CN115611794B - Continuous purification process of peroxide initiator for vinyl chloride polymerization - Google Patents
Continuous purification process of peroxide initiator for vinyl chloride polymerization Download PDFInfo
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- 239000003999 initiator Substances 0.000 title claims abstract description 43
- 238000000746 purification Methods 0.000 title claims abstract description 29
- 150000002978 peroxides Chemical class 0.000 title claims abstract description 27
- 238000006116 polymerization reaction Methods 0.000 title abstract description 16
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 title abstract description 14
- 238000005406 washing Methods 0.000 claims abstract description 62
- 239000012071 phase Substances 0.000 claims abstract description 55
- 239000007788 liquid Substances 0.000 claims abstract description 21
- 239000011550 stock solution Substances 0.000 claims abstract description 17
- 238000004065 wastewater treatment Methods 0.000 claims abstract description 15
- 239000012295 chemical reaction liquid Substances 0.000 claims abstract description 10
- 239000012074 organic phase Substances 0.000 claims abstract description 9
- 230000018044 dehydration Effects 0.000 claims abstract description 8
- 238000006297 dehydration reaction Methods 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims abstract description 7
- 238000000605 extraction Methods 0.000 claims description 17
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 239000000243 solution Substances 0.000 claims description 13
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 8
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 239000000110 cooling liquid Substances 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 5
- 239000012670 alkaline solution Substances 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 239000007853 buffer solution Substances 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 4
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 4
- 235000017550 sodium carbonate Nutrition 0.000 claims description 3
- 238000003860 storage Methods 0.000 claims description 3
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 2
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 2
- 239000000872 buffer Substances 0.000 claims description 2
- 239000003638 chemical reducing agent Substances 0.000 claims description 2
- 239000003599 detergent Substances 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 239000001632 sodium acetate Substances 0.000 claims description 2
- 235000017281 sodium acetate Nutrition 0.000 claims description 2
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 claims description 2
- JVBXVOWTABLYPX-UHFFFAOYSA-L sodium dithionite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])=O JVBXVOWTABLYPX-UHFFFAOYSA-L 0.000 claims description 2
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims description 2
- 239000004289 sodium hydrogen sulphite Substances 0.000 claims description 2
- 229940001584 sodium metabisulfite Drugs 0.000 claims description 2
- 235000010262 sodium metabisulphite Nutrition 0.000 claims description 2
- 235000010265 sodium sulphite Nutrition 0.000 claims description 2
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 claims description 2
- 235000019345 sodium thiosulphate Nutrition 0.000 claims description 2
- 239000002351 wastewater Substances 0.000 abstract description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 9
- 230000000694 effects Effects 0.000 description 8
- -1 bis (2-ethyl) hexyl peroxydicarbonate Chemical compound 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 3
- 239000012934 organic peroxide initiator Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- NOBYOEQUFMGXBP-UHFFFAOYSA-N (4-tert-butylcyclohexyl) (4-tert-butylcyclohexyl)oxycarbonyloxy carbonate Chemical compound C1CC(C(C)(C)C)CCC1OC(=O)OOC(=O)OC1CCC(C(C)(C)C)CC1 NOBYOEQUFMGXBP-UHFFFAOYSA-N 0.000 description 2
- RPBWMJBZQXCSFW-UHFFFAOYSA-N 2-methylpropanoyl 2-methylpropaneperoxoate Chemical compound CC(C)C(=O)OOC(=O)C(C)C RPBWMJBZQXCSFW-UHFFFAOYSA-N 0.000 description 2
- 241000251468 Actinopterygii Species 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000011164 primary particle Substances 0.000 description 2
