CN109503654B - Method for separating catalyst in esterification reaction system - Google Patents
Method for separating catalyst in esterification reaction system Download PDFInfo
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- CN109503654B CN109503654B CN201811621879.6A CN201811621879A CN109503654B CN 109503654 B CN109503654 B CN 109503654B CN 201811621879 A CN201811621879 A CN 201811621879A CN 109503654 B CN109503654 B CN 109503654B
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- organic solvent
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- crown ether
- ester
- dichloropropyl
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- 239000003054 catalyst Substances 0.000 title claims abstract description 25
- 238000000034 method Methods 0.000 title claims abstract description 24
- 238000005886 esterification reaction Methods 0.000 title claims abstract description 10
- 150000002148 esters Chemical class 0.000 claims abstract description 23
- DHNUXDYAOVSGII-UHFFFAOYSA-N tris(1,3-dichloropropyl) phosphate Chemical compound ClCCC(Cl)OP(=O)(OC(Cl)CCCl)OC(Cl)CCCl DHNUXDYAOVSGII-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000003960 organic solvent Substances 0.000 claims abstract description 19
- 238000003756 stirring Methods 0.000 claims abstract description 16
- 238000005406 washing Methods 0.000 claims abstract description 16
- 238000001914 filtration Methods 0.000 claims abstract description 9
- 239000000243 solution Substances 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 239000003513 alkali Substances 0.000 claims abstract description 7
- 150000003608 titanium Chemical class 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 150000003983 crown ethers Chemical class 0.000 claims description 16
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 claims description 12
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 10
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 8
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- 238000011084 recovery Methods 0.000 claims description 6
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 4
- 239000002351 wastewater Substances 0.000 claims description 3
- XEPXTKKIWBPAEG-UHFFFAOYSA-N 1,1-dichloropropan-1-ol Chemical compound CCC(O)(Cl)Cl XEPXTKKIWBPAEG-UHFFFAOYSA-N 0.000 claims description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 2
- 150000003990 18-crown-6 derivatives Chemical group 0.000 claims 1
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 230000007062 hydrolysis Effects 0.000 abstract description 2
- 230000032050 esterification Effects 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 abstract 1
- 229910000348 titanium sulfate Inorganic materials 0.000 abstract 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 abstract 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 15
- 239000012071 phase Substances 0.000 description 12
- 239000007788 liquid Substances 0.000 description 10
- PHTQWCKDNZKARW-UHFFFAOYSA-N isoamylol Chemical compound CC(C)CCO PHTQWCKDNZKARW-UHFFFAOYSA-N 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- XEZNGIUYQVAUSS-UHFFFAOYSA-N 18-crown-6 Chemical group C1COCCOCCOCCOCCOCCO1 XEZNGIUYQVAUSS-UHFFFAOYSA-N 0.000 description 7
- 238000004821 distillation Methods 0.000 description 7
- 239000003063 flame retardant Substances 0.000 description 7
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 5
- 238000000354 decomposition reaction Methods 0.000 description 5
- -1 alkyl phosphate Chemical compound 0.000 description 4
- 239000012043 crude product Substances 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229910019142 PO4 Inorganic materials 0.000 description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 2
- 239000002841 Lewis acid Substances 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000007517 lewis acids Chemical class 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229920002994 synthetic fiber Polymers 0.000 description 2
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229920005830 Polyurethane Foam Polymers 0.000 description 1
- 229910003074 TiCl4 Inorganic materials 0.000 description 1
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium chloride Substances Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 235000011147 magnesium chloride Nutrition 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 150000002924 oxiranes Chemical class 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 239000011496 polyurethane foam Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- XHFLOLLMZOTPSM-UHFFFAOYSA-M sodium;hydrogen carbonate;hydrate Chemical compound [OH-].[Na+].OC(O)=O XHFLOLLMZOTPSM-UHFFFAOYSA-M 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 235000011150 stannous chloride Nutrition 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- ASLWPAWFJZFCKF-UHFFFAOYSA-N tris(1,3-dichloropropan-2-yl) phosphate Chemical compound ClCC(CCl)OP(=O)(OC(CCl)CCl)OC(CCl)CCl ASLWPAWFJZFCKF-UHFFFAOYSA-N 0.000 description 1
- JZZBTMVTLBHJHL-UHFFFAOYSA-N tris(2,3-dichloropropyl) phosphate Chemical compound ClCC(Cl)COP(=O)(OCC(Cl)CCl)OCC(Cl)CCl JZZBTMVTLBHJHL-UHFFFAOYSA-N 0.000 description 1
- 229920006305 unsaturated polyester Polymers 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 1
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
- C07F9/091—Esters of phosphoric acids with hydroxyalkyl compounds with further substituents on alkyl
Landscapes
- 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)
- Catalysts (AREA)
Abstract
The invention discloses a method for separating a catalyst in an esterification reaction system, which comprises the steps of adding an organic solvent into a crude ester product, fully stirring and uniformly mixing at room temperature, adjusting the pH of the system to 6.8-7.2 by using a dilute alkali solution to fully hydrolyze the catalyst in the system, filtering, standing and layering to obtain an ester-containing organic solvent clear solution, and distilling to remove the organic solvent to obtain a light yellow transparent product, wherein the esterification system is a crude ester system of tris (1, 3-dichloropropyl) phosphate; the catalyst is soluble titanium salt such as titanium sulfate or titanium chloride. According to the method, the organic solvent is added, so that the hydrolysis efficiency of the catalyst in the system is increased, and the washing yield of the product is improved; the method has the advantages of mild process conditions, simplicity, easy operation, safety, environmental protection, low cost and easy realization of industrial production.
