CN112745346A - Phosphate preparation equipment and preparation method thereof - Google Patents
Phosphate preparation equipment and preparation method thereof Download PDFInfo
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- CN112745346A CN112745346A CN201911044414.3A CN201911044414A CN112745346A CN 112745346 A CN112745346 A CN 112745346A CN 201911044414 A CN201911044414 A CN 201911044414A CN 112745346 A CN112745346 A CN 112745346A
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- esterification reaction
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- condenser
- monohydric alcohol
- hydrogen chloride
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- 229910019142 PO4 Inorganic materials 0.000 title claims abstract description 34
- 239000010452 phosphate Substances 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 title claims description 13
- 238000005886 esterification reaction Methods 0.000 claims abstract description 136
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 107
- 239000007789 gas Substances 0.000 claims abstract description 97
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims abstract description 75
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims abstract description 75
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 64
- 238000010521 absorption reaction Methods 0.000 claims abstract description 57
- 238000005406 washing Methods 0.000 claims abstract description 50
- 239000002994 raw material Substances 0.000 claims abstract description 41
- 239000000203 mixture Substances 0.000 claims abstract description 36
- 239000007788 liquid Substances 0.000 claims abstract description 27
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 claims abstract description 24
- -1 phosphate ester Chemical class 0.000 claims abstract description 22
- 239000006227 byproduct Substances 0.000 claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims description 80
- 239000007791 liquid phase Substances 0.000 claims description 62
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 43
- 239000012071 phase Substances 0.000 claims description 41
- 239000000047 product Substances 0.000 claims description 31
- 239000002253 acid Substances 0.000 claims description 30
- 230000032050 esterification Effects 0.000 claims description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 29
- 238000007670 refining Methods 0.000 claims description 26
- 229910052757 nitrogen Inorganic materials 0.000 claims description 20
- 238000001704 evaporation Methods 0.000 claims description 19
- 230000008020 evaporation Effects 0.000 claims description 19
- 239000000463 material Substances 0.000 claims description 16
- 238000000746 purification Methods 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 15
- 239000007792 gaseous phase Substances 0.000 claims description 12
- 238000010992 reflux Methods 0.000 claims description 12
- AFCIMSXHQSIHQW-UHFFFAOYSA-N [O].[P] Chemical compound [O].[P] AFCIMSXHQSIHQW-UHFFFAOYSA-N 0.000 claims description 10
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims description 10
- 229910052753 mercury Inorganic materials 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 9
- 238000007701 flash-distillation Methods 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 238000000926 separation method Methods 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 8
- 238000005201 scrubbing Methods 0.000 claims description 7
- 238000007710 freezing Methods 0.000 claims description 6
- 230000008014 freezing Effects 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 4
- 238000011084 recovery Methods 0.000 claims description 4
- 230000009469 supplementation Effects 0.000 claims description 4
- 238000007033 dehydrochlorination reaction Methods 0.000 claims description 3
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 claims description 3
- 239000002351 wastewater Substances 0.000 abstract description 10
- 239000002910 solid waste Substances 0.000 abstract description 7
- 239000002912 waste gas Substances 0.000 abstract description 6
- DKAGJZJALZXOOV-UHFFFAOYSA-N hydrate;hydrochloride Chemical compound O.Cl DKAGJZJALZXOOV-UHFFFAOYSA-N 0.000 abstract description 3
- 239000002699 waste material Substances 0.000 abstract description 3
- 239000008235 industrial water Substances 0.000 abstract description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 44
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 14
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 14
- 239000006096 absorbing agent Substances 0.000 description 11
- 239000012528 membrane Substances 0.000 description 11
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 7
- 238000010586 diagram Methods 0.000 description 6
- 238000006386 neutralization reaction Methods 0.000 description 6
- 238000007086 side reaction Methods 0.000 description 6
- 239000003513 alkali Substances 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- 229910001392 phosphorus oxide Inorganic materials 0.000 description 4
- 238000004064 recycling Methods 0.000 description 4
- VSAISIQCTGDGPU-UHFFFAOYSA-N tetraphosphorus hexaoxide Chemical compound O1P(O2)OP3OP1OP2O3 VSAISIQCTGDGPU-UHFFFAOYSA-N 0.000 description 4
- 238000006482 condensation reaction Methods 0.000 description 3
- 229910001873 dinitrogen Inorganic materials 0.000 description 3
- 150000003014 phosphoric acid esters Chemical class 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 229920000388 Polyphosphate Polymers 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 239000007770 graphite material Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 239000001205 polyphosphate Substances 0.000 description 1
- 235000011176 polyphosphates Nutrition 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 238000011272 standard treatment Methods 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/08—Esters of oxyacids of phosphorus
- C07F9/09—Esters of phosphoric acids
- C07F9/11—Esters of phosphoric acids with hydroxyalkyl compounds without further substituents on alkyl
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Treating Waste Gases (AREA)
Abstract
The invention relates to a phosphate ester preparation device and a preparation method thereof, the device comprises a multi-stage esterification reaction unit, a dealcoholization device and a gas washing device for recovering hydrogen chloride and monohydric alcohol, wherein the multi-stage esterification reaction unit is formed by sequentially arranging a plurality of esterification reaction units which are connected in series; wherein, the raw material input port of one esterification reaction unit positioned at the head part is connected with the raw material delivery outlet of the gas washing device, and the mixture input port of the gas washing device is used for being connected with the mixture output ports of all the esterification reaction units and the dealcoholization device in parallel; the raw material input port of the dealcoholization device is connected with an esterification reaction unit positioned at the tail part. According to the invention, unreacted monohydric alcohol carried in the volatilization of the hydrogen chloride is recovered by using the gas washing device, phosphorus oxychloride in the absorption liquid is carried in the industrial hydrochloric acid water when the hydrogen chloride is volatilized, and then the volatilized hydrogen chloride is absorbed by using the industrial water, so that the industrial-grade qualified byproduct hydrochloric acid can be prepared, the waste of raw materials is reduced, and the yield of waste gas, waste water and solid waste is reduced.
Description
Technical Field
The invention relates to the field of chemical industry, in particular to phosphate ester preparation equipment and a phosphate ester preparation method.
Background
The phosphate esters are useful as extractants for rare metals, solvents, plasticizers for chlorinated rubbers and polyvinyl chloride, and industrial defoamers.
The traditional preparation method for preparing phosphate by reacting phosphorus oxide with monohydric alcohol adopts an esterification section, an alkali addition neutralization section, a dealcoholization section and a rectification separation section, and the method is generally improved from the aspects of reaction temperature, reaction mixing mode, reaction time, the proportion of the raw material phosphate and monohydric alcohol, reaction heat transfer and the like.
