CN1717379A - Process for preparing bisphenol A - Google Patents
Process for preparing bisphenol A Download PDFInfo
- Publication number
- CN1717379A CN1717379A CN 200380104506 CN200380104506A CN1717379A CN 1717379 A CN1717379 A CN 1717379A CN 200380104506 CN200380104506 CN 200380104506 CN 200380104506 A CN200380104506 A CN 200380104506A CN 1717379 A CN1717379 A CN 1717379A
- Authority
- CN
- China
- Prior art keywords
- phenol
- dihydroxyphenyl propane
- exchange resin
- acid
- type ion
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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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 abstract description 9
- 238000004519 manufacturing process Methods 0.000 title abstract 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 48
- 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 claims abstract description 43
- 239000003456 ion exchange resin Substances 0.000 claims abstract description 42
- 229920003303 ion-exchange polymer Polymers 0.000 claims abstract description 42
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 36
- 238000000034 method Methods 0.000 claims abstract description 29
- 238000006243 chemical reaction Methods 0.000 claims abstract description 26
- -1 amine compound Chemical class 0.000 claims abstract description 23
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 19
- 239000011593 sulfur Substances 0.000 claims abstract description 19
- MNAHQWDCXOHBHK-UHFFFAOYSA-N 1-phenylpropane-1,1-diol Chemical compound CCC(O)(O)C1=CC=CC=C1 MNAHQWDCXOHBHK-UHFFFAOYSA-N 0.000 claims description 44
- 238000005406 washing Methods 0.000 claims description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- 239000007788 liquid Substances 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 238000002360 preparation method Methods 0.000 claims description 5
- 239000003054 catalyst Substances 0.000 abstract description 5
- 238000012986 modification Methods 0.000 description 12
- 230000004048 modification Effects 0.000 description 12
- 239000011347 resin Substances 0.000 description 10
- 229920005989 resin Polymers 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 238000002425 crystallisation Methods 0.000 description 8
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 6
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 6
- 230000008025 crystallization Effects 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 150000002989 phenols Chemical class 0.000 description 3
- 239000001294 propane Substances 0.000 description 3
- 230000008961 swelling Effects 0.000 description 3
- VBAOEVKQBLGWTH-UHFFFAOYSA-N 2-pyridin-4-ylethanethiol Chemical compound SCCC1=CC=NC=C1 VBAOEVKQBLGWTH-UHFFFAOYSA-N 0.000 description 2
- 241001550224 Apha Species 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- 239000003377 acid catalyst Substances 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 229940106691 bisphenol a Drugs 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 238000006482 condensation reaction Methods 0.000 description 2
- UFULAYFCSOUIOV-UHFFFAOYSA-N cysteamine Chemical group NCCS UFULAYFCSOUIOV-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229960003151 mercaptamine Drugs 0.000 description 2
- 239000004431 polycarbonate resin Substances 0.000 description 2
- 229920005668 polycarbonate resin Polymers 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- OGYGFUAIIOPWQD-UHFFFAOYSA-N 1,3-thiazolidine Chemical compound C1CSCN1 OGYGFUAIIOPWQD-UHFFFAOYSA-N 0.000 description 1
- MLCQXUZZAXKTSG-UHFFFAOYSA-N 2-[2-(4-hydroxyphenyl)propan-2-yl]phenol Chemical compound C=1C=CC=C(O)C=1C(C)(C)C1=CC=C(O)C=C1 MLCQXUZZAXKTSG-UHFFFAOYSA-N 0.000 description 1
- CQOZJDNCADWEKH-UHFFFAOYSA-N 2-[3,3-bis(2-hydroxyphenyl)propyl]phenol Chemical compound OC1=CC=CC=C1CCC(C=1C(=CC=CC=1)O)C1=CC=CC=C1O CQOZJDNCADWEKH-UHFFFAOYSA-N 0.000 description 1
- VRVRGVPWCUEOGV-UHFFFAOYSA-N 2-aminothiophenol Chemical compound NC1=CC=CC=C1S VRVRGVPWCUEOGV-UHFFFAOYSA-N 0.000 description 1
- CGQWZVMVSJLPKO-UHFFFAOYSA-N 2-methylpyridine-3-thiol Chemical compound CC1=NC=CC=C1S CGQWZVMVSJLPKO-UHFFFAOYSA-N 0.000 description 1
- WQQJXTMFJYSLPT-UHFFFAOYSA-N 2-pyridin-3-ylethanethiol Chemical compound SCCC1=CC=CN=C1 WQQJXTMFJYSLPT-UHFFFAOYSA-N 0.000 description 1
- AXSMNPPSEOLAGB-UHFFFAOYSA-N 2-pyridin-4-ylethanethiol;hydrochloride Chemical compound Cl.SCCC1=CC=NC=C1 AXSMNPPSEOLAGB-UHFFFAOYSA-N 0.000 description 1
- IYGAMTQMILRCCI-UHFFFAOYSA-N 3-aminopropane-1-thiol Chemical compound NCCCS IYGAMTQMILRCCI-UHFFFAOYSA-N 0.000 description 1
- WCDSVWRUXWCYFN-UHFFFAOYSA-N 4-aminobenzenethiol Chemical compound NC1=CC=C(S)C=C1 WCDSVWRUXWCYFN-UHFFFAOYSA-N 0.000 description 1