- BWJUFXUULUEGMA-UHFFFAOYSA-N propan-2-yl propan-2-yloxycarbonyloxy carbonate Chemical compound CC(C)OC(=O)OOC(=O)OC(C)C BWJUFXUULUEGMA-UHFFFAOYSA-N 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- OPQYOFWUFGEMRZ-UHFFFAOYSA-N tert-butyl 2,2-dimethylpropaneperoxoate Chemical compound CC(C)(C)OOC(=O)C(C)(C)C OPQYOFWUFGEMRZ-UHFFFAOYSA-N 0.000 description 2
- NMOALOSNPWTWRH-UHFFFAOYSA-N tert-butyl 7,7-dimethyloctaneperoxoate Chemical compound CC(C)(C)CCCCCC(=O)OOC(C)(C)C NMOALOSNPWTWRH-UHFFFAOYSA-N 0.000 description 2
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 2
- HGTUJZTUQFXBIH-UHFFFAOYSA-N (2,3-dimethyl-3-phenylbutan-2-yl)benzene Chemical group C=1C=CC=CC=1C(C)(C)C(C)(C)C1=CC=CC=C1 HGTUJZTUQFXBIH-UHFFFAOYSA-N 0.000 description 1
- YQTCQNIPQMJNTI-UHFFFAOYSA-N 2,2-dimethylpropan-1-one Chemical group CC(C)(C)[C]=O YQTCQNIPQMJNTI-UHFFFAOYSA-N 0.000 description 1
- AQKYLAIZOGOPAW-UHFFFAOYSA-N 2-methylbutan-2-yl 2,2-dimethylpropaneperoxoate Chemical compound CCC(C)(C)OOC(=O)C(C)(C)C AQKYLAIZOGOPAW-UHFFFAOYSA-N 0.000 description 1
- ZIDNXYVJSYJXPE-UHFFFAOYSA-N 2-methylbutan-2-yl 7,7-dimethyloctaneperoxoate Chemical compound CCC(C)(C)OOC(=O)CCCCCC(C)(C)C ZIDNXYVJSYJXPE-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- DTOJBTUWYBSXIZ-UHFFFAOYSA-N cumene;7,7-dimethyloctaneperoxoic acid Chemical compound CC(C)C1=CC=CC=C1.CC(C)(C)CCCCCC(=O)OO DTOJBTUWYBSXIZ-UHFFFAOYSA-N 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000003104 hexanoyl group Chemical group O=C([*])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C407/00—Preparation of peroxy compounds
- C07C407/003—Separation; Purification; Stabilisation; Use of additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F14/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
- C08F14/02—Monomers containing chlorine
- C08F14/04—Monomers containing two carbon atoms
- C08F14/06—Vinyl chloride
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/28—Oxygen or compounds releasing free oxygen
- C08F4/32—Organic compounds
- C08F4/34—Per-compounds with one peroxy-radical
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention discloses a continuous purification process of a peroxide initiator for vinyl chloride polymerization, and belongs to the technical field of initiators. The process comprises the following steps: (1) Centrifugally dewatering the reaction liquid to obtain an organic phase I for washing and a heavy phase I for wastewater treatment; (2) Adding a washing liquid I into the organic phase I for washing, and then, carrying out next washing on the obtained light phase II and carrying out wastewater treatment on the heavy phase II; (3) Adding a second washing liquid into the second light phase for washing, and then, carrying out next washing on the obtained third light phase, and carrying out wastewater treatment on the third heavy phase; (4) Adding a washing liquid III into the light phase III for washing, and then, further dehydrating the obtained light phase IV and treating the heavy phase IV with wastewater; (5) And after centrifugal dehydration of the light phase IV, storing the obtained light phase V, and treating the heavy phase V with wastewater. The whole purification process is continuously carried out, so that the purification process time is shortened; the obtained initiator stock solution has higher purity and can be used for preparing solvent-type initiator.
Description
Technical Field
The invention belongs to the technical field of initiators, and particularly relates to a continuous purification process of a peroxide initiator for vinyl chloride polymerization.
Background
The initiator is a compound which is easily decomposed into free radicals (i.e., primary free radicals) by heating, can be used for initiating the free radical polymerization of vinyl monomers, and is mainly divided into organic peroxides and azo initiators. At present, in the vinyl chloride polymerization process, an organic peroxide initiator is mainly used for initiating the polymerization reaction, and the common organic peroxide initiator is mainly dicumyl peroxyneodecanoate, bis (2-ethyl) hexyl peroxydicarbonate, bis (3, 5-trimethyl hexanoyl) peroxide, diisobutyryl peroxide, tert-butyl peroxyneodecanoate, 1, 3-tetramethylbutyl peroxyneodecanoate, pivaloyl peroxyneodecanoate, bis (4-tert-butylcyclohexyl) peroxydicarbonate, diisopropyl peroxydicarbonate, bis (2, 4-dichlorobenzoyl) pivaloyl peroxide, tert-butyl peroxypivaloate and the like, and the production process mainly comprises three steps of synthesis, purification and configuration.