The conventional method for removing hydrogen chloride is to react phosphorus oxychloride with monohydric alcohol under reduced pressure and elevated temperature so as to continuously remove hydrogen chloride from the reaction mixture, but the above reaction method has the following disadvantages:
if the use temperature of the hydrogen chloride is high after the removal, the hydrogen chloride after gasification and condensation is absorbed by the monohydric alcohol, and the monohydric alcohol is recycled to participate in the secondary esterification reaction, thereby influencing the reaction conversion rate; the use of elevated temperatures to remove hydrogen chloride also results in the production of a certain amount of high boiling phosphoric acid, which can cause pyrolysis of the reaction mass during distillation, which is also detrimental to the production of phosphate esters, resulting in a considerable loss of monohydric alcohols.
And (II) alkali neutralization reaction is adopted, so that hydrogen chloride and phosphoric acid in the mixed material are absorbed by a solvent, although acidolysis of a reaction product is avoided by using the alkali neutralization reaction, the neutralization of a reaction mixture increases the cost of neutralizing alkali, a large amount of wastewater is generated, the standard treatment of the wastewater increases the production cost, and solid waste is generated to cause serious pollution.
And (III) because the monohydric alcohol has certain solubility in water, part of the monohydric alcohol is remained in the neutralized water, and the loss of raw materials is brought.
Disclosure of Invention
The applicant carries out research and improvement aiming at the existing problems and provides phosphate ester preparation equipment and a preparation method thereof.
The technical scheme adopted by the invention is as follows:
a phosphate ester preparation device comprises a multistage esterification reaction unit, a dealcoholization device and a gas washing device for recovering hydrogen chloride and monohydric alcohol, wherein the multistage esterification reaction unit is formed by sequentially arranging a plurality of esterification reaction units which are connected in series; wherein, a raw material input port of one esterification reaction unit positioned at the head part is connected with a raw material delivery outlet of a gas washing device, and a mixture input port of the gas washing device is used for being connected with mixture output ports of all esterification reaction units and dealcoholization devices in parallel; and a raw material input port of the dealcoholization device is connected with an esterification reaction unit positioned at the tail part.
The further technical scheme is as follows:
the device also comprises a product refining device for manufacturing the product and an acid making device for preparing the industrial-grade hydrochloric acid, wherein a raw material input port of the acid making device is connected with a raw material output port of the gas washing device, and a raw material input port of the product refining device is connected with a raw material input port of the dealcoholization device;
the multistage esterification reaction unit comprises a first-stage esterification reaction unit, a second-stage esterification reaction unit and a third-stage esterification reaction unit;
the primary esterification reaction unit and the secondary esterification reaction unit are both composed of a plurality of characteristic reaction units which are connected in series;
the three-stage esterification reaction unit comprises a characteristic reaction unit and a plurality of characteristic reaction flash evaporation deacidification units, wherein a plurality of branches are formed at the raw material output port of the characteristic reaction unit and are connected with the raw material input ports of the characteristic reaction flash evaporation deacidification units.
The specific structure of the characteristic reaction unit is as follows:
including reation kettle, first pump, heat exchanger and the first condenser that is used for receiving the raw materials, reation kettle, first pump, heat exchanger establish ties in proper order and form circulation circuit, reation kettle's gaseous phase export and the gaseous phase entry linkage of first condenser, the gaseous phase export intercommunication gas washing device of condenser.
The specific structure of the characteristic reaction flash evaporation deacidification unit is as follows:
including the flash distillation equipment that is used for dehydrochlorination, purification equipment and the second condenser that is used for improving liquid phase concentration, the gaseous phase export of flash distillation equipment, purification equipment communicates with the gaseous phase entry of second condenser respectively, the gaseous phase exit linkage scrubbing device of second condenser, a liquid phase exit linkage purification equipment of flash distillation equipment, another liquid phase export of flash distillation equipment and the liquid phase export of purification equipment are connected dealcoholize the device jointly.
The dealcoholization device has the following specific structure:
the characteristic rectification unit consists of a rectification tower, a first reboiler and a third condenser which are connected in series in one or more stages, wherein the bottom of the rectification tower is connected with a liquid phase inlet of the first reboiler which is connected in series in one or more stages, a liquid phase outlet of each first reboiler is connected with a product refining device, the top of the rectification tower is connected with a gas phase inlet of the third condenser, and a gas phase outlet of the third condenser is connected with a gas scrubbing device;
the liquid phase outlet of the first reboiler can be connected with the inlet of a second pump through a pipeline, and the outlet of the second pump is connected with the liquid phase inlet of the first reboiler to form a circulating loop;
the rectifying tower is also connected with a second reboiler in series to form a circulation loop, a preheater is further connected at the inlet of the rectifying tower, and the liquid phase inlet of the third condenser can be respectively connected with the rectifying tower through a branch for reflux or recovery to the esterification reaction unit.
The gas washing device comprises a first absorption tower, a first circulating tank, a third pump, a fourth condenser, a buffer tank, a second circulating tank, a second absorption tower and a fourth pump, wherein a liquid phase outlet of the first absorption tower is connected with a liquid phase inlet of the first circulating tank, a liquid phase outlet of the first circulating tank is connected with an inlet of the third pump, and an outlet of the third pump is connected with a liquid phase inlet of the first absorption tower; the gas phase outlet of the first absorption tower is connected with the liquid phase inlet of the first circulating tank through a fourth condenser; and a gas phase outlet of the fourth condenser is connected with a gas phase inlet of the second circulating tank through a buffer tank, a liquid phase inlet of the second circulating tank is connected with a liquid phase outlet of the second absorption tower, and a liquid phase inlet of the second absorption tower is connected with the second circulating tank through a fourth pump to form a circulating loop.
