CN101704839B - High purity triisobutyl phosphate preparation technology - Google Patents
High purity triisobutyl phosphate preparation technology Download PDFInfo
- Publication number
- 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
- Authority
- CN
- China
- Prior art keywords
- temperature
- reaction
- phosphoric acid
- esterification
- dealcoholysis
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a high purity triisobutyl phosphate preparation technology which comprises the following steps of: carrying out esterification on phosphorus oxychloride and excess isobutanol; recovering hydrogen chloride gas generated in the reaction by an absorption device; extracting excess isobutanol of a esterification product through dealcoholization; recovering and reusing the excess isobutanol; and crudely distilling the material after dealcoholization and fine distilling to obtain a qualified product by fine distilling materials after dealcoholization after crude distillation. A production process comprises an esterification process, a dealcoholization process, a hydrochloric acid absorption process, a crude distillation process and a fine distillation process. The preparation technology has the advantages of high product yield, energy saving, consumption reduction, high product purity, little three waste emission, environmental protection and the like. The purity of the prepared triisobutyl phosphate is 99.9 percent.
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.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009102467332A CN101704839B (en) | 2009-09-23 | 2009-11-23 | High purity triisobutyl phosphate preparation technology |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910067575 | 2009-09-23 | ||
| CN200910067575.4 | 2009-09-23 | ||
| CN2009102467332A CN101704839B (en) | 2009-09-23 | 2009-11-23 | High purity triisobutyl phosphate preparation technology |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101704839A CN101704839A (en) | 2010-05-12 |
| CN101704839B true CN101704839B (en) | 2012-05-30 |
Family
ID=42375098
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2009102467332A Active CN101704839B (en) | 2009-09-23 | 2009-11-23 | High purity triisobutyl phosphate preparation technology |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101704839B (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BR112013007313B1 (en) * | 2010-09-27 | 2020-03-10 | Gcp Applied Technologies Inc. | ADDITIVE COMPOSITION OF CEMENT MILLING AND METHODS FOR MANUFACTURING A CEMENT |
| 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 |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1415616A (en) * | 2002-10-25 | 2003-05-07 | 无锡市红星化工厂 | Method for producing ethyl phosphate with high purity |
| CN1544439A (en) * | 2003-11-14 | 2004-11-10 | 无锡市红星化工厂 | High purity tributyl phosphate production method |
| CN1951801A (en) * | 2006-06-15 | 2007-04-25 | 浙江工业大学 | Process for preparing high purity hydrochloric acid by circularly absorbing hydrogen chloride by-product |
| CN101381375A (en) * | 2008-09-25 | 2009-03-11 | 无锡市红星化工厂 | Preparation method of Tri-iso-butyl phosphate |
-
2009
- 2009-11-23 CN CN2009102467332A patent/CN101704839B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1415616A (en) * | 2002-10-25 | 2003-05-07 | 无锡市红星化工厂 | Method for producing ethyl phosphate with high purity |
| CN1544439A (en) * | 2003-11-14 | 2004-11-10 | 无锡市红星化工厂 | High purity tributyl phosphate production method |
| CN1951801A (en) * | 2006-06-15 | 2007-04-25 | 浙江工业大学 | Process for preparing high purity hydrochloric acid by circularly absorbing hydrogen chloride by-product |
| CN101381375A (en) * | 2008-09-25 | 2009-03-11 | 无锡市红星化工厂 | Preparation method of Tri-iso-butyl phosphate |
Non-Patent Citations (1)
| Title |
|---|
| JP昭5242779 1977.10.26 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101704839A (en) | 2010-05-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101704839B (en) | High purity triisobutyl phosphate preparation technology | |
| CN103553138B (en) | Comprehensive utilization method for separating, concentrating and purifying manganese sulfate, magnesium sulfate and calcium sulfate in high-salt waste water | |
| CN102145912B (en) | Process for preparing calcium chloride solution by utilizing ammonia soda filtration mother liquor | |
| CN101654305B (en) | Process for changing phenolic nitrate effluent into useful material by extracting, evaporating, crystallizing and coupling | |
| CN101735045B (en) | Method for producing ethyl acetate by using entrainer | |
| CN108358176B (en) | Dilute sulfuric acid vacuum concentrating device and method | |
| CN103848864A (en) | Preparation process of high-purity triisobutyl phosphate | |
| CN103435642B (en) | Production method of trioctyl phosphate | |
| CN104710471A (en) | Production method of phosphotriester | |
| CN103274898A (en) | Process for recovering distillation waste liquid generated by producing 1,4-butanediol | |
| CN109503409A (en) | Sucralose is esterified reaction acid DMF processing method and processing device | |
| CN112876357A (en) | Production process for producing plasticizer from PTA oxidation residues | |
| CN101549929A (en) | Method for distilling absorption type negative-pressure thermal cycle coking wastewater | |
| CN111995492A (en) | Method for recovering solvent dichloromethane in acesulfame potassium production | |
| CN103524478B (en) | Device and method for shortening ketalation time in ibuprofen synthesis process | |
| CN104557538A (en) | Industrial production method for producing butyl acrylate by in-column reaction rectification | |
| CN111302965A (en) | Novel preparation process of naphthol | |
| CN107805231A (en) | The system and method for furfural is continuously prepared with the pentose solution containing acid | |
| CN105777540A (en) | Energy-saving efficient isopropenyl acetate synthesis method | |
| CN103819042B (en) | A kind of hydrochloride waste purifying treatment method | |
| CN208055237U (en) | The system for continuously preparing furfural with the pentose solution containing acid | |
| CN111320152B (en) | Method for preparing hydroxylamine hydrochloride by gas-phase continuous hydrolysis of ketoxime | |
| CN105217654B (en) | Alkylation waste sulfuric acid recycling treatment device and method | |
| CN211338795U (en) | Hydrogen chloride production system | |
| CN104524797B (en) | Energy-conservation concentration and evaporation method in zirconium oxychloride production process |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |