WO2023236938A1 - 磷酸三(丁氧基乙基)酯生产过程中的副产物2-丁氧基氯乙烷的分离提纯工艺 - Google Patents
磷酸三(丁氧基乙基)酯生产过程中的副产物2-丁氧基氯乙烷的分离提纯工艺 Download PDFInfo
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- WO2023236938A1 WO2023236938A1 PCT/CN2023/098549 CN2023098549W WO2023236938A1 WO 2023236938 A1 WO2023236938 A1 WO 2023236938A1 CN 2023098549 W CN2023098549 W CN 2023098549W WO 2023236938 A1 WO2023236938 A1 WO 2023236938A1
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- WIPO (PCT)
- Prior art keywords
- butoxyethyl
- ethylene glycol
- glycol monobutyl
- monobutyl ether
- chloride
- Prior art date
Links
- OJMVRGXLTANFRG-UHFFFAOYSA-N 1-(2-chloroethoxy)butane Chemical compound CCCCOCCCl OJMVRGXLTANFRG-UHFFFAOYSA-N 0.000 title claims abstract description 62
- WTLBZVNBAKMVDP-UHFFFAOYSA-N tris(2-butoxyethyl) phosphate Chemical compound CCCCOCCOP(=O)(OCCOCCCC)OCCOCCCC WTLBZVNBAKMVDP-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 238000000034 method Methods 0.000 title claims abstract description 33
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 13
- 239000006227 byproduct Substances 0.000 title claims abstract description 8
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 claims abstract description 92
- 238000005406 washing Methods 0.000 claims abstract description 71
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 claims abstract description 67
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 60
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 48
- 239000003513 alkali Substances 0.000 claims abstract description 42
- 238000004821 distillation Methods 0.000 claims abstract description 34
- 239000000463 material Substances 0.000 claims abstract description 32
- 239000000047 product Substances 0.000 claims abstract description 28
- 239000002351 wastewater Substances 0.000 claims abstract description 22
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims abstract description 19
- 238000003756 stirring Methods 0.000 claims abstract description 17
- 235000011121 sodium hydroxide Nutrition 0.000 claims abstract description 16
- 239000007788 liquid Substances 0.000 claims abstract description 14
- 239000002585 base Substances 0.000 claims abstract description 10
- 239000000203 mixture Substances 0.000 claims abstract description 3
- 238000000926 separation method Methods 0.000 claims description 18
- -1 2-butoxyethane chloride Chemical compound 0.000 claims description 17
- 238000005292 vacuum distillation Methods 0.000 claims description 14
- 238000000746 purification Methods 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 3
- TVAJJUOMNRUGQA-UHFFFAOYSA-N 2-butoxyethyl dihydrogen phosphate Chemical compound CCCCOCCOP(O)(O)=O TVAJJUOMNRUGQA-UHFFFAOYSA-N 0.000 claims description 2
- 238000004090 dissolution Methods 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- 238000009413 insulation Methods 0.000 abstract description 3
- 238000010438 heat treatment Methods 0.000 abstract description 2
- 238000007599 discharging Methods 0.000 abstract 2
- RNXHHJQBVBRJMB-UHFFFAOYSA-N 1-dichlorophosphoryloxybutane Chemical compound CCCCOP(Cl)(Cl)=O RNXHHJQBVBRJMB-UHFFFAOYSA-N 0.000 abstract 1
- 238000001816 cooling Methods 0.000 abstract 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 22
- 229910052698 phosphorus Inorganic materials 0.000 description 22
- 239000011574 phosphorus Substances 0.000 description 22
- 238000004817 gas chromatography Methods 0.000 description 21
- 238000001514 detection method Methods 0.000 description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical group Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 13
- 238000002474 experimental method Methods 0.000 description 13
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 13
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 13
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 10
- 239000012043 crude product Substances 0.000 description 9
- 239000012535 impurity Substances 0.000 description 7
- 238000002798 spectrophotometry method Methods 0.000 description 7
- 239000007789 gas Substances 0.000 description 5
- 238000004064 recycling Methods 0.000 description 5
- 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 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 101150042817 NFS1 gene Proteins 0.000 description 4
- 101100126298 Rickettsia conorii (strain ATCC VR-613 / Malish 7) iscS gene Proteins 0.000 description 4
- 101150114492 SPL1 gene Proteins 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 238000005886 esterification reaction Methods 0.000 description 4
- 239000003063 flame retardant Substances 0.000 description 4
- 238000013517 stratification Methods 0.000 description 4
- 238000004065 wastewater treatment Methods 0.000 description 4
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 238000010812 external standard method Methods 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000004480 active ingredient Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 238000012805 post-processing Methods 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 238000010926 purge Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 239000001488 sodium phosphate Substances 0.000 description 2
- 229910000162 sodium phosphate Inorganic materials 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- PZHIWRCQKBBTOW-UHFFFAOYSA-N 1-ethoxybutane Chemical compound CCCCOCC PZHIWRCQKBBTOW-UHFFFAOYSA-N 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- CLBRCZAHAHECKY-UHFFFAOYSA-N [Co].[Pt] Chemical compound [Co].[Pt] CLBRCZAHAHECKY-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000011609 ammonium molybdate Substances 0.000 description 1
- 235000018660 ammonium molybdate Nutrition 0.000 description 1
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 1
- 229940010552 ammonium molybdate Drugs 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 125000006226 butoxyethyl group Chemical group 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- HRYZWHHZPQKTII-UHFFFAOYSA-N chloroethane Chemical compound CCCl HRYZWHHZPQKTII-UHFFFAOYSA-N 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- RCJVRSBWZCNNQT-UHFFFAOYSA-N dichloridooxygen Chemical group ClOCl RCJVRSBWZCNNQT-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 229960003750 ethyl chloride Drugs 0.000 description 1