- RIRRYXTXJAZPMP-UHFFFAOYSA-N 4-aminobutane-1-thiol Chemical compound NCCCCS RIRRYXTXJAZPMP-UHFFFAOYSA-N 0.000 description 1
- 125000004203 4-hydroxyphenyl group Chemical group [H]OC1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 206010062717 Increased upper airway secretion Diseases 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000005341 cation exchange Methods 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- MYRTYDVEIRVNKP-UHFFFAOYSA-N divinylbenzene Substances C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000005183 environmental health Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-M phenolate Chemical group [O-]C1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-M 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 208000026435 phlegm Diseases 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 150000008442 polyphenolic compounds Chemical class 0.000 description 1
- 235000013824 polyphenols Nutrition 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000006277 sulfonation reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 150000003548 thiazolidines Chemical class 0.000 description 1
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/11—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms
- C07C37/20—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms using aldehydes or ketones
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
A method for producing bisphenol a, comprising reacting phenol and acetone using an acid-type ion exchange resin partially modified with a sulfur-containing amine compound as a catalyst, wherein the acid-type ion exchange resin is washed with phenol before starting the reaction. According to the process of the present invention, bisphenol A which is less colored and has high quality and high purity can be produced.
Description
Technical field
The present invention relates to the method for a kind of preparation dihydroxyphenyl propane [2,2-two (4-hydroxyphenyl) propane], relate more specifically to prepare still less painted and have the method for high quality and highly purified dihydroxyphenyl propane.
Background technology
Known dihydroxyphenyl propane is as the engineering plastics important compound of the raw material of polycarbonate resin and poly-allylat thing (polyallylate) resin or Resins, epoxy for example, in recent years, tends to increase more and morely to the needs of dihydroxyphenyl propane.
Known by at acid catalyst and the promotor of using if desired for example sulphur compound in the presence of condensation excessive phenol and acetone prepare this dihydroxyphenyl propane.
Up to now, for example sulfuric acid and hydrochloric acid are as the acid catalyst of this reaction for mineral acid, and in recent years, Zeo-karb arouses attention and begins and uses with technical scale.
On the other hand, known have substituting group or do not have substituent mercaptan that for example thiomethyl alcohol, sulfur alcohol and Thiovanic acid are effective as the sulphur compound as promotor.These mercaptan have the speed of response of increasing and improve optionally effect.For example, in the preparation dihydroxyphenyl propane, mainly produce 2-(2-hydroxyphenyl)-2-(4-hydroxyphenyl) propane (ortho position and para-isomeride), produce triphenol and polyphenol in addition as byproduct of reaction.Especially, when as the raw material of polycarbonate resin and poly-allylat resin, need have these by products of less content and still less painted and have a highly purified dihydroxyphenyl propane.Therefore, use mercaptan, suppresses aforesaid by product and improves selectivity to increase speed of response as promotor.
Yet these mercaptan cause corrosion of equipment and produce for example smell of environmental health problem.Therefore, in recent years, the acid-type ion-exchange resin of multiple modification (wherein sulfur-containing group being introduced in the part sulfonic group of acid-type ion-exchange resin) is as the alternative of aforesaid Zeo-karb that is used in combination separately and mercaptan.
Is known with the partially modified acid-type ion-exchange resin of the amine compound of sulfur-bearing as a kind of (for example with reference to the unsettled publication number 35533/1982 of Japanese patent application and the unsettled publication number 246458/1999 of Japanese patent application) of the acid-type ion-exchange resin of these modifications.Yet, have such problem with the partially modified acid-type ion-exchange resin of the amine compound of sulfur-bearing, if promptly the impurity of sulfur-bearing or nitrogen component is separated out from above-mentioned resin, quality product variation so.
