CN1024542C - Method for preparing polycarbonate-grade bisphenol A - Google Patents
Method for preparing polycarbonate-grade bisphenol A Download PDFInfo
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- CN1024542C CN1024542C CN 92106030 CN92106030A CN1024542C CN 1024542 C CN1024542 C CN 1024542C CN 92106030 CN92106030 CN 92106030 CN 92106030 A CN92106030 A CN 92106030A CN 1024542 C CN1024542 C CN 1024542C
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- washing
- phenol
- chloride
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- dihydroxyphenyl propane
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- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 238000000034 method Methods 0.000 title claims description 23
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 71
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 52
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 46
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 30
- 150000001735 carboxylic acids Chemical class 0.000 claims abstract description 14
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims abstract description 13
- 229910001510 metal chloride Inorganic materials 0.000 claims abstract description 11
- 238000004519 manufacturing process Methods 0.000 claims abstract description 10
- 239000002904 solvent Substances 0.000 claims abstract description 9
- 238000005406 washing Methods 0.000 claims description 66
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 56
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 45
- MNAHQWDCXOHBHK-UHFFFAOYSA-N 1-phenylpropane-1,1-diol Chemical compound CCC(O)(O)C1=CC=CC=C1 MNAHQWDCXOHBHK-UHFFFAOYSA-N 0.000 claims description 42
- 238000010790 dilution Methods 0.000 claims description 30
- 239000012895 dilution Substances 0.000 claims description 30
- 229930185605 Bisphenol Natural products 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 238000007598 dipping method Methods 0.000 claims description 18
- 238000007670 refining Methods 0.000 claims description 16
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 15
- 238000002425 crystallisation Methods 0.000 claims description 15
- 230000008025 crystallization Effects 0.000 claims description 15
- 238000006482 condensation reaction Methods 0.000 claims description 14
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 claims description 12
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 9
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 7
- -1 carboxylate salt Chemical class 0.000 claims description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 5
- 229920000515 polycarbonate Polymers 0.000 claims description 5
- 239000004417 polycarbonate Substances 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 4
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 claims description 4
- 239000001110 calcium chloride Substances 0.000 claims description 4
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 229910052736 halogen Inorganic materials 0.000 claims description 4
- 150000002367 halogens Chemical class 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 4
- 235000019270 ammonium chloride Nutrition 0.000 claims description 3
- 229910001626 barium chloride Inorganic materials 0.000 claims description 3
- 229940045511 barium chloride Drugs 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- 241000370738 Chlorion Species 0.000 claims description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- VVUILVMDMIIETB-UHFFFAOYSA-K [Ti].Cl[Al](Cl)Cl Chemical compound [Ti].Cl[Al](Cl)Cl VVUILVMDMIIETB-UHFFFAOYSA-K 0.000 claims description 2
- 150000003863 ammonium salts Chemical class 0.000 claims description 2
- 150000001492 aromatic hydrocarbon derivatives Chemical class 0.000 claims description 2
- 229910052788 barium Inorganic materials 0.000 claims description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052794 bromium Inorganic materials 0.000 claims description 2
- 239000011575 calcium Substances 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 239000000460 chlorine Substances 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 239000011737 fluorine Substances 0.000 claims description 2
- 229910000765 intermetallic Inorganic materials 0.000 claims description 2
- HWSZZLVAJGOAAY-UHFFFAOYSA-L lead(II) chloride Chemical compound Cl[Pb]Cl HWSZZLVAJGOAAY-UHFFFAOYSA-L 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- 239000011592 zinc chloride Substances 0.000 claims description 2
- 235000005074 zinc chloride Nutrition 0.000 claims description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims 2
- 238000007865 diluting Methods 0.000 claims 1
- 150000002148 esters Chemical class 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 3
- 150000007942 carboxylates Chemical class 0.000 abstract description 2
- 238000009833 condensation Methods 0.000 description 40
- 230000005494 condensation Effects 0.000 description 40
- 239000000047 product Substances 0.000 description 18
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 16