- 238000013332 literature search Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000010606 normalization Methods 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000008031 plastic plasticizer Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920003225 polyurethane elastomer Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000010421 standard material Substances 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/34—Separation; Purification; Stabilisation; Use of additives
- C07C41/44—Separation; Purification; Stabilisation; Use of additives by treatments giving rise to a chemical modification
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/34—Separation; Purification; Stabilisation; Use of additives
- C07C41/38—Separation; Purification; Stabilisation; Use of additives by liquid-liquid treatment
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/34—Separation; Purification; Stabilisation; Use of additives
- C07C41/40—Separation; Purification; Stabilisation; Use of additives by change of physical state, e.g. by crystallisation
- C07C41/42—Separation; Purification; Stabilisation; Use of additives by change of physical state, e.g. by crystallisation by distillation
-
- 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
Definitions
- step 2) Perform vacuum distillation on the material in step 1) to separate the crude 2-butoxyethane chloride and the bottom solution;
- step 2) Add liquid caustic soda and water to the crude 2-butoxyethyl chloride in step 2), stir and wash with alkali, then leave to separate the discharge layer and the alkali wash wastewater layer, add water to the separated discharge layer After stirring and washing, let it stand to separate the finished product of 2-butoxyethyl chloride and the washing wastewater;
- step 4) Add titanium tetrachloride to excess pure ethylene glycol monobutyl ether, then control the temperature to 10-15°C, and dropwise add the base solution in step 2). After the dropwise addition is completed, keep the temperature for 1.5h and raise the temperature in stages. reaction, and then distilled under reduced pressure to remove ethylene glycol monobutyl ether to obtain crude tris(butoxyethyl)phosphate, and then undergo alkali washing, water washing, distillation, and filtration to obtain the finished product tris(butoxyethyl)phosphate.
- the mass ratio of the total mass of ethylene glycol monobutyl ether to phosphorus oxychloride in the recovery of ethylene glycol monobutyl ether in step 1) is 1.3-1.6:1, and the addition amount of titanium tetrachloride is oxychloride.
- the mass ratio of phosphorus added is 0.2-0.4%.
- the proportion of unreacted phosphorus oxychloride in the total amount of phosphorus oxychloride added is too small, which will lead to an increase in the content of ethylene glycol monobutyl ether in the vacuum distillation fraction, and finally butoxy
- the residual amount of ethylene glycol monobutyl ether in the finished product after washing with ethylene chloride is too large, and the purity of the finished product is unqualified; when the proportion of unreacted phosphorus oxychloride in the total amount of phosphorus oxychloride added is too large, the loss of phosphorus oxychloride will result If it is too large, it will be hydrolyzed into sodium phosphate and sodium chloride during washing of the crude product, causing unnecessary waste.
- step 2) vacuum distillation is 60-80°C.
- the mass ratio of the added amounts of pure ethylene glycol monobutyl ether and titanium tetrachloride described in step 4) is 800-1000:3.
- step 4 the process of the staged temperature-raising reaction in step 4) is to raise the temperature to 30-35°C and keep it for 0.5h, then continue to raise the temperature to 75-80°C and keep it for 0.5h, and the vacuum distillation temperature is 160-170°C.
- step 4 the specific process of alkali washing, water washing, distillation and filtration in step 4) is to add water and liquid alkali for alkali washing, stir to separate the alkali washing material layer, add water for water washing, let it stand after the water washing is completed, and the upper material layer is Distill under reduced pressure, control the temperature at 105-110°C, and filter the lower material layer.
- alkali washing wastewater and water washing wastewater in step 3) and the water washing wastewater in step 4) are used back to the washing process of the crude tris(butoxyethyl)phosphate.
- the separation and preparation process is carried out under vacuum conditions, and the vacuum degree is -0.094 to -0.096Mpa.
- the beneficial effects of the present invention are:
- Phosphorus oxychloride purity 99.5%
- Titanium tetrachloride purity 99.5%.
- the vacuum degree is -0.094Mpa. Raise the system temperature to 75°C to distill off the 2-butoxyethyl chloride component until no fraction is evaporated. End the distillation to obtain 2 -Crude butoxyethane chloride A2 weighed 35.56g, and the remaining base material B1 weighed 150.53g. A2 sampling was detected using gas chromatography: the purity of 2-butoxyethyl chloride was 92.79%, and ethylene glycol monobutyl was detected. The ether residue is 6.28%, and the remaining substances are 0.93% (phosphorus oxychloride, hydrogen chloride).
- B2 raises the temperature to 160°C under a vacuum of -0.094 to -0.096Mpa to recover ethylene glycol monobutyl ether under reduced pressure until no more ethylene glycol monobutyl ether is distilled.
- the residual amount of ether is 2.44%, which is qualified.
- the distillation is completed, 265.37g of crude phosphate flame retardant TBEP is obtained, and 109.5g of ethylene glycol monobutyl ether is recovered;
- TBEP content is detected by gas chromatography to be 98.52% (industry standard: >98.00%), and moisture is measured by Karl Fischer. 0.05% (industry standard: ⁇ 0.2%), acid value 0.03KOHmg/g (industry standard: ⁇ 0.1KOHmg/g), color number 45 (industry standard: ⁇ 60).
- Example 2 only proceeds to step (4). The difference is:
- step (1) the addition amount of phosphorus oxychloride is changed to 105.06g, and the addition amount of titanium tetrachloride is changed to 0.315g.
- the crude product A2 of 2-butoxyethyl chloride distilled out in step (3) weighed 33.81 grams.
- Gas chromatography detected the purity of 2-butoxyethyl chloride was 97.61%, and the residual ethylene glycol monobutyl ether was 1.1%.