The preparation method by using the phosphate preparation equipment comprises the following steps:
the first step is as follows: primary esterification: phosphorus oxychloride with the phosphorus trichloride content of 0-0.5 wt% and monohydric alcohol with the water content of 0-0.3 wt%, wherein each mole of phosphorus oxychloride reacts with 2-9 moles of monohydric alcohol, the temperature of the freezing water of a reflux condenser is-40-10 ℃ under the negative pressure of mercury column of 400-758 mm, the mixture of volatile component monohydric alcohol and hydrogen chloride obtained after the reaction returns to the first-stage esterification reaction unit by cooling the first-stage esterification reaction unit, the temperature of a reaction kettle in the first-stage esterification reaction unit is-20-50 ℃ for reaction, and the mixture of volatile component monohydric alcohol and hydrogen chloride obtained after the reaction returns to the first-stage esterification reaction unit for 8-12 hours and then is transferred to second-stage esterification; removing monohydric alcohol from a mixture of uncondensed monohydric alcohol and hydrogen chloride by a gas washing device, wherein the temperature of a condenser in the gas washing device is-10 ℃, the temperature of an oxygen-phosphorus absorption liquid is 5-30 ℃, then entering an acid preparation device, and obtaining industrial byproduct hydrochloric acid under the negative pressure condition of the mercury column with the temperature of 5-30 ℃ and the pressure of 200-;
the second step is that: secondary esterification: mixing the material after the first-stage esterification reaction with monohydric alcohol with the water content of 0-0.3 wt%, and dropwise adding the monohydric alcohol according to the first-stage esterification molar ratio of 2-5 times for reaction; under the negative pressure of 400-758 mm Hg, the temperature of the chilled water of the reflux condenser is-20-30 ℃, the mixture of the monohydric alcohol and the hydrogen chloride, which are volatile components, obtained after the reaction returns to the secondary esterification reaction unit by cooling the secondary esterification reaction unit, wherein the temperature of a reaction kettle in the secondary esterification reaction unit is-20-50 ℃, and the secondary esterification reaction time is 8-12 hours and then the mixture is transferred to the tertiary esterification; removing residual monohydric alcohol from the mixture of the uncondensed monohydric alcohol and the hydrogen chloride through a gas washing device; the temperature of a condenser in the gas washing device is-20-30 ℃, the temperature of an oxygen-phosphorus absorption liquid is 5-30 ℃, then the oxygen-phosphorus absorption liquid enters an acid making device, and industrial byproduct hydrochloric acid is obtained under the negative pressure condition of the liquid absorption liquid with the temperature of 5-30 ℃ and the pressure of 200-740 mm mercury columns;
the third step: tertiary esterification: the third-stage esterification reaction unit receives the materials after the second-stage esterification reaction, the temperature of the freezing water of the reflux condenser is-20-30 ℃ under the negative pressure of 400-758 mm Hg, the materials are cooled down to the third-stage esterification reaction unit, the temperature of a reaction kettle in the third-stage esterification reaction unit is-20-50 ℃, and the materials are obtained after the reactionReturning the mixture of the monohydric alcohol and the hydrogen chloride as volatile components to the third-stage esterification reaction unit and entering into flash evaporation equipment to separate the hydrogen chloride in the mixture and recovering the monohydric alcohol; nitrogen is also supplemented in the three-stage esterification step, and the nitrogen supplementation amount is 0-50 m3Removing the residual monohydric alcohol from the mixture of the uncondensed monohydric alcohol and the hydrogen chloride by a gas washing device, wherein the temperature of a condenser in the gas washing device is-20-30 ℃, then entering an acid making device, and obtaining the industrial byproduct hydrochloric acid under the negative pressure condition of the liquid absorption liquid temperature of 5-30 ℃ and the pressure of 200-740 mm mercury column;
the fourth step: dealcoholizing and acid-dispelling: a rectifying tower in the dealcoholization device receives the materials reacted by the three-stage esterification unit, nitrogen is supplemented to enter the rectifying tower, the temperature of the top of the rectifying tower is 20-50 ℃, the temperature of the middle part of the rectifying tower is 60-110 ℃, the temperature of the bottom of the rectifying tower is 115-160 ℃, the negative pressure is 600-750 mm Hg, the rectifying tower produces phosphate with the main content of 90-99% by weight and separates monohydric alcohol and hydrogen chloride from the phosphate, and part of monohydric alcohol is condensed by a condenser and returns to the first-stage esterification reaction unit for continuous reaction; nitrogen is also supplemented in the step of dealcoholizing and acid-removing, and the nitrogen supplementation amount is 0-50 m3Returning hydrogen chloride and the residual monohydric alcohol to the primary esterification reaction unit for continuous reaction, then feeding the residual hydrogen chloride and a small amount of monohydric alcohol into a gas washing device, wherein the temperature of a condenser in the gas washing device is-20-10 ℃, the temperature of an oxygen-phosphorus absorption liquid is 5-30 ℃, and the phosphate enters a product refining device;
the fifth step: rectification and separation: and in the fourth step, the phosphate ester with hydrogen chloride and monohydric alcohol removed is continuously fed and purified by a product refining device to obtain recycled light components, high-boiling-point substances capable of being packaged and the phosphate ester with the purity of 99.9 percent.
The invention has the following beneficial effects:
according to the invention, the gas washing device is added, the unreacted monohydric alcohol carried in the volatilization of the hydrogen chloride is recovered by the gas washing device, the phosphorus oxychloride in the absorption liquid is carried in the industrial hydrochloric acid water when the industrial hydrochloric acid water absorbs the volatilization of the hydrogen chloride, and then the volatilized hydrogen chloride is absorbed by the industrial water, so that the industrial-grade qualified byproduct hydrochloric acid can be prepared, the waste of raw materials is reduced, and the yield of waste gas, waste water and solid waste is reduced.
In the reaction process, the method effectively removes hydrogen chloride by means of multi-stage esterification reaction, flash evaporation, reaction temperature change, nitrogen protection and the like, prevents side reaction at a high temperature, optimizes the parameters of the rectifying tower during dealcoholization, realizes deep separation of alcohol and ester, prevents side reaction at a high temperature by nitrogen protection, greatly reduces the amount of waste water and improves the conversion rate of the reaction.
By adopting phosphorus oxychloride and monohydric alcohol as raw materials and carrying out multistage esterification reaction, dealcoholization and hydrogen chloride removal, rectification separation and hydrogen chloride tail gas absorption, the effective removal of hydrogen chloride can be realized, the acidolysis of phosphate and the decomposition of heat-sensitive effect are greatly reduced, the generation of side reaction is reduced, a neutralization working section in the traditional process is omitted, the recovery rate of the monohydric alcohol as the raw material is improved, the generation of waste water, solid waste and waste gas can be reduced, the purity of the obtained high-purity phosphate as a main product is 99.9%, the generated light components can be continuously recycled, high-boiling substances can be packaged and sold, the excessive ratio of the monohydric alcohol is ensured to be as small as possible through continuous reaction, the preparation method is scientific, reasonable, economic and environment-friendly, zero emission is achieved, and the device can ensure intermittent production and simultaneously meet the advantages of large-scale continuous industrial production.
Drawings
FIG. 1 is a schematic flow diagram of the preparation of phosphate esters according to the present invention.
FIG. 2 is a schematic structural flow diagram of a primary esterification unit according to the present invention.