- 238000011084 recovery Methods 0.000 description 14
- 239000012452 mother liquor Substances 0.000 description 10
- 239000001294 propane Substances 0.000 description 9
- 238000001816 cooling Methods 0.000 description 8
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 8
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 8
- 235000013849 propane Nutrition 0.000 description 8
- 239000013078 crystal Substances 0.000 description 7
- 235000011149 sulphuric acid Nutrition 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 4
- 150000001555 benzenes Chemical class 0.000 description 4
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000012074 organic phase Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- DPDMMXDBJGCCQC-UHFFFAOYSA-N [Na].[Cl] Chemical compound [Na].[Cl] DPDMMXDBJGCCQC-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- JGDITNMASUZKPW-UHFFFAOYSA-K aluminium trichloride hexahydrate Chemical class O.O.O.O.O.O.Cl[Al](Cl)Cl JGDITNMASUZKPW-UHFFFAOYSA-K 0.000 description 2
- USYKECCERZFPQQ-UHFFFAOYSA-L barium(2+);2-sulfanylacetate Chemical class [Ba+2].[O-]C(=O)CS.[O-]C(=O)CS USYKECCERZFPQQ-UHFFFAOYSA-L 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- CNYFJCCVJNARLE-UHFFFAOYSA-L calcium;2-sulfanylacetic acid;2-sulfidoacetate Chemical class [Ca+2].[O-]C(=O)CS.[O-]C(=O)CS CNYFJCCVJNARLE-UHFFFAOYSA-L 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229960002337 magnesium chloride Drugs 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 208000006558 Dental Calculus Diseases 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000004826 Synthetic adhesive Substances 0.000 description 1
- NOJZFGZMTUAHLD-UHFFFAOYSA-N [Li].[Cl] Chemical compound [Li].[Cl] NOJZFGZMTUAHLD-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 229940063656 aluminum chloride Drugs 0.000 description 1
- 229940009861 aluminum chloride hexahydrate Drugs 0.000 description 1
- 238000004176 ammonification Methods 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 239000002585 base Chemical group 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003729 cation exchange resin Substances 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- FSXWCUSOFGPQKK-UHFFFAOYSA-N ethanebis(thioic s-acid) Chemical compound SC(=O)C(S)=O FSXWCUSOFGPQKK-UHFFFAOYSA-N 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 125000004464 hydroxyphenyl group Chemical group 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229940073589 magnesium chloride anhydrous Drugs 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- GNBVPFITFYNRCN-UHFFFAOYSA-M sodium thioglycolate Chemical compound [Na+].[O-]C(=O)CS GNBVPFITFYNRCN-UHFFFAOYSA-M 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A process for preparing polycarbonate-grade bisphenol A from phenol and acetone features that the sulfuric acid, metal chloride or hydrochloric acid is used as main catalyst, the mercapto-contained carboxylic acid or its carboxylate is used as auxiliary catalyst, and the phenol and acetone are condensed in the solvent of aromatic hydrocarbon or its derivative to obtain bisphenol A.
Description
The invention relates to a kind of phenol, acetone of adopting is the productive method of chemical engineering that raw material is produced polycarbonate-grade bis phenol A.
Dihydroxyphenyl propane, formal name used at school 2, two [4-the hydroxy phenyl]-propane of 2-.The dihydroxyphenyl propane of present industrial production generally is to be raw material with phenol, acetone, forms through condensation under an acidic catalyst effect.Dihydroxyphenyl propane is owing to use the catalyzer difference, divide sulfuric acid process, hydrogen chloride, cation exchange resin processes etc., it is 91106075.8 " a kind of dihydroxyphenyl propane method of producing " that the shortcoming that the present inventor once existed at aforementioned production method is developed number of patent application, this patent application is improved primary sulfuric acid process dihydroxyphenyl propane technology, keeping its flow process short, equipment is few, under the prerequisite of characteristics such as technology is simple, produce the high quality dihydroxyphenyl propane that meets the polycarbonate production service requirements, but still having, this technology need improve part, in the technology after making crude bisphenol, need and to put into the aromatic hydrocarbon solvent of crystallization reaction jar after the dihydroxyphenyl propane washing, dissolving, cooling, crystallization, isolated aromatic hydrocarbon mother liquor is put in the alkali cleaning retort again, leaves standstill regeneration after alkali cleaning.So not only make complex technical process, and need to consume important chemical material sodium hydroxide.The nascent state hydrogenchloride that utilizes sulfuric acid and Repone K or sodium-chlor to produce in condensation reaction is separately made main catalyzer, and setting-up point is higher, and the reaction times is longer.