- Other components phosphorus oxychloride, hydrogen chloride) 1.29%.
- the distillation bottom material B1 weighed 159.1g.
- step (4) 14.49g of water and 2.42g of sodium hydroxide aqueous solution with a mass concentration of 30% were added to A2 for alkaline washing, and 16.9g of water was added for water washing.
- the 2-butoxyethane chloride content was measured by gas chromatography to be 99.29 %, ethylene glycol monobutyl ether 0.56%, using the Karl Fischer method to measure the water content of 0.15%, and obtained 33.24g of 2-butoxyethyl chloride finished product.
- the separated lower alkali washing wastewater was tested for total phosphorus to determine the actual content of phosphorus oxychloride in A2. The total phosphorus was measured using spectrophotometry to be 1246 mg/kg.
- step (5) the added amount of ethylene glycol monobutyl ether was changed to 289g, the added amount of titanium tetrachloride was changed to 0.867g, and a total of 159.1g of B1 was added.
- Step (7) distillation recovers 118.95g of ethylene glycol monobutyl ether and 282.17g of crude TBEP.
- Step (8) Add 94.06g of alkali washing water, 8.27g of liquid caustic soda, and 90.93g of water washing to obtain 277g of TBEP finished product.
- the TBEP gas chromatography content in the finished product is 98.52%, and the ethylene glycol monobutyl ether content is 1.48%. Acid value 0.03, moisture 0.053%, color number 45.
- step (1) the addition amount of phosphorus oxychloride is changed to 108.43g, and the addition amount of titanium tetrachloride is changed to 0.325g.
- the crude product A2 of 2-butoxyethyl chloride distilled out in step (3) weighed 34.03 grams.
- the distillation bottom material B1 weighed 160.4g.
- step (4) 12.45g of water and 4.56g of liquid caustic soda with a mass concentration of 30% were added to A2 for alkaline washing. 17.02g of water was added for water washing. After A2 was washed, the 2-butoxyethane chloride content was measured by gas chromatography to be 99.57%. Ethylene glycol monobutyl ether 0.28%, water content measured using Karl Fischer method is 0.15%. 33.14g of 2-butoxyethyl chloride finished product was obtained. The separated lower alkali washing wastewater was tested for total phosphorus to determine the actual content of phosphorus oxychloride in A2. The total phosphorus was measured using spectrophotometry to be 5963 mg/kg.
- the crude product A2 of 2-butoxyethyl chloride distilled out in step (3) weighed 34.02 grams. After gas chromatography detection, the purity of 2-butoxyethyl chloride in A2 was 97%, and no ethylene glycol monobutyl was detected. Ether, other impurities 3% (phosphorus oxychloride, hydrogen chloride).
- the distillation bottom material B1 weighs 162g.
- step (4) 11.54g of water and 5.47g of liquid caustic soda with a mass concentration of 30% were added to A2 for alkaline washing, and 17.01g of water was added for water washing.
- the 2-butoxyethane chloride content was measured by gas chromatography to be 99.85%.
- the water content was measured to be 0.15% using the Karl Fischer method, and 33.05g of the finished product 2-butoxyethyl chloride was obtained.
- the separated lower alkali washing wastewater was tested for total phosphorus to determine the actual content of phosphorus oxychloride in A2.
- the total phosphorus was measured using spectrophotometry to 7902 mg/kg.
- step (1) the addition amount of phosphorus oxychloride is changed to 113.78g, and the addition amount of titanium tetrachloride is changed to 0.34g.
- the crude product A2 of 2-butoxyethyl chloride distilled out in step (3) weighed 34.02 grams. After gas chromatography detection, the purity of 2-butoxyethyl chloride in A2 was 96.5%. Other impurities (phosphorus oxychloride, Hydrogen chloride) 3.5%, the distillation bottom material B1 weighed 165.41g.
- Example 1 The experiment only proceeds to step (4) to complete the alkali washing and stratification. The difference is: the vacuum distillation temperature of A1 is changed to 60°C, 24 grams of fractions are collected, and 2 in A2 after gas chromatography detection -The purity of butoxyethyl chloride is 90.69%, ethylene glycol monobutyl ether is 9.3%, other impurities (phosphorus oxychloride, hydrogen chloride) are 0.012%, and the distillation bottom material B1 weighs 164.3g. A2 was subjected to alkali washing, and the total phosphorus measured in the alkali washing water layer was 30 mg/kg.
- Example 1 The experiment only proceeds to step (4) to complete alkali washing and stratification. The difference is: the vacuum distillation temperature of A1 is changed to 65°C. It is found that 29 grams of fractions are collected. After gas chromatography detection, A2 The purity of 2-butoxyethyl chloride is 92.3%, ethylene glycol monobutyl ether is 7.69%, other impurities (phosphorus oxychloride, hydrogen chloride) are 0.01%, and the distillation bottom material B1 weighs 159.3g. A2 was subjected to alkali washing, and the total phosphorus measured in the alkali washing water layer was 32mg/kg.
- Example 1 Other processes are consistent with Example 1. The experiment only proceeds to step (4) to complete alkali washing and stratification. The difference is: the vacuum distillation temperature of A1 is changed to 70°C. It is found that 31 grams of fractions are collected. After gas chromatography detection, A2 The purity of 2-butoxyethyl chloride is 92.79%, ethylene glycol monobutyl ether is 7.2%, other impurities (phosphorus oxychloride, hydrogen chloride) are 0.01%, and the distillation bottom material B1 weighs 157.3g. A2 was subjected to alkali washing, and the total phosphorus measured in the alkali washing water layer was 33mg/kg.