FIG. 3 is a schematic structural flow diagram of a secondary esterification unit according to the present invention.
FIG. 4 is a schematic structural flow diagram of a three-stage esterification unit according to the present invention.
FIG. 5 is a schematic flow diagram of the dealcoholization apparatus of the present invention.
FIG. 6 is a schematic flow diagram of a product refining apparatus according to the present invention.
FIG. 7 is a schematic view of the structure of the scrubber of the present invention.
FIG. 8 is a schematic structural view of an acid making apparatus according to the present invention.
Wherein: 1. a primary esterification reaction unit; 2. a secondary esterification reaction unit; 121. a first condenser; 122. a reaction kettle; 123. a first pump; 124. a heat exchanger; 125. a vacuum pump; 3. a tertiary esterification reaction unit; 301. flash evaporation equipment; 302. purification equipment; 303. a second condenser; 4. a dealcoholization device; 401. a preheater; 402. a rectifying tower; 403. a first reboiler; 404. a second pump; 405. a second reboiler; 406. a third condenser; 5. a product refining device; 6. a gas washing device; 601. a first absorption tower; 602. a first circulation tank; 603. a third pump; 604. a fourth condenser; 605. a buffer tank; 606. a second recycle tank; 607. a second absorption tower; 608. a fourth pump; 7. an acid making device; 701. a high efficiency membrane bubble absorber; 702. a transfer tank; 703. a fifth pump; 704. a sixth pump; 705. a water jet vacuum pump; 706. a fan.
Detailed Description
The following describes specific embodiments of the present invention.
As shown in figure 1, a phosphate ester preparation equipment includes a multi-stage esterification reaction unit, a dealcoholization device 4, a gas washing device 6 for recovering hydrogen chloride and monohydric alcohol, the multi-stage esterification reaction unit is composed of a plurality of esterification reaction units which are arranged in sequence and are connected in series; wherein, the raw material input port of one esterification reaction unit positioned at the head part is connected with the raw material delivery port of the gas washing device 6, and the mixture input port of the gas washing device 6 is used for being connected with the mixture output ports of each esterification reaction unit and the dealcoholization device 4 in parallel; the raw material input port of the dealcoholization device 4 is connected with an esterification reaction unit positioned at the tail part.
As shown in fig. 2, fig. 3 and fig. 4, the multi-stage esterification reaction unit includes a first-stage esterification reaction unit 1, a second-stage esterification reaction unit 2 and a third-stage esterification reaction unit 3;
the primary esterification reaction unit 1 and the secondary esterification reaction unit 2 are both composed of a plurality of characteristic reaction units which are connected in series;
the third-stage esterification reaction unit 3 comprises a characteristic reaction unit and a plurality of characteristic reaction flash evaporation deacidification units, wherein a plurality of branches are formed at the raw material output port of the characteristic reaction unit and are connected with the raw material input ports of the characteristic reaction flash evaporation deacidification units.
Wherein, the specific structure of the characteristic reaction unit is as follows:
the device comprises a reaction kettle 122 for receiving raw materials, a first pump 123, a heat exchanger 124 and a first condenser 121, wherein the reaction kettle 122, the first pump 123 and the heat exchanger 124 are sequentially connected in series to form a circulation loop, a gas phase outlet of the reaction kettle 122 is connected with a gas phase inlet of the first condenser 121, in the primary esterification reaction unit 1, the gas phase outlet of the first condenser 121 is communicated with a gas washing device 6, as shown in fig. 3, a gas phase outlet of the first condenser 121 in the secondary esterification reaction unit 2 is connected with an inlet of a vacuum pump 125, a gas phase outlet of the vacuum pump 125 is communicated with the gas washing device 6, and a liquid phase outlet of the vacuum pump 125 flows into the reaction kettle 122. The monohydric alcohol carried over by the hydrogen chloride will largely become a liquid reflux at the outlet of the vacuum pump 125, while the remaining portion of the monohydric alcohol enters the scrubbing unit.
The heat exchanger 124 is made of graphite material and PPH by composite combination.
The specific structure of the characteristic reaction flash evaporation deacidification unit is as follows:
the device comprises a flash evaporation device 301 for dehydrochlorination, a purification device 302 for improving liquid phase concentration and a second condenser 303, wherein gas phase outlets of the flash evaporation device 301 and the purification device 302 are respectively communicated with a gas phase inlet of the second condenser 303, a gas phase outlet of the second condenser 303 is connected with a gas washing device 6, one liquid phase outlet of the flash evaporation device 301 is connected with the purification device 302, and the other liquid phase outlet of the flash evaporation device 301 and a liquid phase outlet of the purification device 302 are jointly connected with a dealcoholization device 4. As shown in fig. 4, a vacuum pump 125 is also provided in the three-stage esterification reaction unit 3, the second condenser 303 and the gas phase outlet of the first condenser 121 in the characteristic reaction unit are collectively communicated with the gas phase inlet of the vacuum pump 125, the gas phase outlet of the vacuum pump 125 is communicated with the gas washing device 6, and the liquid phase outlet of the vacuum pump 125 flows into the reaction kettle 122. The monohydric alcohol carried over by the hydrogen chloride will largely become a liquid reflux at the outlet of the vacuum pump 125, while the remaining portion of the monohydric alcohol enters the scrubbing unit.
As shown in fig. 5, the dealcoholization apparatus 4 has the following specific structure:
the characteristic rectification unit consists of a rectification tower 402, a first reboiler 403 and a third condenser 406 which are connected in series in one or more stages, wherein the bottom of the rectification tower 402 is connected with a liquid phase inlet of the first reboiler 403 which is connected in series in one or more stages, a liquid phase outlet of each first reboiler 403 is connected with a product refining device 5, and the top of the rectification tower 402 is connected with a gas phase inlet of the third condenser 406; the liquid phase outlet of the first reboiler 403 may be connected to the inlet of the second pump 404 through a pipeline, the outlet of the second pump 404 is connected to the liquid phase inlet of the first reboiler 403 to form a circulation loop, and the second pump 404 is a high temperature, vacuum resistant, corrosion resistant pump. As shown in fig. 5, the gas phase outlet of the third condenser 406 is also connected to the gas washing device 6 through a vacuum pump 125, and the liquid phase outlet of the vacuum pump 125 is communicated with the reaction kettle 122 in the primary esterification reaction unit 1 through a pipeline. The monohydric alcohol carried over by the hydrogen chloride will largely become a liquid reflux at the outlet of the vacuum pump 125, while the remainder will enter the scrubbing unit.