Disclosure of the Invention
Consider that situation is finished the present invention as mentioned above, the object of the invention provides by using with the partially modified acid-type ion-exchange resin catalyzer of the amine compound of sulfur-bearing phenol and acetone is reacted, and prepares less painted and have a method of high quality and highly purified dihydroxyphenyl propane.
The inventor finds after repeating further investigation, using with the amine compound of sulfur-bearing partially modified acid-type ion-exchange resin catalyzer that phenol and acetone are reacted preparing among the dihydroxyphenyl propane, by before beginning to react, realizing above-mentioned purpose of the present invention effectively with the aforesaid acid-type ion-exchange resin of wash phenol.Therefore finished the present invention.
That is to say that main points of the present invention are as described below.
1. method for preparing dihydroxyphenyl propane, wherein use with the amine compound of sulfur-bearing partially modified acid-type ion-exchange resin catalyzer make phenol and acetone reaction with the preparation dihydroxyphenyl propane among, before beginning to react, use aforesaid this acid-type ion-exchange resin of wash phenol.
2. the method for preparing dihydroxyphenyl propane of above-mentioned project 1, wherein continuous washing is reduced to 0.01 to 5ppm scope until the nitrogen component that phenol contained that is used for washing.
3. the method for preparing dihydroxyphenyl propane of above-mentioned project 1, wherein continuous washing is reduced to 0.05 to 3ppm scope until the nitrogen component that phenol contained that is used for washing.
4. the method for preparing dihydroxyphenyl propane of above-mentioned project 1 is wherein with 0.02 to 5 hour
-1Liquid time speed (LHSV) in the scope is used the wash phenol acid-type ion-exchange resin.
5. the method for preparing dihydroxyphenyl propane of above-mentioned project 1 is wherein with 0.05 to 2 hour
-1Liquid time speed (LHSV) in the scope is used the wash phenol acid-type ion-exchange resin.
6. the method for preparing dihydroxyphenyl propane of above-mentioned project 1 is wherein used the wash phenol acid-type ion-exchange resin under the temperature in 45 to 110 ℃ of scopes.
7. the method for preparing dihydroxyphenyl propane of above-mentioned project 1 is wherein used the wash phenol acid-type ion-exchange resin under the temperature in 55 to 90 ℃ of scopes.
Implement best mode of the present invention
Method of the present invention is wherein to use with the partially modified acid-type ion-exchange resin catalyzer of the amine compound of sulfur-bearing to come condensation reaction phenol and acetone to prepare the method for dihydroxyphenyl propane.Acid-type ion-exchange resin as the matrix of aforesaid modification acid-type ion-exchange resin is not had particular restriction, can use so far usually compound as bisphenol A catalyst.Especially, with regard to catalyst activity, for the sulfonic acid ion exchange resin of strong acid is suitable.
Above-mentioned sulfonic acid ion exchange resin there is not particular restriction, as long as it is to have sulfonic strong-acid ion exchange resin, can be for example sulfonated phenylethylene-divinyl benzene copolymer, sulfonation crosslinked styrene polymers, phenol-methane amide-sulfonate resin and phenyl aldehyde-sulfonate resin.
On the other hand, the amine compound of the sulfur-bearing that is used for partially modified acid-type ion-exchange resin is not as mentioned above had particular restriction, can use to be selected from usually any of the known compound that can be used for the modification acid-type ion-exchange resin suitably.The amine compound of above-mentioned sulfur-bearing comprises mercaptoalkylpyridin for example 3-mercapto-methyl pyridine, 3-(2-mercaptoethyl) pyridine and 4-(2-mercaptoethyl) pyridine, alkyl mercaptoamine is 2-mercaptoethylamine, 3-sulfydryl propylamine and 4-sulfydryl butylamine for example, thiazolidines is thiazolidine, 2 for example, 2-dimethylthiazole alkane, 2-methyl-2-phenyl thiazole alkane and 3-phenyl thiazole alkane and aminothiophenol be the 4-aminothiophenol for example.Wherein, preferred 2-mercaptoethylamine, 2,2-dimethylthiazole alkane and 4-(2-mercaptoethyl) pyridine.The amine compound of these sulfur-bearings can have for example adduct form of hydrochloric acid and quaternary ammonium salt of free state form or acid substance.
Method to the partially modified acid-type ion-exchange resin of the amine compound that uses these sulfur-bearings (it is aforesaid matrix) does not have particular restriction, can use common known method.