- Example 1 Other processes are consistent with Example 1. The experiment only proceeds to step (4) to complete alkali washing and stratification. The difference is: the vacuum distillation temperature of A1 is changed to 80°C. It is found that 35 grams of fractions are collected. After gas chromatography detection, A2 The purity of 2-butoxyethyl chloride is 91.67%, ethylene glycol monobutyl ether is 6.2%, other impurities (phosphorus oxychloride, hydrogen chloride) are 2.136%, and the distillation bottom material B1 weighs 152.3g. A2 was subjected to alkali washing, and the total phosphorus measured in the alkali washing water layer was 8304mg/kg.
- Acid value detection in step (8) Petroleum product acid value detection method, GB264-83;
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Abstract
本发明公开了一种磷酸三(丁氧基乙基)酯生产过程中的副产物2-丁氧基氯乙烷的分离提纯工艺,包括如下步骤:在含2-丁氧基氯乙烷浓度≥30%的回收乙二醇单丁醚中加入四氯化钛,溶解彻底后,降温,然后滴加过量的三氯氧磷,滴加完成后保温一段时间,继续升温,将物料中的乙二醇单丁醚彻底反应成丁氧基磷酸二酰氯,减压蒸馏,分离出2-丁氧基氯乙烷粗品和底料,底料用于制备TBEP,2-丁氧基氯乙烷粗品中加入液碱和水,搅拌碱洗洗涤,而后静置分离出出料层和碱洗废水层,分出的出料层加水搅拌洗涤后静置,分出2-丁氧基氯乙烷成品和水洗废水。本发明紧密结合磷酸三(丁氧基乙基)酯生产工艺,利用现有设备,生产间歇集中处理回收乙二醇单丁醚。
Description
本发明属于分离提纯技术领域,具体涉及一种磷酸三(丁氧基乙基)酯生产过程中的副产物2-丁氧基氯乙烷的分离提纯工艺。
磷酸三(丁氧基乙基)酯(TBEP)主要用于塑料增塑剂、塑料溶剂及阻燃聚氨酯橡胶、纤维素、聚乙烯醇等的阻燃和增塑,具有良好的低温特点。
磷酸三(丁氧基乙基)酯工业化生产工艺,通常使用过量的乙二醇单丁醚在四氯化钛催化下与三氯氧磷反应生成磷酸三(丁氧基乙基)酯,副产物氯化氢,反应过程中伴随乙二醇单丁醚与氯化氢反应生产2-丁氧基氯乙烷和水的副反应,反应方程式如下:
HCL+HOC2H4OC4H9→CH3CH2CH2CH2OCH2CH2CL+H2O
过量的乙二醇单丁醚通过减压蒸馏回收并套用到下一批磷酸三(丁氧基乙基)酯反应过程中,2-丁氧基氯乙烷会与乙二醇单丁醚被蒸出,由于2-丁氧基氯乙烷不与三氯氧磷反应,因此2-丁氧基氯乙烷浓度会随着乙二醇单丁醚的不断回收套用而增加,当回收乙二醇单丁醚中2-丁氧基氯乙烷的浓度增大到30%以上时,会导致磷酸三(丁氧基乙基)酯酯化反应无法反应到终点,必须全部替换成纯乙二醇单丁醚确保反应正常进行,由于生产装置设计时未考虑过2-丁氧基氯乙烷的处理问题,同时其中含有氯化氢呈酸性,因此报废的回收乙二醇单丁醚作为废水处理合格后排放。
报废的回收乙二醇单丁醚经过实验室验证,无法通过加氢氧化钠水溶液将2-丁氧基氯乙烷重新反应成乙二醇单丁醚,因此只能考虑将2-丁氧基氯乙烷与乙二醇单丁醚分离才能进行回收利用。
通过检索与磷酸三(丁氧基乙基)酯酯化反应相关的文献和专利后,发现没有副产物2-丁氧基氯乙烷进行回收再利用或如何分离提纯的相关报道。
2-丁氧基氯乙烷,沸点50℃,闪点46℃,通过文献检索,发现国内外2-丁氧基氯乙烷相关合成工艺的专利和文献报道较少,能查到得有以下工艺路线:①DE537696;Fortschr.Teerfarbenfabr.Verw.Industriezweige,vol.18,p.158
②Harrison,Charles R.;Hodge,Philip;Hunt,Barry J.;Khoshdel,Ezzatollah;Richardson,Graham Journal of Organic Chemistry,1983,vol.48,#21p.3721–3728
③美国1956年专利:US2768174
以上三种工艺路线中,第二种使用乙二醇单丁醚与氯化物进行反应工艺与磷酸三(丁氧基乙基)酯的合成过程中副反应相近,但其分离出纯度较高的2-丁氧基氯乙烷通常采用精馏法直接获取,与结合磷酸三(丁氧基乙基)酯生产工艺进行分离的工艺路线显著不同。