The purpose of this invention is to provide a kind of improved method of producing dihydroxyphenyl propane, it has widened the variety range of catalyzer, solvent, and technology is simpler, reduced setting-up point, reduce the reaction times, further improved the quality and the yield of product, reduced material cost.
The object of the present invention is achieved like this, adopt sulfuric acid and metal chloride or hydrochloric acid as main catalyzer, the carboxylate salt that contains the carboxylic acid of sulfydryl or contain sulfydryl is a cocatalyst, in the solvent of aromatic hydrocarbons or derivatives thereof, make phenol and acetone chemical equivalent according to 1: 0.5 mol ratio, under 5-30 ℃ of temperature, carry out generating in condensation reaction 1-6 hour dihydroxyphenyl propane, the crude bisphenol that generates is through the dilution washing, crystallization, the washing back is flooded with methylene dichloride once more, obtains meeting the dihydroxyphenyl propane of polycarbonate production service requirements.
The present invention is because employing sulfuric acid and metal chloride or hydrochloric acid are main catalyzer, under hydrogenchloride that in its condensation reaction, takes place and the effect of vitriolic dual catalytic, strengthened the main reaction of condensation, speed is fast, and the time is short, and temperature of reaction is low, so further suppressed the generation of by product, the quality of product is good, and yield height, dihydroxyphenyl propane meet the requirement that polycarbonate production is used.Technology of the present invention is simpler, compare with hydrogen chloride, base exchange method have that flow process is short, equipment is few, characteristics such as reduced investment, production cost are low.With the sulfuric acid of formerly applying for a patent, nascent state hydrogen chloride relatively, realized the chemical equivalent proportioning of phenol and acetone, the use kind of catalyzer has been widened in the low temperature condensation reaction, is easier to apply.
Below the invention will be further described:
1. condensation
The main catalyzer of condensation reaction is sulfuric acid and hydrogenchloride, and hydrogenchloride is that the sulfuric acid and the metal chloride that drop into take place through chemical reaction in condensation course, and perhaps sulfuric acid of Tou Ruing and hydrochloric acid take place through chemical analytic function in condensation reaction.Metal chloride is meant that chlorine lithium, calcium chloride, magnesium chloride, zinc chloride, lead chloride, bariumchloride, iron(ic) chloride, aluminum chloride, titanium aluminum chloride, titanium tetrachloride and ammonification ammonium or other contain the metallic compound of chlorion, and the action effect of these metal chlorides all is better than Repone K, sodium-chlor.Cocatalyst is the metal carboxylate that contains the carboxylic acid of sulfydryl or contain sulfydryl, the carboxylic acid that contains sulfydryl is meant the carboxylic acid that has been replaced hydrogen atom on the carbon bond by sulfydryl, the number that sulfydryl replaced is 1-2, the carbonatoms of carboxylic acid is 1-8, and the hydroxy acid salt that contains sulfydryl is meant potassium, sodium, calcium, barium, the ammonium salt of above-mentioned carboxylic acid.The solvent of condensation reaction is the aromatic hydrocarbons or derivatives thereof, arene derivatives is meant that hydrogen atom on the carbon bond of benzene,toluene,xylene, ethylbenzene is by derivative that halogen replaced, halogen is fluorine, chlorine, bromine, substituted radical is 1-3, has widened the variety range of catalyzer, solvent.