At present, in the production process of an organic peroxide initiator for vinyl chloride polymerization, the synthesis and purification of the initiator are mainly finished in a reaction kettle, wherein the purification process mainly comprises the following steps: (1) standing the reaction solution after the reaction is finished, and separating water to remove a lower water phase, wherein the process is about 30min; (2) adding the washing liquid I into a reaction kettle, stirring for about 10min, standing for about 30-60 min, and removing the lower water phase; (3) adding the second washing liquid into a reaction kettle, stirring for 10min, standing for about 30-60 min, and removing the lower water phase; (4) adding the washing liquid III into a reaction kettle, stirring for 10min, standing for about 30-60 min, removing the lower water phase, and then introducing the upper organic phase into a stock solution storage tank. The whole purification process is batch operation, the time is 2.6-6 hours, if the solution is seriously emulsified in the process, the standing water diversion time is increased. And the initiator stock solution obtained after the final purification contains about 83% of initiator and about 17% of impurities, the main component is water, and the water contains part of unreacted cumene hydroperoxide and chloride ions, so that the effective content of the initiator is reduced due to the existence of the cumene hydroperoxide, and the use effect is reduced; the existence of chloride ions is unfavorable for a vinyl chloride polymerization system, and leads to exceeding indexes such as resin fish eyes, screen residues and the like in the polymerization process. Meanwhile, the lower initiator concentration in the stock solution can lead to the increase of the initiator dosage in the vinyl chloride polymerization process, thereby leading to the reduction of the average particle size, primary particles, oil absorption rate, molecular weight and heat stability time of the PVC resin; the lower initiator concentration in the stock solution is also detrimental to the preparation of solvent-borne initiators.
Therefore, there is a need to explore a continuous purification process for peroxide initiators for vinyl chloride polymerization that can provide high purity initiators, are inexpensive to produce, and are short-lived.
Disclosure of Invention
Aiming at the problems existing in the prior art, the invention provides a continuous purification process of a peroxide initiator for vinyl chloride polymerization. The whole purification process is continuously carried out, so that the purification process time is shortened; the initiator stock solution obtained by the purification process has low pseudo-activity content and high initiator activity; the purity of the initiator stock solution obtained by the purification process is up to 99.53 percent, and the initiator stock solution can be used for preparing solvent type initiator.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
a process for purifying a peroxide initiator, comprising the steps of:
(1) The reaction liquid is separated: centrifugally dewatering the reaction liquid to obtain an organic phase I for washing and a heavy phase I for wastewater treatment;
(2) Washing for the first time: adding a washing liquid I into the organic phase I for washing, and then, carrying out next washing on the obtained light phase II and carrying out wastewater treatment on the heavy phase II;
(3) And (3) washing for the second time: adding a second washing liquid into the second light phase for washing, and then, carrying out next washing on the obtained third light phase, and carrying out wastewater treatment on the third heavy phase;
(4) And (3) washing for the third time: adding a washing liquid III into the light phase III for washing, and then, further dehydrating the obtained light phase IV and treating the heavy phase IV with wastewater;
(5) Dehydrating: and after centrifugal dehydration of the light phase IV, storing the obtained light phase V, and treating the heavy phase V with wastewater.
Further, the peroxide initiator includes Cumene Peroxyneodecanoate (CPN), bis (2-ethyl) hexyl peroxydicarbonate, bis (3, 5-trimethylhexanoyl), diisobutyryl peroxide, t-butyl peroxyneodecanoate, 1, 3-tetramethylbutyl peroxyneodecanoate, t-amyl peroxyneodecanoate, bis (4-t-butylcyclohexyl) peroxydicarbonate, diisopropyl peroxydicarbonate, bis (2, 4-dichlorobenzoyl) t-amyl peroxypivalate, t-butyl peroxypivalate.
Further, in the step (1), the content of the peroxide initiator in the reaction solution is 30-70 wt%, the content of unreacted substances is 4-8 wt%, the content of salt generated by the reaction is 7-12 wt%, and the balance is water; wherein the unreacted substances are reactants containing active oxygen, including hydrogen peroxide, cumene hydroperoxide, tert-butyl hydroperoxide and the like, and the salts generated by the reaction include sodium chloride, potassium chloride and the like.
Further, cooling liquid is introduced outside the equipment in the washing processes in the steps (2) - (4), and the temperature of the cooling liquid is between-20 ℃ and 20 ℃.
Further, in the step (2), the first washing liquid is an alkaline solution, the concentration of the alkaline solution is 2.5-15 wt%, and the alkaline substance is one or more of sodium hydroxide, potassium hydroxide, sodium carbonate and potassium carbonate.
Further, the purpose of the first wash in step (2) is to remove unreacted peroxide feed.