2-丁氧基氯乙烷现有工业化生产方式中,几乎都会通过精馏分离出高纯度2-丁氧基氯乙烷,而此种方法也适用上述报废回收乙二醇单丁醚中分离出2-丁氧基氯乙烷和乙二醇单丁醚,从而能废物利用。但使用精馏方式分离2-丁氧基氯乙烷,需要专门的精馏装置投资较大,设备闲置时间较多,精馏能耗大,控制复杂,综合考虑并不太合适现有的磷酸三(丁氧基乙基)酯生产线进行对应改造后使用。
发明内容
为解决副产物2-丁氧基氯乙烷的回收问题,本发明的目的在于提供一种磷酸三(丁氧基乙基)酯生产过程中的副产物2-丁氧基氯乙烷的分离提纯工艺。
为达到上述目的,提出以下技术方案:
一种磷酸三(丁氧基乙基)酯生产过程中的副产物2-丁氧基氯乙烷的分离提纯工艺,包括如下步骤:
1)在含2-丁氧基氯乙烷浓度≥30%的回收乙二醇单丁醚中加入四氯化钛,溶解彻底后,将混合物料降温到10-15℃,然后滴加过量的三氯氧磷,滴加完成后保温1-2h,继续升温至50-55℃,将物料中的乙二醇单丁醚彻底反应成丁氧基乙基磷酸酯二酰氯,通过过量三氯氧磷将回收乙二醇单丁醚中的乙二醇单丁醚成分彻底反应生成高沸点的丁氧基乙基磷酸酯二酰氯,然后采用简单的减压蒸馏分离2-丁氧基氯乙烷,而避免采用精馏分离2-丁氧基氯乙烷和乙二醇单丁醚,且蒸馏产物纯度较高;
2)对步骤1)的物料进行减压蒸馏,分离出2-丁氧基氯乙烷粗品和底料溶液;
3)向步骤2)中的2-丁氧基氯乙烷粗品中加入液碱和水,搅拌碱洗洗涤,而后静置分离出出料层和碱洗废水层,分出的出料层加水搅拌洗涤后静置,分出2-丁氧基氯乙烷成品和水洗废水;
4)过量的纯乙二醇单丁醚中加入四氯化钛,而后控制温度为10-15℃,滴加步骤2)中的底料溶液,滴加完成后,保温1.5h,阶段式升温反应,而后减压蒸馏脱出乙二醇单丁醚,获得磷酸三(丁氧基乙基)酯粗品,而后经过碱洗、水洗、蒸馏、过滤获得磷酸三(丁氧基乙基)酯成品。
进一步地,步骤1)中回收乙二醇单丁醚中乙二醇单丁醚的总质量与三氯氧磷的质量比为1.3-1.6:1,四氯化钛的加入量为三氯氧磷加入量的质量比为0.2-0.4%,未反应的三氯氧磷占加入三氯氧磷总量比例太小时,会导致减压蒸馏馏分中乙二醇单丁醚含量增加,最后丁氧基氯乙烷洗涤后成品中乙二醇单丁醚残留量过大,成品纯度不合格;未反应的三氯氧磷占加入三氯氧磷总量比例过大时,导致三氯氧磷损耗过大,在粗品洗涤时水解反应成磷酸钠和氯化钠,造成不必要的浪费。
进一步地,步骤2)减压蒸馏的温度为60-80℃。
进一步地,步骤3)中的液碱为氢氧化钠溶液,加入液碱和水后,在25-35℃下,搅拌20-30min,控制pH=9-10;出料层搅拌15-30min,控制pH=7。
进一步地,步骤4)中所述的纯乙二醇单丁醚与四氯化钛的加入量的质量比为800-1000:3。
进一步地,步骤4)中的阶段式升温反应的过程为升温至30-35℃保温0.5h,再继续升温至75-80℃保温0.5h,减压蒸馏温度为160-170℃。
进一步地,步骤4)的碱洗、水洗、蒸馏、过滤具体过程为加入水和液碱进行碱洗,搅拌分出碱洗料层,加入水进行水洗,水洗完成后静置,上层料层进行减压蒸馏,温度控制在105-110℃,下层料层进行过滤。
进一步地,步骤3)中的碱洗废水和水洗废水以及步骤4)中的水洗废水套用回磷酸三(丁氧基乙基)酯粗品的洗涤环节。
进一步地,分离制备过程在真空条件下进行,真空度为-0.094到-0.096Mpa。本发明的有益效果在于:
1)紧密结合磷酸三(丁氧基乙基)酯生产工艺,利用现有设备,不增加新设备,在磷酸三(丁氧基乙基)酯生产间歇时,集中处理报废的过量乙二醇单丁醚,将其中的乙二醇单丁醚反应成磷酸三(丁氧基乙基)酯成品,而后分离获得高纯度2-丁氧基氯乙烷。
2)避免使用精馏分离方式,能大大减少能耗和新设备投入成本。
3)2-丁氧基氯乙烷粗品洗涤产生的废水可套用回TBEP粗品的洗涤环节,不会额外产生废水。
4)由于报废的回收乙二醇单丁醚需要逐步加到碱性废水中,稀释一定浓度后,才能由生化处理到合格,废水处理周期长,处理难度大,成本较高,通过报废回收乙二醇单丁醚的再利用减少了废水处理的成本,大大降低了废水处理的压力。
图1为本发明的流程示意图。
下面结合说明书附图和实施例对本发明做进一步地说明,但本发明的保护范围并不仅限于此。
以下实施例所采用的原料:
回收乙二醇单丁醚:乙二醇单丁醚含量:67.61%、2-丁氧基氯乙烷含量:30%、氯化氢:2.24%、水分:0.15%;
三氯氧磷:纯度99.5%;
纯乙二醇单丁醚:纯度99.95%、水份0.05%;
四氯化钛:纯度99.5%。
实施例1
通过如图1所示的流程进行。
1)酯化滴加三氯氧磷:
取回收乙二醇单丁醚110g,0.3g的四氯化钛,放入500ml四口瓶中,开启搅拌,瓶内真空保持-0.094Mpa,以上底料使用冰浴降温到10-15℃后,将100.3g三氯氧磷缓慢滴入底料中,约1.5h滴加完成,滴加过程需要控制真空-0.094Mpa、温度15℃,滴加完成后,维持温度15℃进行保温1.5h;