Phenol and the acetone amount according to 1: 0.5 mol ratio is joined in the retort, and according to phenol and sulfuric acid 1: the amount of 0.1-1.5 mol ratio adds sulfuric acid, according to sulfuric acid and metal chloride or hydrochloric acid 1: the amount of 0.0025-0.25 mol ratio adds metal chloride or hydrochloric acid, 0.04-4% according to the phenol input amount adds the carboxylate salt that contains the carboxylic acid of sulfydryl or contain sulfydryl, 1-4 according to the phenol input amount extraordinarily goes into the aromatic hydrocarbons or derivatives thereof, under 5-30 ℃ of temperature stirring reaction 1-6 hour, after condensation reaction finishes, add 2-6 doubly to the water of resultant crude bisphenol, dilute washing at 70-100 ℃, washing time 0.1-2 hour, crude bisphenol is dissolved in the organic phase of aromatic hydrocarbons or derivatives thereof, sulfuric acid and corresponding salt or hydrochloric acid, be soluble in the aqueous phase, two are separated, lower floor is a water, tell as by-product and be used, form the method reclaim(ed) sulfuric acid of putting as employing and produce vitriolate of tartar or ammonium sulfate, upper organic phase adds the water of 2-6 times of resultant crude bisphenol again, still under 70-100 ℃, washed 0.1-2 hour, so washing is 1-3 time, then organic phase is stirred and be cooled to 10-25 ℃ in 0.1-4 hour, the crude bisphenol crystallization is separated out, obtain crude bisphenol after extracting aromatic hydrocarbons or derivatives thereof solvent out, the aromatic hydrocarbons or derivatives thereof leaves standstill told moisture content in 1-24 hour, dropped into condensation reaction again and recycled.
2. washing
With the crude bisphenol in the condensation jar, by the 4-10 of its weight extraordinarily entry wash once more, wash temperature 70-100 ℃, washed time 0.1-2 hour, the washing back solid-liquid separation that finishes obtains wet dihydroxyphenyl propane, washing water are the recyclable processing of phenolic wastewater.
3. refining
To contain wet dihydroxyphenyl propane joins in the impregnating autoclave, 0.2-1 according to the dihydroxyphenyl propane quantum of output extraordinarily goes into methylene dichloride, flooded 0.1-4 hour down at 5-35 ℃, after finishing, dipping leaches the methylene dichloride mother liquor, and drying gets the finished product dihydroxyphenyl propane, methylene dichloride mother liquor distillation recycling use, distillation residue can be used for synthetic adhesive.
Now describe technological process of the present invention in conjunction with the embodiments in detail.
Embodiment 1
47.5 kilograms of phenol with 99%, 14.8 kilograms in 98% acetone, 49 kilograms of 98% industrial sulphuric acids, 9.2 kilograms of 98% Aluminum Chloride Hexahydrates, 103.4 kilograms of toluene, 0.5 kilogram of Thiovanic acid, 30 kilograms of methylene dichloride, get 51.6 kilograms of finished product dihydroxyphenyl propanes through condensation, dilution washing, crystal refining, product yield is 90.6%; Reclaim 96.5 kilograms of toluene, the rate of recovery 93.4%; Reclaim 27.2 kilograms of methylene dichloride, the rate of recovery 90.7%.
The main technique condition of present embodiment is:
(1), condensation
The condensation mol ratio, phenol: acetone=1: 0.5
Phenol: sulfuric acid=1: 1
Sulfuric acid: Aluminum Chloride Hexahydrate=1: 0.075
Condensation weight ratio: phenol: toluene=1: 2.2
Phenol: Thiovanic acid=1: 0.01
Setting-up point: 15-30 ℃
Condensation churning time: 6 hours.