Description
Technical Field
The invention belongs to the field of chemical separation and purification, and particularly relates to a separation method of a catalyst in an esterification reaction system, in particular to a separation treatment method of a catalyst in a system for preparing tris (1, 3-dichloropropyl) phosphate by catalyzing the reaction of dichloropropanol and phosphorus oxychloride with titanium salt.
Background
With the development of the synthetic material industry such as plastics, rubber and fiber, these materials are widely used in the fields of construction, transportation, electrical appliances, etc., and because of their inherent flammability, they have a high burning rate and are difficult to extinguish, and thus the potential fire hazard caused by these materials has become a global concern. The phosphorus flame retardant has become a hotspot for research and development of national flame retardant scientific research units in China in recent ten years. The phosphate flame retardant has the advantages of low smoke, no toxicity, good compatibility with materials, lasting flame retardant effect, water resistance, heat resistance, migration resistance and the like, so the phosphate flame retardant accords with the development direction of the flame retardant and has good development prospect.
The tris (1, 3-dichloropropyl) phosphate belongs to alkyl phosphate flame retardants, has excellent flame retardance and flame retardance plasticity, and is widely applied to unsaturated polyesters, hard and soft polyurethane foams, epoxy resins, phenolic resins, soft polyvinyl chloride and the like.
Common phosphoric acid tris (1, 3-dichloropropyl) esterThe synthesis methods include a phosphorus pentoxide method, a phosphoric acid method, a phosphorus trichloride method, a phosphorus oxychloride method and the like. The Stauffer chemical company in the United states and the Daba chemical company in Japan have been already produced, and in recent years, China has few scholars researching the synthesis of the tris (1, 3-dichloropropyl) phosphate, but the research on the post-treatment of the catalyst in the synthesis of crude ester is not mature enough, the catalyst is difficult to separate from the tris (1, 3-dichloro-2-propyl) phosphate, and the performance of the material is greatly influenced if the catalyst is brought into a synthetic material. Chinese patent with publication number CN107556338A describes the use of epichlorohydrin and phosphorus oxychloride as raw materials and TiCl4Preparing the phosphoric acid tri (1, 3-dichloropropyl) ester for the catalyst, and taking a distillation process and an activated carbon adsorption process as a post-treatment process of a crude product. Chinese patent with publication number CN102863468A introduces the use of epichlorohydrin and phosphorus oxychloride as raw materials and AlCl3Preparing a mixed solution of tris (1, 3-dichloropropyl) phosphate for a catalyst, adding alkali liquor to perform alkaline washing until the solution is neutral, standing for layering, and removing a water layer; washing the oil layer with water, standing for demixing again, removing the water layer, distilling the oil layer to obtain liquid tris (2, 3-dichloropropyl) phosphate, and introducing nitrogen gas for purification. Chinese patent with publication number CN102807581B, the method uses a catalyst to catalyze the ring-opening reaction of phosphorus oxychloride and epoxide to generate phosphoric acid triester, wherein the catalyst is ionic liquid [ A ] formed by Lewis acid (AlCl 3, FeCl3, MgCl2, ZnCl2, SnCl2 or TiCl 4) and amine and derivatives thereof, imidazole and derivatives thereof or pyridine and derivatives thereof]-x [ Lewis acid]. The above patents do not relate to the problem of post-treatment of the product, or simply mention, or have complicated steps, complicated operation and a large amount of waste water to aggravate the environmental protection problem.
Disclosure of Invention
In order to solve the technical problem, the invention provides a method for separating a catalyst in an esterification reaction system.
A method for separating a catalyst in an esterification reaction system comprises the following steps:
(1) at room temperature, adding an organic solvent into a crude ester product to be separated, and fully stirring and uniformly mixing;
(2) adding a dilute alkali water solution to adjust the pH of the system to 6.8-7.2, and then continuing stirring for 1-2 hours;
(3) filtering, standing for layering, taking an oil layer containing an ester organic solvent, and washing the oil layer for multiple times by using water;
(4) distilling to remove the organic solvent to obtain a light yellow transparent refined ester product.