The rectifying tower 402 is also connected with a second reboiler 405 in series to form a circulation loop, the inlet of the rectifying tower 402 is also connected with a preheater 401, and the liquid phase inlet of the third condenser 406 can be respectively connected with the rectifying tower 402 through a branch for reflux or recovery to the esterification reaction unit.
As shown in fig. 7, the scrubber 6 includes a first absorption tower 601, a first circulation tank 602, a third pump 603, a fourth condenser 604, a buffer tank 605, a second circulation tank 606, a second absorption tower 607, and a fourth pump 608, a liquid phase outlet of the first absorption tower 601 is connected to a liquid phase inlet of the first circulation tank 602, a liquid phase outlet of the first circulation tank 602 is connected to an inlet of the third pump 603, and an outlet of the third pump 603 is connected to a liquid phase inlet of the first absorption tower 601; a gas phase outlet of the first absorption tower 601 is connected with a liquid phase inlet of the first circulation tank 602 through a fourth condenser 604; the gas phase outlet of the fourth condenser 604 is connected to the gas phase inlet of the second circulation tank 606 through the buffer tank 605, the liquid phase inlet of the second circulation tank 606 is connected to the liquid phase outlet of the second absorption tower 607, and the liquid phase inlet of the second absorption tower 607 is further connected to the second circulation tank 606 through the fourth pump 608 to form a circulation loop.
As shown in fig. 1, the device further comprises a product refining device 5 for manufacturing products and an acid making device 7 for preparing industrial-grade hydrochloric acid, wherein a raw material input port of the acid making device 7 is connected with a raw material output port of the gas washing device 6, and a raw material input port of the product refining device 5 is connected with a raw material input port of the dealcoholization device 4. As shown in fig. 6, the product refining device 5 is formed by connecting at least two stages of characteristic rectification units in series, wherein one stage of characteristic rectification unit is used for product refining, the other stage of characteristic rectification unit is used for refining high-boiling-point substances, and the first stage of characteristic rectification unit is used for light component recycling.
As shown in fig. 8, the acid preparation apparatus 7 includes a plurality of high-efficiency membrane bubble absorbers 701 connected in series, a gas phase inlet of the high-efficiency membrane bubble absorber 701 located at the head is communicated with a gas phase outlet of the second absorption tower 607 in the gas washing apparatus 6, a gas phase outlet of the high-efficiency membrane bubble absorber 701 located at the tail is connected with a gas phase inlet of a water jet vacuum pump 705, and a gas phase outlet of the water jet vacuum pump 705 is connected with a tail gas treatment apparatus through a fan 706. As shown in fig. 8, the water tank of the water jet vacuum pump 705 is further added with water and then connected to the liquid phase inlet of the high efficiency membrane bubble absorber 701 located at the tail through the sixth pump 704, the liquid phase inlets and outlets between the adjacent high efficiency membrane bubble absorbers 701 are communicated with each other, the gas phase inlets and outlets between the adjacent high efficiency membrane bubble absorbers 701 are communicated with each other, the liquid phase outlet of the high efficiency membrane bubble absorber 701 located at the head is communicated with the inlet of the fifth pump 703 through the transfer tank 702, and 31% of qualified industrial grade hydrochloric acid flows out through the outlet of the fifth pump 703.
Example 1:
the method for preparing tributyl phosphate by using the tributyl phosphate preparing apparatus according to the embodiment of claim 1, comprising the steps of:
as shown in fig. 2, the first step: primary esterification: phosphorus oxychloride with phosphorus trichloride content of 0.5% with flow rate of 0.23m3Butanol with a water content of 0.3% by weight at a flow rate of 0.45m3The reaction kettle 122 can be composed of a two-square reaction kettle and two five-square reaction kettles which are connected in series and can enable the phosphorus oxychloride and the butanol to continuously react, and the pump 123 adopts a multi-stage series transfer pump or any one of level differencesAnd the continuous conveying of the esterification reactants is realized, each reaction kettle is provided with a first condenser 121 (the first condenser 121 is only arranged on the reaction kettle 122 for illustration in the figure), the temperature of the first condenser 121 connected with each reaction kettle is-40 ℃ under the negative pressure of 400 mmHg, the mixture of the volatile components butanol and hydrogen chloride obtained from the reaction returns to the reaction kettle 122 through the first condenser by cooling the primary esterification reaction unit, and the mixture is transferred to the secondary esterification reaction unit after the reaction time is 8 hours. Part of the mixture of non-condensed butanol and hydrogen chloride is removed by a gas washing device 6 for recycling, as shown in fig. 7, firstly, oxygen phosphorus is added into a first circulation tank 602, the temperature of an oxygen phosphorus absorption liquid is 5 ℃, the temperature of a third condenser 604 is-10 ℃, the mixture is continuously circulated through the first circulation tank 602 and a third pump 603, a liquid phase after condensation reaction returns to the first circulation tank 602, a gas phase enters a second buffer tank 605 and enters a second absorption tower 607 through a second circulation tank 606 and a fourth pump 608, dilute acid is added at the second circulation tank 606 to react the materials to form phosphoric acid, the phosphoric acid enters a product refining device, hydrogen chloride in the second absorption tower 607 enters an acid making device 7 through a gas phase outlet, hydrogen chloride bubbles in the acid making device 7 through a high efficiency membrane absorber 701, the negative pressure of 200 mm of mercury column, the temperature of water absorption liquid is 5 ℃, the water flow circulation absorption is 1100kg/h, under the condition that the circulating amount of the weak acid is absorbed by 950kg/h, the by-product hydrochloric acid with the content of 31 percent is produced.