Dilution washing temperature: 95 ℃
Dilution washing times: 3 times
Each dilution washing time: 1 hour
Temperature is separated out in the dihydroxyphenyl propane crystallization: 10-25 ℃
The dihydroxyphenyl propane cooling and stirring time: 1 hour
The toluene mother liquor leaves standstill the branch water time: 16 hours
(2), washing
Wash water consumption: 6 times/crude bisphenol
Washing temperature: 90 ℃
The washing time: 2 hours
(3), refining
Methylene dichloride consumption: 0.58 times/dihydroxyphenyl propane
Dipping temperature: 25-30 ℃
Dipping time: 1.5 hours
Embodiment 2
189.9 kilograms of phenol with 99%, 59.2 kilograms in 98% acetone, 180 kilograms of 98% industrial sulphuric acids, 20 kilograms of Calcium Chloride Powder Anhydrouss (content 95%), 376 kilograms of toluene, 3 kilograms of barium thioglycolates, 92 kilograms of methylene dichloride, through condensation, dilution washing, crystal refining gets 201.1 kilograms of finished product dihydroxyphenyl propanes, and product yield is 88.2%; Reclaim 352.7 kilograms of toluene, the rate of recovery 93.8%; Reclaim 84.1 kilograms of methylene dichloride, the rate of recovery 91.4%.
The main technique condition of present embodiment is:
(1), condensation
Condensation mol ratio: phenol: acetone=1: 0.5
Phenol: sulfuric acid=1: 0.9
Sulfuric acid: Calcium Chloride Powder Anhydrous=1: 0.1
Condensation weight ratio: phenol: toluene=1: 2
Phenol: barium thioglycolate=1: 0.015
Setting-up point: 20-30 ℃
Condensation churning time: 1 hour.
Dilution washing temperature: 92 ℃
Dilution washing times: 4 times
Each dilution washing time: 1 hour
Temperature is separated out in the dihydroxyphenyl propane crystallization: 10-25 ℃
The dihydroxyphenyl propane cooling and stirring time: 1.5 hours
The toluene mother liquor leaves standstill the branch water time: 24 hours
(2), washing
Wash water consumption: 6.5 times/crude bisphenol
Washing temperature: 90 ℃
The washing time: 2 hours
(3), refining
Methylene dichloride consumption: 0.45 times/dihydroxyphenyl propane
Dipping temperature: 20-25 ℃
Dipping time: 2.5 hours
Embodiment 3
166.2 kilograms of phenol with 99%, 44.4 kilograms in 98% acetone, 154.3 kilograms of 98% industrial sulphuric acids, 24.3 kilograms of Magnesium Chloride Anhydrouss (content 98%), 427.7 kilograms of benzene, 2.3 kilograms of calcium mercaptoacetates, 72.2 kilograms of methylene dichloride, through condensation, dilution washing, crystal refining gets 150.5 kilograms of finished product dihydroxyphenyl propanes, and product yield is 88%; Reclaim 394.8 kilograms of toluene, the rate of recovery 92.3%; Reclaim 65.8 kilograms of methylene dichloride, the rate of recovery 91.1%.
The main technique condition of present embodiment is:
(1), condensation
The condensation mol ratio, phenol: acetone=1: 0.5
Phenol: sulfuric acid=1: 0.85
Sulfuric acid: Magnesium Chloride Anhydrous=1: 0.15
Condensation weight ratio: phenol: benzene=1: 2.6
Phenol: calcium mercaptoacetate=1: 0.014
Setting-up point: 10-25 ℃
Condensation churning time: 4 hours.
