature control curve is: be warming up to 20 ℃, isothermal reaction control 5 hours; The 3rd step: after middle temperature is accomplished; By the reaction liquid pump material is pumped into temperature rise heat exchanger and heat up, temperature of reaction is at 35 ℃, and constantly circulating reaction is accomplished up to esterification; Reaction times is 5 hours; System pressure is a normal pressure, and esterification is continuously pumped into the dealcoholysis system by esterification material pump after accomplishing, and said catalyzer is Vanadium Pentoxide in FLAKES, titanium tetrachloride, aluminum trichloride (anhydrous) or tetrabutyl titanate;
(2) dealcoholysis operation: utilize hydrogenchloride, alcohol and the thick ester boiling-point difference of three iso-butyl ester of phosphoric acid big; Adopt heating method, the esterification material is controlled at 110～115 ℃ through washing pure tower, dealcoholize column through the heating dealcoholysis with the dealcoholysis column bottom temperature; Make and the alcohol excess of the reaction do not participated in to deviate from reuse in the thick ester of raw phosphoric acid three isobutylates; And react the hydrogenchloride that is dissolved in material that generates and all tell, make raw phosphoric acid three isobutylates, side reaction takes place in temperature-rise period for avoiding alcohol, hydrogenchloride and three iso-butyl ester of phosphoric acid; The dealcoholysis process is the high negative pressure state, and vacuum tightness is-0.098Mpa;
(3) hydrochloric acid absorbs operation: with HCL gas under low-temperature condition in water the high characteristics of solubleness; After the HCL gas that produces in esterification and the dealcoholysis operation was total to the absorption of Pyatyi absorption tower via a concentrated hydrochloric acid absorption tower, two Hydrogen chloride absorption towers, a soda-wash tower and a water wash column, HCL was absorbed fully in the gas, and the water vapour of waste gas is extracted out by the vacuum unit with the HCL gas of trace; Drain into atmosphere through aiutage; Concentrated hydrochloric acid is reclaimed on the concentrated hydrochloric acid absorption tower, and the Hydrogen chloride part of two Hydrogen chloride absorption towers, a soda-wash tower and a water wash column formation recycles, and a part gets into the concentrated hydrochloric acid absorption tower; The HCL recovery is 99.85%; In operating process, regularly measure simultaneously the pH value of alkali lye circulation groove, assurance pH value＞7 switch to another alkali lye circulation groove when pH value≤7; Again carry out environmental protection treatment and recycle, whole process has only a small amount of discharge of wastewater up to standard;
(4) simple distillation operation: thick ester material sucks the thick tower that steams with vacuum continuously through under meter; Heating steams three iso-butyl ester of phosphoric acid; The control blanking temperature is at 160～180 ℃; Thick ester vacuum and main vacuum are consistent, and gas is condensed into raw phosphoric acid three isobutylates through thick evaporation condenser and flows into thick ester groove, and high boiling acid phosphoric acid ester flows into crude steam kettle and continues to steam three iso-butyl ester of phosphoric acid;
(5) smart distillation process: the small amounts of phosphoric acid diester that contains in the material, different according to three iso-butyl ester of phosphoric acid with the phosphodiester boiling point, with the principle of rectifying three iso-butyl ester of phosphoric acid is separated from cat head; High boiling phosphodiester is stayed at the bottom of the still, because of the SULPHOSUCCINIC ACID ESTER boiling point is high, so native system adopts rectification under vacuum; In the operating process: vacuum tightness is-0.098Mpa, adopts foreshot after the intensification earlier, and temperature in the kettle is controlled at 110 ℃; When temperature in the kettle reached 120 ℃～125 ℃, quantity of reflux reached 400kg/h, adopted foreshot entirely; Analyze and go out finished product after qualified, 150～168 ℃ of terminal point still temperature controls.
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| CN103108846B (en) * | 2010-09-27 | 2015-09-16 | 格雷斯公司 | Dilute stable cement compositions of additives |
| CN103351402A (en) * | 2013-06-19 | 2013-10-16 | 天津市联瑞阻燃材料有限公司 | Method for production of phosphate flame retardant by excess phosphorus oxychloride |
| CN103833784B (en) * | 2014-03-20 | 2016-04-27 | 扬州晨化新材料股份有限公司 | A kind of production method of phosphorus flame retardant |
| CN106279265A (en) * | 2016-08-24 | 2017-01-04 | 浙江万盛股份有限公司 | A kind of preparation method of flame-retardant plasticizer tricresyl phosphate (2 propyl group 1 heptan) ester |
| CN108129511B (en) * | 2018-02-12 | 2020-06-16 | 海安县中丽化工材料有限公司 | Method for preparing trialkyl phosphate |
| CN108997083A (en) * | 2018-07-11 | 2018-12-14 | 三门峡中达化工有限公司 | A kind of technique with butanol in TRI N BUTYL PHOSPHATE extraction and separation hydrochloric acid |
| CN110386949B (en) * | 2019-07-29 | 2021-08-06 | 江苏澄星磷化工股份有限公司 | Production method of phosphorus flame retardant |
| CN112745346A (en) * | 2019-10-30 | 2021-05-04 | 邓华萍 | Phosphate preparation equipment and preparation method thereof |
| CN115584646B (en) * | 2022-10-18 | 2024-03-19 | 英德市东鸿化工科技有限公司 | Penetrant produced by utilizing industrial side ester |
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