As shown in fig. 3, the second step: second-stage esterification, mixing the material after the first-stage esterification reaction with butanol with the water content of 0.1 percent by weight, dropwise adding the butanol according to the first-stage esterification molar ratio of 2-5 times for reaction, wherein the butanol is 0.62m in the embodiment3Dropwise adding reaction for 8 hours, namely cooling the secondary esterification reaction unit at the temperature of-20 ℃ in a first condenser 121 in the secondary esterification reaction unit under the negative pressure of 600 mm Hg, cooling the secondary esterification reaction unit, reacting at the temperature of 10 ℃ in a first reaction kettle 122 in the secondary esterification reaction unit, returning the mixture of volatile components butanol and hydrogen chloride obtained after the reaction to the secondary esterification reaction unit, and transferring to tertiary esterification after the secondary esterification reaction time is 8 hours; the mixture of non-condensable components butanol and hydrogen chloride was passed through a scrubber to remove butanol, as shown in FIG. 7, first in the first recycle tankAdding oxygen and phosphorus into 602, keeping the temperature of an oxygen and phosphorus absorption liquid at 5 ℃, keeping the temperature of a third condenser 604 at-10 ℃, continuously circulating through a first circulating tank 602 and a third pump 603, returning a liquid phase after condensation reaction to the first circulating tank 602, allowing a gas phase to enter a second buffer tank 605, allowing the gas phase to enter a second absorption tower 607 through a second circulating tank 606 and a fourth pump 608, adding dilute acid into the second circulating tank 606 to allow the materials to react to form phosphoric acid, allowing the phosphoric acid to enter a product refining device, allowing hydrogen chloride in the second absorption tower 607 to enter an acid making device 7 through a gas phase outlet, allowing the hydrogen chloride to pass through a high-efficiency membrane bubble absorber 701 in the acid making device 7, and generating by-product hydrochloric acid with the content of 31% under the conditions of 200 mm Hg column negative pressure, water absorption liquid temperature of 5 ℃, water flow circulation absorption of 1100kg/h, and weak acid circulation absorption of 950 kg.
As shown in fig. 4, the third step: tertiary esterification: the third-stage esterification reaction unit receives the materials after the second-stage esterification reaction, the temperature of the freezing water of the first condenser 121 in the third-stage esterification reaction unit 3 is-20 ℃ under the negative pressure of 400 mmHg, the temperature is 15 ℃ for reaction by cooling the third-stage esterification reaction unit, nitrogen is introduced into the third-stage esterification device, and the nitrogen supplement amount is 50m3The hydrogen chloride dissolved in the reaction liquid is desorbed and removed by supplementing nitrogen, the mixture of volatile components butanol and hydrogen chloride obtained after the reaction returns to the third-stage esterification reaction unit and enters the flash evaporation equipment 301 to be separated from the hydrogen chloride in the mixture, the hydrogen chloride in the liquid phase is reduced by the purification equipment 302 to improve the concentration of the liquid phase, the gas phase in the purification equipment 302 is mostly hydrogen chloride and contains a small amount of butanol, the temperature of the freezing water passing through the second condenser 303 is-10 ℃, the butanol carried in the gas phase is cooled by the second condenser 303 and recovered, the mixture of the uncondensed components butanol and the hydrogen chloride is removed by a gas washing device, as shown in figure 7, phosphorus oxide is firstly added into the first circulation tank 602, the temperature of the phosphorus oxide absorption liquid is 5 ℃, the temperature of the third condenser 604 is-10 ℃, and the circulation is continuously carried out through the first circulation tank 602 and the third pump 603, the liquid phase after the condensation reaction returns to the first circulating tank 602, the gas phase enters the second buffer tank 605 and enters the second absorption tower 607 through the second circulating tank 606 and the fourth pump 608, and dilute acid is added at the second circulating tank 606 to react the materialsPhosphoric acid is formed, the phosphoric acid enters a product refining device, hydrogen chloride in the second absorption tower 607 enters an acid making device 7 through a gas phase outlet, and the hydrogen chloride in the acid making device 7 produces by-product hydrochloric acid with the content of 31% through a high-efficiency membrane bubbling absorber 701 under the conditions of 200 mm Hg negative pressure, the temperature of water absorption liquid of 5 ℃, water circulation absorption of 1100kg/h and light acid circulation absorption of 950 kg/h.
As shown in fig. 5, the fourth step: dealcoholizing and acid-dispelling: a rectifying tower 402 in the dealcoholization device receives the materials after the reaction of the three-stage esterification unit and simultaneously replenishes nitrogen gas of 40m3The gas enters a rectifying tower, nitrogen is added to protect acidolysis and heat sensitive effect of tributyl phosphate and blow off a small amount of hydrogen chloride gas, the product quality can be controlled by improving the temperature through a preheater 401 before entering the rectifying tower, and the temperature of the preheater 401 is controlled to be 40 ℃. In this embodiment, the upper part of the rectifying tower 402 is a rectifying section, the lower part is a stripping section, the bottom part produces a material mainly containing tributyl phosphate, the temperature of the top of the rectifying tower 402 is 20 ℃, the temperature of the separating tower is 60 ℃, the pressure of the rectifying tower is 735 mm of mercury column under negative pressure, volatile components of butanol and hydrogen chloride in the reaction mixture are removed, and the top of the rectifying tower produces 0.45m3Controlling butanol to return to the esterification unit through a third condenser 406 to continuously participate in the reaction, wherein the flow rate is 0.12m3Hydrogen chloride enters a gas washing device and an acid making device through phosphorus oxide, the temperature at the bottom of a rectifying tower is 130 ℃, excessive butanol and hydrogen chloride in the esterification reaction are separated from tributyl phosphate, and the bottom of the rectifying tower produces 0.72m3A tributyl phosphate, the main content of which is 95% by weight. In the alcohol removal and acid removal step, nitrogen gas is added for protection when the first reboiler 403 is heated, and the nitrogen gas is supplemented in an amount of 55m3And h, preventing side reaction by adding inert gas protection. Secondly, blowing off trace hydrogen chloride.
As shown in fig. 6, the fifth step: rectification and separation: the tributyl phosphate from which hydrogen chloride and butanol are removed in the fourth step is fed into a product refining device for continuous feeding and purification, as shown in fig. 6, in order to meet higher requirements of customers, a characteristic rectification unit for light component removal is added, which aims to return a reactant with low product component content to continue to enter a dealcoholization device 4, specifically:
primary rectification: the crude product enters a rectifying tower in a characteristic rectifying unit for light component removal, the temperature of the top of the rectifying tower is controlled to be 70 ℃, the negative pressure is controlled to be 720 mm Hg, the temperature of the bottom of the rectifying tower is 140 ℃, 95.5 content of tributyl phosphate is extracted at 0.6m3/h from the bottom of the rectifying tower and enters the characteristic rectifying unit for product refining, and the top of the rectifying tower is 0.03m3And (4) extracting alcohol ester azeotrope (light components) for recycling.
Secondary rectification: tributyl phosphate produced at the bottom of the tower after the first-stage rectification enters a rectifying tower of a characteristic rectifying unit for product refining by adding nitrogen protection, wherein the nitrogen flow is 50m3The temperature of the top of the rectifying tower of the characteristic rectifying unit for product refining is 180 ℃, the negative pressure is controlled to be 745 mm Hg, the temperature of the bottom of the rectifying tower is 220 ℃, and the thickness of the top of the rectifying tower is 0.641m3A tributyl phosphate content of 99.9% was withdrawn,/h, corresponding to a yield of 95%, based on the use of phosphorus oxychloride. The column bottom is at a height of 0.04m3And h, extracting high-boiling-point substances (heavy component polyphosphate) and entering a characteristic rectification unit for high-boiling refining, packaging the generated high-boiling-point substances, and continuously returning light components to the dealcoholization device 4.