Dilution washing temperature: 88 ℃
Dilution washing times: 3 times
Each dilution washing time: 1.5 hours
Temperature is separated out in the dihydroxyphenyl propane crystallization: 10-25 ℃
The dihydroxyphenyl propane cooling and stirring time: 2 hours
The benzene mother liquor leaves standstill the branch water time: 18 hours
(2), washing
Wash water consumption: 5.5 times/crude bisphenol
Washing temperature: 80 ℃
The washing time: 1.5 hours
(3), refining
Methylene dichloride consumption: 0.48 times/dihydroxyphenyl propane
Dipping temperature: 10-20 ℃
Dipping time: 2.5 hours
Embodiment 4
118.7 kilograms of phenol with 99%, 37.4 kilograms in 98% acetone, 150 kilograms of 98% industrial sulphuric acids, 18.7 kilograms of 98% barium chlorides, 329 kilograms of dimethylbenzene, 1.5 kilograms of Thioglycolic acid sodium salts, 69.8 kilograms of methylene dichloride, through condensation, dilution washing, crystal refining gets 126.8 kilograms of finished product dihydroxyphenyl propanes, and product yield is 89%; Reclaim 312.9 kilograms of dimethylbenzene, the rate of recovery 95.1%; Reclaim 64.4 kilograms of methylene dichloride, the rate of recovery 92.2%.
The main technique condition of present embodiment is:
(1), condensation
The condensation mol ratio, phenol: acetone=1: 0.5
Phenol: sulfuric acid=1: 1.2
Sulfuric acid: barium chloride=1: 0.05
Condensation weight ratio: phenol: dimethylbenzene=1: 2.8
Phenol: Thioglycolic acid sodium salt=1: 0.013
Setting-up point: 10-20 ℃
Condensation churning time: 6 hours.
Dilution washing temperature: 95 ℃
Dilution washing times: 3 times
Each dilution washing time: 2 hours
Temperature is separated out in the dihydroxyphenyl propane crystallization: 10-25 ℃
The dihydroxyphenyl propane cooling and stirring time: 2.5 hours
The dimethylbenzene mother liquor leaves standstill the branch water time: 8 hours
(2), washing
Wash water consumption: 6 times/crude bisphenol
Washing temperature: 85 ℃
The washing time: 1 hour
(3), refining
Methylene dichloride consumption: 0.55 times/dihydroxyphenyl propane
Dipping temperature: 5-15 ℃
Dipping time: 4 hours
Embodiment 5
71.2 kilograms of phenol with 99%, 22.2 kilograms in 98% acetone, 97.5 kilograms of 98% industrial sulphuric acids, 10.4 kilograms of 99% ammonium chlorides, 211.5 kilograms in ethylbenzene, two mercaptos are for 0.35 kilogram of oxalic acid, 52.4 kilograms of methylene dichloride, through condensation, dilution washing, crystal refining gets 74.9 kilograms of finished product dihydroxyphenyl propanes, and product yield is 87.6%; Reclaim 203.7 kilograms in ethylbenzene, the rate of recovery 96.3%; Reclaim 48.6 kilograms of methylene dichloride, the rate of recovery 92.7%.
The main technique condition of present embodiment is:
(1), condensation
The condensation mol ratio, phenol: acetone=1: 0.5
Phenol: sulfuric acid=1: 1.3
Sulfuric acid: ammonium chloride=1: 0.2
Condensation weight ratio: phenol: ethylbenzene=1: 3
Phenol: dithio oxalic acid=1: 0.005
Setting-up point: 10-25 ℃
Condensation churning time: 4 hours.
Dilution washing temperature: 98 ℃
Dilution washing times: 2 times
Each dilution washing time: 1.5 hours
Temperature is separated out in the dihydroxyphenyl propane crystallization: 10-25 ℃
The dihydroxyphenyl propane cooling and stirring time: 3 hours
The ethylbenzene mother liquor leaves standstill the branch water time: 12 hours
(2), washing
Wash water consumption: 6 times/crude bisphenol
Washing temperature: 90 ℃
The washing time: 0.5 hour
(3), refining
Methylene dichloride consumption: 0.7 times/dihydroxyphenyl propane
Dipping temperature: 10-25 ℃
Dipping time: 2.5 hours
Embodiment 6
23.7 kilograms of phenol with 99%, 7.4 kilograms in 98% acetone, 35 kilograms of 98% industrial sulphuric acids, 0.67 kilogram of titanium tetrachloride, 42.2 kilograms of chlorinated benzene, 0.28 kilogram of sulfydryl butyric acid, 20.5 kilograms of methylene dichloride, through condensation, dilution washing, crystal refining gets 25.7 kilograms of finished product dihydroxyphenyl propanes, and product yield is 90.1%; Reclaim 40.4 kilograms of chlorinated benzene, the rate of recovery 95.8%; Reclaim 18.6 kilograms of methylene dichloride, the rate of recovery 90.6%.