Wherein, the esterification reaction system refers to a crude ester system of tris (1, 3-dichloropropyl) phosphate.
More preferably, the crown ether is added in step (1) in a volume ratio of 0.05 to 0.1:1 with respect to the organic solvent.
Wherein, the water-compatible low organic solvent can be any one of n-butanol, isobutanol, isoamyl alcohol, dichloromethane and dichloroethane.
Wherein, the catalyst is soluble titanium salt.
Wherein the mass ratio of the organic solvent to the crude ester in the step (1) is 1-4: 1.
Wherein, the dilute alkali aqueous solution in the step (2) can be 3-10% sodium carbonate, sodium bicarbonate or sodium hydroxide aqueous solution by mass percentage.
Wherein the crown ether is 18-crown-6.
After the crown ether is used, because the crown ether is toxic, in the step (3), the crown ether needs to be washed away by water for many times, and the wastewater containing the crown ether is recycled and can be reused.
According to the invention, an organic solvent with poor water solubility is added into an ester system, so that on one hand, the viscosity of an organic phase is reduced, titanium salt dissolved in the oil phase is contacted with an aqueous solution adjusted to be alkaline in the stirring process to be hydrolyzed, titanium oxide precipitate and sodium chloride which are salts insoluble in the oil phase are generated, and then the oil phase containing the ester is obtained by filtering, standing and layering, and the oil phase is distilled, so that the tris (1, 3-dichloropropyl) phosphate with high purity is obtained.
More, the crown ether can be added into an organic solvent, the crown ether is 18-crown-6, because the titanium salt is wrapped by the oil phase, even if the organic solvent is used for reducing the viscosity, the titanium salt cannot contact with the water phase across the interface, the next hydrolysis reaction is not facilitated, and the 18-crown-6 can not combine sodium ions in alkali liquor, can combine titanium ions in the oil phase, is better pulled out from the oil phase and contacts with the water phase for hydrolysis.
Advantageous effects
(1) The catalyst removal rate is high and reaches 90 percent;
(2) the method is simple and convenient to operate, simple in conditions, strong in operability and suitable for large-scale production and use;
(3) although the crown ether in the oil phase and the water phase is toxic, the final treatment uses closed distillation, the oil phase containing residual crown ether is recovered and can be recycled, and a large amount of water washing is used for reducing the concentration of the crown ether and reducing the toxicity to the minimum;
(4) the used reagent can be recycled, and the cost is greatly saved.
Detailed Description
The production method of the present invention will be further described with reference to examples, but the following description is only for the purpose of explaining the present invention and does not limit the contents thereof.
Example 1
(1) At room temperature, adding 200g of crude tris (1, 3-dichloropropyl) phosphate, 300g of isobutanol and 5g of 18-crown ether-6 into a beaker, starting stirring, and uniformly mixing;
(2) adding a sodium hydroxide aqueous solution with the mass percentage concentration of 5% to adjust the pH value of the system to 6.8-7.2, and stirring for reaction for about 1.5 hours;
(3) filtering to remove the decomposition product of the catalyst, standing the obtained liquid for layering to obtain an oil layer, namely an alcohol solution of the tris (1, 3-dichloropropyl) phosphate, and washing the oil layer for multiple times by deionized water and then distilling to obtain the refined ester.
172.30g of phosphoric acid tri (1, 3-dichloropropyl) ester with light yellow and transparent appearance is obtained after distillation, and the washing rate (the mass ratio of the refined ester to the crude ester) is 89.15 percent; 271.41g of isobutanol was recovered, and the recovery rate of isobutanol was 90.47%. The waste liquid containing 18-crown ether-6 separated from the water-washed oil layer is recycled after simple treatment.
Example 2
(1) Under the condition of room temperature, adding 200g of a tris (1, 3-dichloropropyl) phosphate crude product and 400g of isoamyl alcohol into a beaker, starting stirring, and uniformly mixing;
(2) adding a sodium carbonate aqueous solution with the mass percentage concentration of 8% to adjust the pH value of the system to 6.8-7.2, and stirring for reaction for about 2 hours;
(3) filtering to remove the decomposition product of the catalyst, standing the obtained liquid for layering to obtain an oil layer, namely an alcohol solution of the tris (1, 3-dichloropropyl) phosphate, and washing the oil layer for multiple times by deionized water and then distilling to obtain the refined ester.
170.78g of phosphoric acid tri (1, 3-dichloropropyl) ester with light yellow and transparent appearance is obtained after distillation, and the washing rate is 80.39%; 364.84g of isoamyl alcohol is recovered, and the recovery rate of the isoamyl alcohol is 90.21%.