2)酯化保温:
保持系统真空度不变,温度上升到50℃后保温1h,取样进行气相色谱检测乙二醇单丁醚没有残留,制备得到中间体A1,称重186.09g;
3)减压蒸馏分离2-丁氧基氯乙烷:
将中间体A1移入减压蒸馏装置,真空度在-0.094Mpa下,将系统温度上升至75℃下将2-丁氧基氯乙烷组分馏出,直至无馏分蒸出,结束蒸馏,获得2-丁氧基氯乙烷粗品A2称重35.56g,剩余底料B1称重150.53g,A2取样使用气相色谱检测:2-丁氧基氯乙烷纯度为92.79%,检测到乙二醇单丁醚残留6.28%,其余物质0.93%(三氯氧磷、氯化氢)。
4)2-丁氧基氯乙烷粗品后处理:
2-丁氧基氯乙烷粗品A2,放入500ml四口瓶中,加入水15.89g和质量浓度30%的氢氧化钠水溶液1.89g,室温25℃下,搅拌20分钟,控制pH=9,保温结束,静置30分钟,分层出上层料层A3进行水洗;分出的下层碱洗废水测总磷,以判断A2中三氯氧磷实际含量,使用分光光度法测得总磷36mg/kg。
料层加入四口瓶中,投入水17.78g,室温下搅拌15分钟,控制pH=7,保温结束,静置30分钟,分出上层2-丁氧基氯乙烷成品34.17g,取样使用气相色谱外标法测得成品中2-丁氧基氯乙烷含量96.59%,乙二醇单丁醚残留量3.26%,使用卡尔费休法测水含0.15%,成品相关指标均达标;
5)向纯乙二醇单丁醚中酯化滴加回收乙二醇单丁醚剩余底料B1:
纯乙二醇单丁醚265g放入1000ml四口瓶中,再投入0.795g四氯化钛作为催化剂,真空度保持-0.094Mpa以上,底料温度15℃,开始缓慢均匀滴加B1共152.75g,滴加过程约1h,滴加完成后,真空度-0.094到-0.096Mpa,温度20℃保温1.5h;
6)升温和保温:
保持真空度,将温度上升至30℃时继续保温0.5h,再将温度上升至75℃保温0.5h,取样进行气相检测中间体残留量≤0.1%后反应结束,获得粗品B2,称重374.87g;
7)减压回收乙二醇单丁醚:
B2在真空度在-0.094到-0.096Mpa下,升温至160℃减压蒸馏回收乙二醇单丁醚,直到没有乙二醇单丁醚馏出,取样,进行粗品气相检测乙二醇单丁醚残留量2.44%,合格,结束蒸馏,获得磷酸酯阻燃剂TBEP粗品265.37g,回收乙二醇单丁醚109.5g;
8)TBEP粗品的后处理:
TBEP粗品B3放入1000ml四口瓶中,投入88.46g水和质量浓度为30%氢氧化钠水溶液7.868g进行碱性洗涤,60℃下搅拌25分钟,分出上层碱洗料层,投入1000ml的四口瓶中,再投入65℃水85.5g,温度控制在65℃,搅拌15min,静置30分钟,上层料层进行减压蒸馏,真空度-0.094Mpa,最高温度控制在105℃,直至观察不到水蒸出,结束蒸馏,制得磷酸酯阻燃剂TBEP成品260.54g,取样进行成品检测,结果如下:气相色谱检测TBEP含量98.52%(行业标准:>98.00%),卡尔费休测水分0.05%(行业标准:<0.2%),酸值0.03KOHmg/g(行业标准:<0.1KOHmg/g),色号45(行业标准:≤60)。
实施例2
其他过程与实施例1一致,实施例2只进行到步骤(4),不同之处在于:
步骤(1)中三氯氧磷加入量改为105.06g,四氯化钛加入量改为0.315g。
步骤(3)中蒸馏脱出2-丁氧基氯乙烷粗品A2称重为34.14克,气相色谱检测:2-丁氧基氯乙烷纯度为96.65%,乙二醇单丁醚残留2.18%,其他组分(三氯氧磷、氯化氢)1.17%。蒸馏底料B1称重157.46g。
步骤(4)中A2碱洗加入水14.83g和质量浓度30%的液碱2.24g,水洗加水17.07g,A2经过洗涤后,取样气相色谱测得2-丁氧基氯乙烷含量98.74%,乙二醇单丁醚1.11%,使用卡尔费休法测水含0.15%,获得2-丁氧基氯乙烷成品33.42g。分出的下层碱洗废水测总磷,以判断A2中三氯氧磷实际含量,使用分光光度法测得总磷837mg/kg。
实施例3
其他过程与实施例1一致,不同之处在于:
步骤(1)中三氯氧磷加入量改为106.73g,四氯化钛加入量改为0.32g。
步骤(3)中蒸馏脱出2-丁氧基氯乙烷粗品A2称重为33.81克,气相色谱检测:2-丁氧基氯乙烷纯度为97.61%,乙二醇单丁醚残留1.1%,其他组分(三氯氧磷、氯化氢)1.29%。蒸馏底料B1称重159.1g。
步骤(4)中A2碱洗加入水14.49g和质量浓度30%的氢氧化钠水溶液2.42g,水洗加水16.9g,A2经过洗涤后,取样气相色谱测得2-丁氧基氯乙烷含量99.29%,乙二醇单丁醚0.56%,使用卡尔费休法测水含0.15%,获得2-丁氧基氯乙烷成品33.24g。分出的下层碱洗废水测总磷,以判断A2中三氯氧磷实际含量,使用分光光度法测得总磷1246mg/kg。
步骤(5)中乙二醇单丁醚加入量改为289g,四氯化钛加入量改为0.867g,加入B1合计159.1g。
步骤(6)反应获得的粗品B2合计401.12g。
步骤(7)蒸馏回收乙二醇单丁醚118.95g,TBEP粗品282.17g。