The main technique condition of present embodiment is:
(1), condensation
The condensation mol ratio, phenol: acetone=1: 0.5
Phenol: sulfuric acid=1: 1.4
Sulfuric acid: titanium tetrachloride=1: 0.025
Condensation weight ratio: phenol: chlorinated benzene=1: 1.8
Phenol: sulfydryl butyric acid=1: 0.012
Setting-up point: 5-20 ℃
Condensation churning time: 2 hours.
Dilution washing temperature: 100 ℃
Dilution washing times: 2 times
Each dilution washing time: 1 hour
Temperature is separated out in the dihydroxyphenyl propane crystallization: 10-25 ℃
The dihydroxyphenyl propane cooling and stirring time: 4 hours
The chlorinated benzene mother liquor leaves standstill the branch water time: 4 hours
(2), washing
Wash water consumption: 6.5 times/crude bisphenol
Washing temperature: 100 ℃
The washing time: 0.5 hour
(3), refining
Methylene dichloride consumption: 0.8 times/dihydroxyphenyl propane
Dipping temperature: 20-35 ℃
Dipping time: 0.5 hour
Embodiment 7
94.9 kilograms of phenol with 99%, 29.6 kilograms in 98% acetone, 110 kilograms of 98% industrial sulphuric acids, 10.7 kilograms of 34% hydrochloric acid, 228 kilograms of toluene, 1.2 kilograms of Thiovanic acids, 45 kilograms of methylene dichloride, through condensation, dilution washing, crystal refining gets 102.5 kilograms of finished product dihydroxyphenyl propanes, and product yield is 89.9%; Reclaim 215 kilograms of toluene, the rate of recovery 94.3%; Reclaim 41 kilograms of methylene dichloride, the rate of recovery 91.1%.
The main technique condition of present embodiment is:
(1), condensation
The condensation mol ratio, phenol: acetone=1: 0.5
Phenol: sulfuric acid=1: 1.1
Sulfuric acid: hydrogenchloride=1: 0.09
Condensation weight ratio: phenol: toluene=1: 2.4
Phenol: Thiovanic acid=1: 0.0125
Setting-up point: 20-30 ℃
Condensation churning time: 3 hours.
Dilution washing temperature: 90 ℃
Dilution washing times: 2 times
Each dilution washing time: 1.5 hours
Temperature is separated out in the dihydroxyphenyl propane crystallization: 10-25 ℃
The dihydroxyphenyl propane cooling and stirring time: 0.5 hour
The toluene mother liquor leaves standstill the branch water time: 12 hours
(2), washing
Wash water consumption: 7.5 times/crude bisphenol
Washing temperature: 85 ℃
The washing time: 1.5 hours
(3), refining
Methylene dichloride consumption: 0.45 times/dihydroxyphenyl propane
Dipping temperature: 20-25 ℃
Dipping time: 2 hours
The dihydroxyphenyl propane of embodiment one, two, three, four, five, six, seven all meets following product quality indicator:
Quality project quality index
156 ± 1 ℃ of fusing points
Content of bisphenol A 〉=99.5%
Colourity≤molten the method for 30APHA(alcohol)
≤ 130APHA(scorification)
Phenol content≤0.1%
Iron level≤3PPm
Moisture content≤0.1%
The appearance white crystalline powder is transparent inorganic tool impurity liquid after 180 ℃ of fusions.