Further, in the step (3), the second washing liquid is a reducing aqueous solution, the concentration of the reducing aqueous solution is 5-30wt%, and the reducing substance is one or more of sodium sulfite, sodium bisulphite, sodium metabisulfite, sodium hydrosulfite and sodium thiosulfate.
Further, the purpose of the second wash in step (3) is to remove peroxide feed remaining after the first wash.
Further, the third washing solution in the step (4) is a buffer solution, the concentration of the buffer solution is 2-7wt%, and the buffer is one or more of sodium bicarbonate, sodium carbonate and sodium acetate.
Further, the purpose of the third wash in step (4) is to adjust the pH of the initiator to a pH of 7 to 10 suitable for vinyl chloride polymerization systems, and the light phase IV.
Further, the mass flow ratio of the reaction liquid in the step (1) to the detergent in the steps (2) to (4) is 1-12:1.
In some specific embodiments, the purification process of the peroxide initiator comprises the steps of:
(1) The reaction liquid is separated: the reaction liquid enters a high-speed centrifuge I for dehydration, water and unreacted substances in the reaction liquid are removed, an organic phase I enters an extraction centrifuge A, and a heavy phase I carries out wastewater treatment;
(2) Washing for the first time: after the organic phase I and the washing liquid I from the high-speed centrifugal machine I enter the extraction centrifugal machine A for full washing, the light phase II enters the next-stage centrifugal machine for washing, and the heavy phase II carries out wastewater treatment;
(3) And (3) washing for the second time: after the light phase II and the washing liquid II from the extraction centrifuge A enter the extraction centrifuge B for full washing, the light phase III enters the next-stage centrifuge for washing, and the heavy phase III carries out wastewater treatment;
(4) And (3) washing for the third time: after the light phase III and the washing liquid III from the extraction centrifuge B enter the extraction centrifuge C for full washing, the light phase IV enters the high-speed centrifuge II, and the heavy phase IV carries out wastewater treatment;
(5) Dehydrating: the light phase IV from the extraction centrifuge C enters a high-speed centrifuge II for further dehydration, the light phase V enters a stock solution storage tank, and the heavy phase V is subjected to sewage treatment.
The high-speed centrifuges I and II are butterfly centrifuges, the main components of the high-speed centrifuges I and II are corrosion-resistant stainless steel 316L, and the motor is an explosion-proof motor; the extraction centrifuge A, B, C is characterized in that a jacket is arranged on the outer side of a cavity, cooling liquid can be introduced into the jacket, and the temperature of the cooling liquid in the cavity is-20 ℃. The main part of the extraction centrifuge A, B, C adopts corrosion-resistant stainless steel 316L, and the centrifuge motor is an explosion-proof motor.
Compared with the prior art, the invention has the following beneficial effects:
(1) The whole purification process is continuously carried out, the water diversion speed is rapid, and the purification process time is greatly shortened;
(2) In the three washing processes of the purification process, the washing liquid and the oil phase are mixed in the inner cavity of the extraction centrifuge through a rotary drum, the rotating speed of the rotary drum can reach 1500rpm/min at the highest, and the mixing effect is good, so that the washing effect is better;
(3) The initiator stock solution obtained by the purification process has low pseudo-activity content and high initiator activity, so that the initiator dosage in the vinyl chloride polymerization process can be reduced, and the cost is saved; meanwhile, the reduction of the average grain diameter, primary particles, oil absorption rate, molecular weight and heat stability time of the PVC resin caused by the increase of the initiator content can be reduced;
(4) The initiator stock solution obtained by the purification process has low chloride ion content, and can reduce the exceeding of indexes such as resin fish eyes, screen residues and the like caused by chloride ions in the vinyl chloride polymerization process;
(5) The purity of the initiator stock solution obtained by the purification process is up to 99.53 percent, and the initiator stock solution can be used for preparing solvent type initiator.
Drawings
FIG. 1 is a schematic diagram of a process for purifying peroxide initiators for vinyl chloride polymerization.
Detailed Description
It is to be noted that the raw materials used in the present invention are all common commercial products, and the sources thereof are not particularly limited.
Specific embodiments of examples 1-3 and comparative examples 1-6 are shown in Table 1, and FIG. 1 is a schematic diagram of the purification process.
TABLE 1
The results of the respective indices of the catalyst stock solutions obtained in examples 1 to 3 and comparative examples 1 to 6 are shown in Table 2.