For example, at suitable solvent, preferred water-containing solvent for example makes the amine compound reaction of acid-type ion-exchange resin and sulfur-bearing in the water, obtaining required degree of modification (10 to 65%), thus can modified ion-exchange resin.Can carry out this reaction at normal temperature, if necessary, can carry out this reaction by heating.Make as the amino reaction in the sulfonic acid of ion-exchange group and the amine compound that is included in sulfur-bearing by this reaction, the group of sulfur-bearing is introduced in the part ion cation exchange groups, thus modified ion-exchange resin.Degree of modification is meant the sulfonic mole degree of modification with the amine compound modification acid-type ion-exchange resin of sulfur-bearing.
In the present invention, importantly will pack in the fixed-bed type reactor, begin to use wash phenol ion exchange resin before the reaction then with acid-type ion-exchange resin (only the being called ion exchange resin hereinafter) catalyzer of the amine compound modification of sulfur-bearing.
In the wash conditions of ion exchange resin, the scope of temperature is preferably 45 to 110 ℃, more preferably 55 to 90 ℃.If temperature is lower than 45 ℃, then phenol solidifies under certain conditions, if temperature surpasses 110 ℃, then ion exchange resin decomposes under certain conditions.
Liquid hourly space velocity degree (LHSV) is preferably 0.02 to 5 hour
-1, more preferably 0.05 to 2 hour
-1If it was less than 0.02 hour
-1, spended time and efficient is relatively poor under certain conditions then.If it was above 5 hours
-1, then need a large amount of phenol under certain conditions.
Wash as mentioned above be reduced to until the nitrogen component that phenol contained that is used for washing preferred 0.01 to 5ppm, more preferably 0.05 to 3ppm scope.If it is less than 0.01ppm, then washing the time and the phenol amount that need increases, so it is disadvantageous economically.If it surpasses 5ppm, the degradation of product under certain conditions then.
Among the condensation reaction of phenol of the present invention and acetone, can use the continuous fixed bed reaction or continuous system, wherein phenol and acetone are added in the reactor that the above-mentioned ion exchange resin of using wash phenol is housed and reaction continuously.In this case, reactor can be a post, two or more posts of perhaps can serial or parallel connection arranging.Is particularly advantageous according to industrial point two or more reactors that above-mentioned ion exchange resin is housed that are connected in series to adopt the fixed bed multistage continuous reaction system.
With the reaction conditions in this continuous fixed bed reaction or continuous system of explanation.
At first, selecting the acetone/phenol mol ratio usually is 1/30 to 1/3, preferred 1/20 to 1/5.If this mol ratio is less than 1/30, speed of response may be too slow, if it is greater than 1/3, the selectivity that produces more impurity and dihydroxyphenyl propane is easy to reduce.
In addition, the selective reaction temperature is 40 to 150 ℃ usually, preferred 55 to 100 ℃.If said temperature is lower than 40 ℃, speed of response is slower, and reaction liquid viscosity increases a lot in addition.Under certain situation, may cause solidifying.If it surpasses 150 ℃, the selectivity of become restive reaction and dihydroxyphenyl propane reduces.In addition, the ion exchange resin of catalyzer decomposes or variation under certain conditions.In addition, selecting the LHSV (liquid hourly space velocity degree) of raw mix usually is 0.2 to 30 hour
-1, preferred 0.5 to 20 hour
-1
In the methods of the invention, the reaction mixture of from reactor, discharging with the known method aftertreatment, and take out dihydroxyphenyl propane.An example of this aftertreatment will be described below.At first, before crystallization, concentrate.Particular restriction should not arranged to concentrating condition, under the pressure of 130 to 170 ℃ temperature and 13 to 53kPa, concentrate usually.If temperature is lower than 130 ℃, then need high vacuum, if it surpasses 170 ℃, then impurity increases or produces painted.The concentration of the dihydroxyphenyl propane in the concentration residue advantageously is 25 to 40wt%.If concentration is less than 25wt%, the rate of recovery of dihydroxyphenyl propane reduces, if it surpasses 40wt%, is difficult to shift slurry after the crystallization.
Usually employing utilizes the latent heat of vaporization under reduced pressure to carry out refrigerative vacuum cooling crystallization method and carry out the crystallization of dihydroxyphenyl propane and phenol adducts from concentration residue.In the vacuum cooling crystallization method, the water of 3 to 30 quality % joined in the above-mentioned concentration residue and usually carry out crystallization treatment in 40 to 70 ℃ temperature and 3 to 13kPa pressure.If the add-on of above-mentioned water is less than 3 quality %, the capacity that then reduces phlegm and internal heat is unsatisfactory, if it surpasses 20 quality %, then the solution loss of dihydroxyphenyl propane increases.Therefore, not preferred.In addition, if Tc is lower than 40 ℃, then the viscosity of crystallized liquid increases and may cause it to solidify, if it surpasses 70 ℃, then the solution loss of dihydroxyphenyl propane increases.Therefore, not preferred.