The process of the invention is compared with the traditional process in the input and output of the material for producing tributyl phosphate as follows:
the traditional process comprises the following steps:
the new process comprises the following steps:
the table shows that the investment of the process is greatly reduced compared with the traditional process, the yield of tributyl phosphate is relatively increased, the yields of waste gas, waste water and solid waste are greatly reduced, and more butanol can be obtained for recycling.
According to the invention, the gas washing device is added, unreacted butanol carried in the hydrogen chloride generated in the process of generation is recycled by the gas washing device, and then the recycled butanol is used for absorbing the hydrogen chloride by water, so that the industrial-grade qualified hydrochloric acid can be prepared, the waste of raw materials is reduced, and the yield of waste gas, waste water and solid waste is reduced.
In the reaction process, the hydrogen chloride is effectively removed by means of multi-stage esterification reaction, flash evaporation, reaction temperature change, nitrogen protection and the like, the parameters of the rectifying tower are optimized during dealcoholization, the deep separation of alcohol and ester is realized, the generation of side reaction at high temperature is prevented by introducing nitrogen protection, and the wastewater amount is greatly reduced.
By adopting phosphorus oxychloride and butanol as raw materials and carrying out multistage esterification reaction, dealcoholization and hydrogen chloride removal, rectification separation and hydrogen chloride tail gas absorption, the method can effectively remove the hydrogen chloride, greatly reduce the acidolysis of tributyl phosphate and reduce the generation of side reaction, and can reduce the generation of waste water, solid waste and waste gas by omitting a neutralization working section in the traditional process, so that the purity of the obtained main product tributyl phosphate is 99.9 percent, the generated light components can be continuously recycled, high-boiling substances can be packaged and sold, the excessive ratio of the butanol is ensured to be as small as possible through continuous reaction, the preparation method is scientific, reasonable, economic and environment-friendly, zero emission is achieved, and the advantage of large-scale continuous industrial production can be met.
The foregoing description is illustrative of the present invention and is not to be construed as limiting thereof, the scope of the invention being defined by the appended claims, which may be modified in any manner without departing from the basic structure thereof.
Claims (10)
1. A phosphate ester preparation equipment is characterized in that: the device comprises a multi-stage esterification reaction unit, a dealcoholization device (4) and a gas washing device (6) for recovering hydrogen chloride and monohydric alcohol, wherein the multi-stage esterification reaction unit is formed by sequentially arranging a plurality of esterification reaction units which are connected in series; wherein, the raw material input port of one esterification reaction unit positioned at the head part is connected with the raw material delivery port of the gas washing device (6), and the mixture input port of the gas washing device (6) is used for being connected with the mixture output ports of each esterification reaction unit and the dealcoholization device (4) in parallel; and a raw material input port of the dealcoholization device (4) is connected with an esterification reaction unit positioned at the tail part.
2. The phosphate ester producing apparatus according to claim 1, wherein: the device is characterized by further comprising a product refining device (5) for manufacturing a product and an acid making device (7) for preparing industrial-grade hydrochloric acid, wherein a raw material input port of the acid making device (7) is connected with a raw material output port of the gas washing device (6), and a raw material input port of the product refining device (5) is connected with a raw material input port of the dealcoholization device (4).
3. The phosphate ester producing apparatus according to claim 1, wherein: the multistage esterification reaction unit comprises a first-stage esterification reaction unit (1), a second-stage esterification reaction unit (2) and a third-stage esterification reaction unit (3);
the primary esterification reaction unit (1) and the secondary esterification reaction unit (2) are both composed of a plurality of characteristic reaction units which are connected in series;
the three-stage esterification reaction unit (3) comprises a characteristic reaction unit and a plurality of characteristic reaction flash evaporation deacidification units, wherein a raw material output port of the characteristic reaction unit forms a plurality of branches and is connected with raw material input ports of the characteristic reaction flash evaporation deacidification units.
4. The phosphate ester producing apparatus according to claim 3, wherein: the specific structure of the characteristic reaction unit is as follows:
including reation kettle (122), first pump (123), heat exchanger (124) and first condenser (121) that are used for receiving the raw materials, reation kettle (122), first pump (123), heat exchanger (124) are established ties in proper order and are formed circulation circuit, the gaseous phase export of reation kettle (122) is connected with the gaseous phase entry of first condenser (121), the gaseous phase export intercommunication scrubbing device (6) of condenser (121).
5. The phosphate ester producing apparatus according to claim 3, wherein: the specific structure of the characteristic reaction flash evaporation deacidification unit is as follows:
including flash distillation equipment (301) that is used for dehydrochlorination, purification equipment (302) and second condenser (303) that are used for improving liquid phase concentration, the gaseous phase export of flash distillation equipment (301), purification equipment (302) communicates with the gaseous phase entry of second condenser (303) respectively, the gaseous phase exit linkage scrubbing device (6) of second condenser (303), purification equipment (302) are connected to a liquid phase exit linkage of flash distillation equipment (301), dealcoholize device (4) are connected jointly with the liquid phase export of purification equipment to another liquid phase export of flash distillation equipment (301).
6. The phosphate ester producing apparatus according to claim 1, wherein: the dealcoholization device (4) has the following specific structure:
the characteristic rectification unit consists of a rectification tower (402), one or more stages of first reboilers (403) connected in series and a third condenser (406), wherein the bottom of the rectification tower (402) is connected with a liquid phase inlet of the one or more stages of first reboilers (403) connected in series, a liquid phase outlet of each first reboilers (403) is connected with a product refining device (5), the top of the rectification tower (402) is connected with a gas phase inlet of the third condenser (406), and a gas phase outlet of the third condenser (406) is connected with a gas washing device (6).
7. The phosphate ester producing apparatus according to claim 6, wherein: the liquid phase outlet of the first reboiler (401) may also be connected to an inlet of a second pump (404) via a line, the outlet of the second pump (404) being connected to the liquid phase inlet of the first reboiler (401) to form a circulation loop.
8. The phosphate ester producing apparatus according to claim 6, wherein: the rectifying tower (402) is also connected with a second reboiler (405) in series to form a circulation loop, a preheater (401) is further connected to an inlet of the rectifying tower (402), and a liquid phase inlet of the third condenser (406) can be respectively connected with the rectifying tower (402) through a branch for reflux or recovery to the esterification reaction unit.