Example 3
(1) Under the condition of room temperature, adding 200g of a tris (1, 3-dichloropropyl) phosphate crude product and 300g of n-butanol into a beaker, starting stirring, and uniformly mixing;
(2) adding a sodium carbonate aqueous solution with the mass percentage concentration of 8%, adjusting the pH value of the system to 6.8-7.2, and stirring for reacting for about 2 hours;
(3) filtering to remove catalyst decomposition product, standing the obtained liquid for layering to obtain oil layer as n-butanol-containing tris (1, 3-dichloropropyl) phosphate liquid, washing the oil layer with deionized water for multiple times, and distilling to obtain refined ester.
173.89g of phosphoric acid tri (1, 3-dichloropropyl) ester with light yellow and transparent appearance is obtained after distillation, and the washing rate is 81.94%; 270.32g of n-butanol was recovered, and the recovery rate of n-butanol was 90.11%.
Example 4
(1) Under the condition of room temperature, adding 200g of a crude product of tris (1, 3-dichloropropyl) phosphate, 600g of dichloroethane and 10g of 18-crown ether-6 into a beaker, starting stirring and uniformly mixing;
(2) adding a sodium bicarbonate water solution with the mass percentage concentration of 8%, adjusting the pH value of the system to 6.8-7.2, and stirring for reacting for about 1 hour;
(3) filtering to remove decomposition products of the catalyst, standing and layering the obtained liquid to obtain an oil layer, namely tris (1, 3-dichloropropyl) phosphate liquid containing a dichloroethane solvent, washing the oil layer with deionized water for multiple times, and distilling to obtain refined ester;
180.24g of phosphoric acid tri (1, 3-dichloropropyl) ester with light yellow and transparent appearance is obtained after distillation, and the washing rate is 90.12%; 535.58g of dichloroethane were recovered, and the recovery rate of dichloroethane was 89.26%. The waste liquid containing 18-crown ether-6 separated from the water-washed oil layer is recycled after subsequent treatment.
Comparative example
(1) Under the condition of room temperature, adding 100g of ethanol into 200g of crude ester to reduce the viscosity of the system, adjusting the pH value of the system to 6.8-7.2 by using a sodium hydroxide aqueous solution with the mass percent concentration of 8% under the stirring condition, reacting for 2 hours, and then removing water and alcohol in the system by vacuum evaporation;
(2) adding 400g of benzene into a beaker, starting stirring, and uniformly mixing;
(3) filtering to remove the decomposition product of the catalyst to obtain an oil layer, namely tris (1, 3-dichloropropyl) phosphate liquid containing a benzene solvent, and distilling to remove benzene to obtain refined ester.
170.54g of tris (1, 3-dichloropropyl) phosphate with turbid appearance is obtained after distillation, and the washing rate is 73.27%; 174.96g of benzene were recovered, and the recovery rate of benzene was 87.48%.
Claims (6)
1. A method for separating a catalyst in an esterification reaction system is characterized by comprising the following steps:
(1) adding crown ether and an organic solvent into a crude ester product to be separated at room temperature, and fully stirring and uniformly mixing; the volume ratio of the crown ether to the organic solvent is 0.05-0.1: 1;
(2) adding a dilute alkali water solution to adjust the pH of the system to 6.8-7.2, and then continuing stirring for 1-2 hours;
(3) filtering, standing for layering, taking an oil layer containing an ester organic solvent, and washing the oil layer for multiple times by using water;
(4) distilling to remove the organic solvent to obtain a light yellow transparent refined ester product;
the esterification reaction system is a system for preparing the tris (1, 3-dichloropropyl) phosphate by using soluble titanium salt to catalyze the reaction of dichloropropanol and phosphorus oxychloride.
2. The method of claim 1, wherein the organic solvent is any one of n-butanol, iso-butanol, dichloromethane and dichloroethane.
3. The method according to claim 1, wherein the mass ratio of the organic solvent to the crude ester in step (1) is 1-4: 1.
4. The method according to claim 1, wherein the dilute aqueous alkali solution in step (2) is an aqueous solution of sodium carbonate, sodium bicarbonate or sodium hydroxide with a concentration of 3-10% by mass.
5. The method of claim 1, wherein said crown ether is 18-crown-6.
6. The method according to claim 1, wherein in the step (3), the crown ether is removed by washing with water for a plurality of times, and the wastewater containing the crown ether is subjected to a recovery treatment and is reused.
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| CN102863468A (en) * | 2011-07-06 | 2013-01-09 | 盐城市大明化工有限公司 | Preparation technology of tris(2,3-dichloropropyl) phosphate |
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