步骤(8)碱洗水加入94.06g,液碱加入8.27g,水洗加入90.93g,TBEP成品获得277g,成品中TBEP气相色谱检测含量98.52%,乙二醇单丁醚含量1.48%。酸值0.03,水分0.053%,色号45。
实施例4
其他过程与实施例1一致,实验只进行到步骤(4),不同之处在于:
步骤(1)中三氯氧磷加入量改为108.43g,四氯化钛加入量改为0.325g。
步骤(3)中蒸馏脱出2-丁氧基氯乙烷粗品A2称重为34.03克,气相色谱检测:2-丁氧基氯乙烷纯度为96.97%,乙二醇单丁醚残留0.559%,其他杂质2.48%。蒸馏底料B1称重160.4g。
步骤(4)中A2碱洗加入水12.45g和质量浓度30%的液碱4.56g,水洗加水17.02g,A2经过洗涤后,取样气相色谱测得2-丁氧基氯乙烷含量99.57%,乙二醇单丁醚0.28%,使用卡尔费休法测水含0.15%。获得2-丁氧基氯乙烷成品33.14g。分出的下层碱洗废水测总磷,以判断A2中三氯氧磷实际含量,使用分光光度法测得总磷5963mg/kg。
实施例5
其他过程与实施例1一致,实验只进行到步骤(4),不同之处在于:
步骤(1)中三氯氧磷加入量改为110.2g,四氯化钛加入量改为0.33g。
步骤(3)中蒸馏脱出2-丁氧基氯乙烷粗品A2称重为34.02克,气相色谱检测后A2中2-丁氧基氯乙烷纯度为97%,没有测出乙二醇单丁醚,其他杂质3%(三氯氧磷、氯化氢)。蒸馏底料B1称重162g。
步骤(4)中A2碱洗加入水11.54g和质量浓度30%的液碱5.47g,水洗加水17.01g,A2经过洗涤后,取样气相色谱测得2-丁氧基氯乙烷含量99.85%,使用卡尔费休法测水含0.15%,获得2-丁氧基氯乙烷成品33.05g。分出的下层碱洗废水测总磷,以判断A2中三氯氧磷实际含量,使用分光光度法测得总磷7902mg/kg。
实施例6
其他过程与实施例1一致,实验只进行到步骤(4),不同之处在于:
步骤(1)中三氯氧磷加入量改为113.78g,四氯化钛加入量改为0.34g。
步骤(3)中蒸馏脱出2-丁氧基氯乙烷粗品A2称重为34.02克,气相色谱检测后A2中2-丁氧基氯乙烷纯度为96.5%,其他杂质(三氯氧磷、氯化氢)3.5%,蒸馏底料B1称重165.41g。
步骤(4)中A2碱洗加入水10.71g和质量浓度30%的液碱6.39g,水洗加水17.1g,A2经过洗涤后,取样气相色谱测得2-丁氧基氯乙烷含量99.85%,使用卡尔费休法测水含0.15%,获得2-丁氧基氯乙烷成品33.05g。分出的下层碱洗废水测总磷,以判断A2中三氯氧磷实际含量,使用分光光度法测得总磷9772mg/kg。
实施例7
其他过程与实施例1一致,实验只进行到步骤(4)完成碱洗分层,不同之处在于:A1减压蒸馏温度改为60℃,馏分收集了24克,气相色谱检测后A2中2-丁氧基氯乙烷纯度为90.69%,乙二醇单丁醚9.3%,其他杂质(三氯氧磷、氯化氢)0.012%,蒸馏底料B1称重164.3g。A2进行碱洗,碱洗水层测总磷30㎎/kg。
实施例8
其他过程与实施例1一致,实验只进行到步骤(4)完成碱洗分层,不同之处在于:A1减压蒸馏温度改为65℃,发现馏分收集了29克,气相色谱检测后A2中2-丁氧基氯乙烷纯度为92.3%,乙二醇单丁醚7.69%,其他杂质(三氯氧磷、氯化氢)0.01%,蒸馏底料B1称重159.3g。A2进行碱洗,碱洗水层测总磷32㎎/kg。
实施例9
其他过程与实施例1一致,实验只进行到步骤(4)完成碱洗分层,不同之处在于:A1减压蒸馏温度改为70℃,发现馏分收集了31克,气相色谱检测后A2中2-丁氧基氯乙烷纯度为92.79%,乙二醇单丁醚7.2%,其他杂质(三氯氧磷、氯化氢)0.01%,蒸馏底料B1称重157.3g。A2进行碱洗,碱洗水层测总磷33㎎/kg。
实施例10
其他过程与实施例1一致,实验只进行到步骤(4)完成碱洗分层,不同之处在于:A1减压蒸馏温度改为80℃,发现馏分收集了35克,气相色谱检测后A2中2-丁氧基氯乙烷纯度为91.67%,乙二醇单丁醚6.2%,其他杂质(三氯氧磷、氯化氢)2.136%,蒸馏底料B1称重152.3g。A2进行碱洗,碱洗水层测总磷8304㎎/kg。
实验中使用到的气相色谱检测方法:
1.步骤(2)、步骤(3)、步骤(6)中面积归一化法和步骤(8)中外标法气相色谱检测设备和参数:
①检测设备及型号:岛津气象色谱仪GC-2010Pro
②设置条件:SPL1温度:280℃
SPL1压力:55.4KPa
N2吹扫流量:3.0mL/min
初始压力:653KPa
总流量:17.7mL/min
色谱柱温度:100℃
③外标法使用标准物质:使用99.9%磷酸三乙酯作为标定物,按10%质量比加入样品中,再使用甲醇1:10稀释后进样。
2.步骤(3)中磷含量检测方法:钼酸铵分光光度法GB 11893-89
3.步骤(4)中气相色谱外标法:
①检测设备及型号:岛津气象色谱仪GC-2010Pro
②设置条件:SPL1温度:280℃
SPL1压力:55.4KPa
N2吹扫流量:3.0mL/min
初始压力:653KPa
总流量:17.7mL/min
色谱柱温度:100℃
④检测方法:
步骤(4)、步骤(8)中水含量卡尔费休法设备型号:870TitroLine KF;
步骤(8)中酸值检测:石油产品酸值检测方法,GB264-83;
步骤(8)中色号检测:铂钴色号检测法考GB 3143-1982。
实验结果分析:
实施例1到实施例6的6组实验中,投入的三氯氧磷99.5%的有效成分与乙二醇单丁醚进行反应的质量都是96.75g,各成分含量如下表1所示
表1实施例1到实施例6的各成分含量
1.三氯氧磷加入量条件确认:
分析:
①比较实验1到6,当三氯氧磷的有效成分相比反应量过量8.90%以上时,2-丁氧基氯乙烷成品主含量超过99%,达到合格范围。
②考虑到过量三氯氧磷会有一部分随着2-丁氧基氯乙烷粗品蒸出,在2-丁氧基氯乙烷粗品A2碱洗环节反应生产磷酸钠和氯化钠。从实验1到实验6的A2碱
洗水总磷数值可看出,总磷值越大代表三氯氧磷损耗越大,造成原料消耗成本上升。
综合考虑成本控制和质量,优选实验3中三氯氧磷投料量为最佳投料比例。
2.步骤(3)蒸馏温度条件选择
对比实施例1、实施例7、实施例8、实施例9、实施例10的蒸馏产物质量、2-丁氧基氯乙烷含量可知,2-丁氧基氯乙烷蒸馏温度低于75℃时会造成底料中残留较多2-丁氧基氯乙烷,影响收率。
对比实施例1、实施例7、实施例8、实施例9、实施例10的步骤(4)碱洗废水总磷数据可知,75℃以前三氯氧磷更多的是被蒸馏夹带,损耗量比较接近;当蒸馏温度80℃后,过量三氯氧磷会由于温度达到真空下沸点附近而大量被蒸出,导致三氯氧磷损耗显著提升。
实施例1控制蒸馏温度75℃既能将2-丁氧基氯乙烷大部分蒸出,又不会导致大量三氯氧磷被夹带蒸出。该条件是针对蒸馏真空-0.094到-0.096Mpa之间得出,当真空效果变差时,最佳温度应大于75℃。
Claims (9)
- 一种磷酸三(丁氧基乙基)酯生产过程中的副产物2-丁氧基氯乙烷的分离提纯工艺,其特征在于包括如下步骤:1)在含2-丁氧基氯乙烷浓度≥30%的回收乙二醇单丁醚中加入四氯化钛,溶解彻底后,将混合物料降温到10-15℃,然后滴加过量的三氯氧磷,滴加完成后保温1-2h,继续升温至50-55℃,将物料中的乙二醇单丁醚彻底反应成丁氧基乙基磷酸酯二酰氯;2)对步骤1)的物料进行减压蒸馏,分离出2-丁氧基氯乙烷粗品和底料溶液;3)向步骤2)中的2-丁氧基氯乙烷粗品中加入液碱和水,搅拌碱洗洗涤,而后静置分离出出料层和碱洗废水层,分出的出料层加水搅拌洗涤后静置,分出2-丁氧基氯乙烷成品和水洗废水;4)过量的纯乙二醇单丁醚中加入四氯化钛,而后控制温度为10-15℃,滴加步骤2)中的底料溶液,滴加完成后,保温1.5h,阶段式升温反应,而后减压蒸馏脱出乙二醇单丁醚,获得磷酸三(丁氧基乙基)酯粗品,而后经过碱洗、水洗、蒸馏、过滤获得磷酸三(丁氧基乙基)酯成品。
- 如权利要求1所述的分离提纯工艺,其特征在于步骤1)中回收乙二醇单丁醚中乙二醇单丁醚的总质量与三氯氧磷的质量比为1.3-1.6:1,四氯化钛的加入量为三氯氧磷加入量的质量比为0.2-0.4%。
- 如权利要求1所述的分离提纯工艺,其特征在于步骤2)减压蒸馏的温度为60-80℃。
- 如权利要求1所述的分离提纯工艺,其特征在于步骤3)中的液碱为氢氧化钠溶液,加入液碱和水后,在25-35℃下,搅拌20-30min,控制pH=9-10;出料层搅拌15-30min,控制pH=7。
- 如权利要求2所述的分离提纯工艺,其特征在于步骤4)中所述的纯乙二醇单丁醚与四氯化钛的加入量的质量比为800-1000:3。
- 如权利要求1所述的分离提纯工艺,其特征在于步骤4)中的阶段式升温反应的过程为升温至30-35℃保温0.5h,再继续升温至75-80℃保温0.5h,减压蒸馏温度为160-170℃。
- 如权利要求1所述的分离提纯工艺,其特征在于步骤4)的碱洗、水洗、 蒸馏、过滤具体过程为加入水和液碱进行碱洗,搅拌分出碱洗料层,加入水进行水洗,水洗完成后静置,上层料层进行减压蒸馏,温度控制在105-110℃,下层料层进行过滤。
- [根据细则91更正 11.07.2023]
如权利要求1所述的分离提纯工艺,其特征在于步骤3)中的碱洗废水和水洗废水以及步骤4)中的水洗废水套用回磷酸三(丁氧基乙基)酯粗品的洗涤环节。 - 如权利要求1所述的分离提纯工艺,其特征在于分离制备过程在真空条件下进行,真空度为-0.094到-0.096Mpa。
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US4421695A (en) * | 1982-04-07 | 1983-12-20 | Fmc Corporation | Production of alkoxyalkyl phosphate esters |
JP2001226387A (ja) * | 2000-02-15 | 2001-08-21 | Daihachi Chemical Industry Co Ltd | リン酸トリ(ブトキシエチル)の精製方法 |
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