TABLE 2
By comparison, it can be seen that:
examples 1, 2 and 3 all gave peroxide initiators of high purity, low peroxide residue and ultra low chloride ion, wherein the raw liquid purity was 99.53% in example 1, the peroxide residue was 0.15% and the chloride ion content was 14ppm. The 1t reaction solution was washed for 1h in the whole process. Comparative example 6 used a conventional washing process, and was far less pure than example 1 in 82.96%, 0.69% peroxide residue and 1210ppm chloride ion higher than example 1. The reaction mixture was washed 1t using conventional techniques for 5.5 hours, which is much higher than 1 hour of example 1.
In comparative example 1, the reaction solution after the completion of the reaction was directly fed into the centrifugal extractor A for the first washing step, and was not fed into the high-speed centrifuge I for water separation, and the water contained a large amount of unreacted peroxide and chloride ions, so that the peroxide residual amount was 0.35%, slightly higher than 0.15% in example 1, and the chloride ion content was 870ppm higher than 14ppm in example 1.
In comparative example 2, the first washing step of the step (2) was removed, and unreacted peroxide in the solution was not sufficiently removed, so that the residual amount of peroxide in the result was 1.58% and the chloride ion content was 159ppm higher than in example 1.
In comparative example 3, the second washing step of the step (3) was omitted, and the unreacted peroxide remained more in the solution, so that the residual peroxide amount of 7.35% was much higher than in example 1 and comparative example 1, and the chloride ion content was 168ppm higher than in example 1.
In comparative example 4, the third washing step of the step (4) was omitted, and the residual peroxide content in the stock solution was 0.58% and the chloride ion content was 163ppm higher than in example 1.
In comparative example 5, the dehydration step of step (5) was omitted, the centrifugal extractor had a weaker dehydration effect than the high-speed centrifuge, and the purity of the stock solution was lowered and the chloride ion content was increased as compared with example 1.
Finally, it should be noted that the above description is only for illustrating the technical solution of the present invention, and not for limiting the scope of the present invention, and that the simple modification and equivalent substitution of the technical solution of the present invention can be made by those skilled in the art without departing from the spirit and scope of the technical solution of the present invention.
Claims (5)
1. A process for purifying a peroxide initiator, comprising the steps of:
(1) The reaction liquid is separated: the reaction liquid enters a high-speed centrifuge I for dehydration, an organic phase I enters an extraction centrifuge A, and a heavy phase I carries out wastewater treatment;
(2) Washing for the first time: after the organic phase I and the washing liquid I from the high-speed centrifugal machine I enter the extraction centrifugal machine A for washing, the light phase II enters the next-stage centrifugal machine for washing, and the heavy phase II carries out wastewater treatment;
(3) And (3) washing for the second time: after the light phase II and the washing liquid II from the extraction centrifuge A enter the extraction centrifuge B for washing, the light phase III enters the next-stage centrifuge for washing, and the heavy phase III carries out wastewater treatment;
(4) And (3) washing for the third time: after the light phase III and the washing liquid III from the extraction centrifuge B enter the extraction centrifuge C for washing, the light phase IV enters the high-speed centrifuge II, and the heavy phase IV carries out wastewater treatment;
(5) Dehydrating: the light phase IV from the extraction centrifuge C enters a high-speed centrifuge II for further dehydration, the light phase V enters a stock solution storage tank, and the heavy phase V is subjected to wastewater treatment;
the washing liquid I in the step (2) is an alkaline solution, the concentration of the alkaline solution is 2.5-15 wt%, and the alkaline substance is one or more of sodium hydroxide, potassium hydroxide, sodium carbonate and potassium carbonate;
the second washing liquid in the step (3) is a reducing aqueous solution, the concentration of the reducing aqueous solution is 5-30wt%, and the reducing substance is one or more of sodium sulfite, sodium bisulphite, sodium metabisulfite, sodium hydrosulfite and sodium thiosulfate;
the third washing solution in the step (4) is a buffer solution, the concentration of the buffer solution is 2-7wt%, and the buffer is one or more of sodium bicarbonate, sodium carbonate and sodium acetate.
2. The purification process according to claim 1, wherein the peroxide initiator content in the reaction solution in step (1) is 30-70 wt%.
3. The purification process according to claim 1, wherein the washing processes in steps (2) to (4) are all carried out by introducing cooling liquid outside the equipment, and the temperature of the cooling liquid is-20 to 20 ℃.
4. The purification process according to claim 1, wherein the pH of the light phase four in step (4) is 7-10.
5. The purification process according to claim 1, wherein the mass flow ratio of the reaction liquid in step (1) to the detergent in steps (2) to (4) is 1 to 12:1.
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