9. The phosphate ester production apparatus according to any one of claims 1 to 8, wherein: the gas washing device (6) comprises a first absorption tower (601), a first circulating tank (602), a third pump (603), a fourth condenser (604), a buffer tank (605), a second circulating tank (606), a second absorption tower (607) and a fourth pump (608), wherein a liquid phase outlet of the first absorption tower (601) is connected with a liquid phase inlet of the first circulating tank (602), a liquid phase outlet of the first circulating tank (602) is connected with an inlet of the third pump (603), and an outlet of the third pump (603) is connected with a liquid phase inlet of the first absorption tower (601); the gas phase outlet of the first absorption tower (601) is connected with the liquid phase inlet of the first circulating tank (602) through a fourth condenser (604); the gas phase outlet of the fourth condenser (604) is connected with the gas phase inlet of the second circulating tank (606) through a buffer tank (605), the liquid phase inlet of the second circulating tank (606) is connected with the liquid phase outlet of the second absorption tower (607), and the liquid phase inlet of the second absorption tower (607) is also connected with the second circulating tank (606) through a fourth pump (608) to form a circulating loop.
10. The method for preparing phosphate ester by using the phosphate ester preparing apparatus as claimed in claim 1, comprising the steps of:
the first step is as follows: primary esterification: phosphorus oxychloride with the phosphorus trichloride content of 0-0.5 wt% and monohydric alcohol with the water content of 0-0.3 wt%, wherein each mole of phosphorus oxychloride reacts with 2-9 moles of monohydric alcohol, the temperature of the freezing water of a reflux condenser is-40-10 ℃ under the negative pressure of mercury column of 400-758 mm, the mixture of volatile component monohydric alcohol and hydrogen chloride obtained after the reaction returns to the first-stage esterification reaction unit by cooling the first-stage esterification reaction unit, the temperature of a reaction kettle in the first-stage esterification reaction unit is-20-50 ℃ for reaction, and the mixture of volatile component monohydric alcohol and hydrogen chloride obtained after the reaction returns to the first-stage esterification reaction unit for 8-12 hours and then is transferred to second-stage esterification; removing monohydric alcohol from a mixture of uncondensed monohydric alcohol and hydrogen chloride by a gas washing device, wherein the temperature of a condenser in the gas washing device is-10 ℃, the temperature of an oxygen-phosphorus absorption liquid is 5-30 ℃, then entering an acid preparation device, and obtaining industrial byproduct hydrochloric acid under the negative pressure condition of the mercury column with the temperature of 5-30 ℃ and the pressure of 200-;
the second step is that: secondary esterification: mixing the material after the first-stage esterification reaction with monohydric alcohol with the water content of 0-0.3 wt%, and dropwise adding the monohydric alcohol according to the first-stage esterification molar ratio of 2-5 times for reaction; under the negative pressure of 400-758 mm Hg, the temperature of the chilled water of the reflux condenser is-20-30 ℃, the mixture of the monohydric alcohol and the hydrogen chloride, which are volatile components, obtained after the reaction returns to the secondary esterification reaction unit by cooling the secondary esterification reaction unit, wherein the temperature of a reaction kettle in the secondary esterification reaction unit is-20-50 ℃, and the secondary esterification reaction time is 8-12 hours and then the mixture is transferred to the tertiary esterification; removing residual monohydric alcohol from the mixture of the uncondensed monohydric alcohol and the hydrogen chloride through a gas washing device; the temperature of a condenser in the gas washing device is-20-30 ℃, the temperature of an oxygen-phosphorus absorption liquid is 5-30 ℃, then the oxygen-phosphorus absorption liquid enters an acid making device, and industrial byproduct hydrochloric acid is obtained under the negative pressure condition of the liquid absorption liquid with the temperature of 5-30 ℃ and the pressure of 200-740 mm mercury columns;
the third step: tertiary esterification: the third-stage esterification reaction unit receives the materials after the second-stage esterification reaction, the temperature of the freezing water of the reflux condenser is-20-30 ℃ under the negative pressure of 400-758 mm Hg, the mixture of volatile component monohydric alcohol and hydrogen chloride obtained after the reaction returns to the third-stage esterification reaction unit and enters flash evaporation equipment to be separated from the hydrogen chloride in the mixture, and the monohydric alcohol is recovered by cooling the third-stage esterification reaction unit, wherein the temperature of a reaction kettle in the third-stage esterification reaction unit is-20-50 ℃ for reaction; nitrogen is also supplemented in the three-stage esterification step, and the nitrogen supplementation amount is 0-50 m3Removing the residual monohydric alcohol from the mixture of the uncondensed monohydric alcohol and the hydrogen chloride by a gas washing device, wherein the temperature of a condenser in the gas washing device is-20-30 ℃, then entering an acid making device, and obtaining the industrial byproduct hydrochloric acid under the negative pressure condition of the liquid absorption liquid temperature of 5-30 ℃ and the pressure of 200-740 mm mercury column;
the fourth step: dealcoholizing and acid-dispelling: a rectifying tower in the dealcoholization device receives the materials reacted by the three-stage esterification unit, nitrogen is supplemented to enter the rectifying tower, the temperature of the top of the rectifying tower is 20-50 ℃, the temperature of the middle part of the rectifying tower is 60-110 ℃, the temperature of the bottom of the rectifying tower is 115-160 ℃, the negative pressure is 600-750 mm Hg, the rectifying tower produces phosphate with the main content of 90-99 percent by weight and separates monohydric alcohol and hydrogen chloride from the phosphate, and part of monohydric alcohol passes through a condenserCondensing the mixture to a first-stage esterification reaction unit for continuous reaction; nitrogen is also supplemented in the step of dealcoholizing and acid-removing, and the nitrogen supplementation amount is 0-50 m3Returning hydrogen chloride and the residual monohydric alcohol to the primary esterification reaction unit for continuous reaction, then feeding the residual hydrogen chloride and a small amount of monohydric alcohol into a gas washing device, wherein the temperature of a condenser in the gas washing device is-20-10 ℃, the temperature of an oxygen-phosphorus absorption liquid is 5-30 ℃, and the phosphate enters a product refining device;
the fifth step: rectification and separation: and in the fourth step, the phosphate ester with hydrogen chloride and monohydric alcohol removed is continuously fed and purified by a product refining device to obtain recycled light components, high-boiling-point substances capable of being packaged and the phosphate ester with the purity of 99.9 percent.
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| CN114057787A (en) * | 2021-11-25 | 2022-02-18 | 浙江万盛股份有限公司 | Preparation method of triethyl phosphate |
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Application publication date: 20210504 |