Claims (4)
1, a kind of with phenol, acetone is the method that raw material is produced polycarbonate-grade bis phenol A, it is characterized in that adopting sulfuric acid and metal chloride or hydrochloric acid as main catalyzer, the carboxylate salt that contains the carboxylic acid of sulfydryl or contain sulfydryl is a cocatalyst, in the solvent of aromatic hydrocarbons or derivatives thereof, make phenol and acetone chemical equivalent according to 1: 0.5 mol ratio, under 5-30 ℃ of temperature, carry out generating in condensation reaction 1-6 hour dihydroxyphenyl propane, the crude bisphenol that generates is through the dilution washing, crystallization, the washing back is flooded with methylene dichloride once more, obtain meeting the dihydroxyphenyl propane of polycarbonate production service requirements, used metal chloride is meant lithium chloride, calcium chloride, magnesium chloride, zinc chloride, lead chloride, bariumchloride, iron(ic) chloride, aluminum chloride, titanium aluminum chloride, titanium tetrachloride and ammonium chloride or other contain the metallic compound of chlorion; The used carboxylic acid that contains sulfydryl is meant the carboxylic acid that has been replaced hydrogen atom on carbon bond by sulfydryl, and the number that sulfydryl replaced is 1-2, and the carbonatoms of carboxylic acid is 1-8, and the carboxylate salt that contains sulfydryl is meant the potassium of above-mentioned carboxylic acid, sodium, calcium, barium, ammonium salt; Used arene derivatives is meant hydrogen atom on the carbon bond of benzene,toluene,xylene, ethylbenzene by the derivative that halogen replaced, and halogen is fluorine, chlorine, bromine, and substituted radical is 1-3; Wherein condensation reaction phenol and vitriolic mol ratio are 1: 0.5-1.5, the mol ratio of sulfuric acid and metal chloride or hydrochloric acid is 1: 0.0025-0.25, the input amount that contains the carboxylic acid of sulfydryl or contain mercaptan carboxylic acid's salt is the 0.04-4% of phenol weight, the input amount of aromatic hydrocarbons or derivatives thereof be phenol weight 1-4 doubly.
2, the method for producing dihydroxyphenyl propane according to claim 1 is characterized in that the resultant dilute with water and the washing of condensation reaction, tells sulfuric acid and its esters or hydrochloric acid, dilutes and washing temperature 70-100 ℃, and the time is 0.1-2 hour.
3, the method for producing dihydroxyphenyl propane according to claim 1, it is characterized in that stirring 0.1-4 hour down at 10-25 ℃, its crystallization is separated out through diluting and washing the crude bisphenol that is dissolved in the aromatic hydrocarbons or derivatives thereof, the crude bisphenol that Crystallization Separation is come out, through washing is refining once more, washing temperature 70-100 ℃, washed time 0.1-2 hour, the methylene dichloride dipping is adopted in the washing back, the methylene dichloride consumption is 0.2-1 a times of dihydroxyphenyl propane quantum of output, dipping temperature 5-35 ℃, and dipping time 0.1-4 hour.
4, the method for producing dihydroxyphenyl propane according to claim 1 is characterized in that the aromatic hydrocarbons or derivatives thereof solvent through condensation reaction, after telling the crude bisphenol crystallization, leaves standstill and tells moisture in 1-24 hour, drops into condensation reaction again and recycles.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 92106030 CN1024542C (en) | 1992-01-22 | 1992-01-22 | Method for preparing polycarbonate-grade bisphenol A |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 92106030 CN1024542C (en) | 1992-01-22 | 1992-01-22 | Method for preparing polycarbonate-grade bisphenol A |
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| Publication Number | Publication Date |
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| CN1062720A CN1062720A (en) | 1992-07-15 |
| CN1024542C true CN1024542C (en) | 1994-05-18 |
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| CN 92106030 Expired - Fee Related CN1024542C (en) | 1992-01-22 | 1992-01-22 | Method for preparing polycarbonate-grade bisphenol A |
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| CN102491879B (en) * | 2011-11-14 | 2014-05-14 | 湘潭大学 | Preparation method for bisphenol F |
| JP6635575B2 (en) * | 2014-04-25 | 2020-01-29 | 日鉄ケミカル＆マテリアル株式会社 | Phenolic compound having good stability and method for producing the same |
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