Then, separate crystalline dihydroxyphenyl propane like this and phenol adducts, carry out carrying out washing treatment with phenol then with known method.Then, the adducts through carrying out washing treatment is carried out separating treatment to be separated into dihydroxyphenyl propane and phenol.In this case, selecting temperature usually is 130 to 200 ℃, and preferred 150 to 180 ℃, on the other hand, usually selective pressure is 3 to 20kPa.
Basically remove residual phenol in the dihydroxyphenyl propane that obtains through separating treatment by stripping fully, thereby obtain high-quality dihydroxyphenyl propane.
Next, reference example is illustrated in greater detail the present invention, but the present invention never is limited to these embodiment.
Embodiment 1
1, suspend in the 000ml flask and stirring 200ml (water swollen) Zeo-karb (Duolite SC400, by Sumitomo Chemical Ind.Co., Ltd. produces) and 400ml ion exchanged water.In 30 minutes to the solution that wherein is added dropwise to 8g hydrochloric acid 4-(2-mercaptoethyl) pyridine and 500ml ion exchanged water.After being added dropwise to complete, further stirred solution is one hour, then by the filtering separation resin.Test the acid amount of filtering resin by titration, thereby find that 17% sour site is modified.
Phenol by allowing 23ml/ hour is at 70 ℃ and 0.3 hour
-1The LHSV current downflow, and in fixed bed flow system washing 140ml this resin 72 hours.Nitrogen concentration in the phenol when finishing washing is 0.3ppm.
After finishing washing, with 75 ℃ temperature of reaction and 4 hours
-1LHSV 15ml/ hour acetone and 277ml/ hour phenol [acetone/phenol (mol ratio)=1/15] are reacted.Reaction result is 98% acetone conversion, 96.5% dihydroxyphenyl propane selectivity and 2.5% ortho position and para-isomeride.The water of removing unreacted acetone, a part of phenol and generation by distillation is to obtain 130 ℃ crystallization raw material.The water of 10 quality % is joined in the crystallization raw material to cool off it to 80 ℃, and cooling solution to the 50 ℃ while under reduced pressure removes and anhydrates with further depositing crystalline then.Then, from phenol adducts and the mother liquor (water content: 4 quality %s) of liquid separation solid matter to obtain dihydroxyphenyl propane.Further molten adduct is removed phenol then.So obtain the APHA colour 10 minutes of dihydroxyphenyl propane 250 ℃ of measurements, find that it is 10.Dihydroxyphenyl propane has 99.9% purity and ortho position and the para-isomeride of 240ppm.
Embodiment 2
With with embodiment 1 in the preparation of identical method with 2, the catalyzer of 2-dimethylthiazole alkane modification.In this catalyzer, 23% sour site is modified.
Phenol by allowing 40ml/ hour is at 70 ℃ and 0.5 hour
-1The LHSV current downflow, and in fixed bed flow system washing 140ml this resin 72 hours.Nitrogen concentration in the phenol when finishing washing is 0.2ppm.
After finishing washing, with 75 ℃ temperature of reaction and 4 hours
-1LHSV 23ml/ hour acetone and 277ml/ hour phenol [acetone/phenol (mol ratio)=1/10] are reacted.Reaction result is 60% acetone conversion, 96.2% dihydroxyphenyl propane selectivity and 2.8% ortho position and para-isomeride.
Then, with embodiment 1 in identical method purify.So obtain the APHA colour 10 minutes of dihydroxyphenyl propane 250 ℃ of measurements, find that it is 10.Dihydroxyphenyl propane has 99.9% purity and ortho position and the para-isomeride of 240ppm.
About aforesaid LHSV, when expanding when changing to the phenol swelling from water-soluble, the catalyzer of modification is reduced to about 56% and about 52% respectively, therefore determines catalyst volume in phenol swelling or raw mix swelling according to raw material phenol or raw mix.
Industrial applicibility
According to the method for preparing bisphenol-A of the present invention, by using the amines section with sulfur-bearing Divide the acid-type ion-exchange resin catalyst of modification to make phenol and acetone reaction, can prepare still less Painted and have high-quality and a highly purified bisphenol-A.
Claims (7)
1. method for preparing dihydroxyphenyl propane, wherein use with the amine compound of sulfur-bearing partially modified acid-type ion-exchange resin catalyzer make phenol and acetone reaction with the preparation dihydroxyphenyl propane among, before beginning reaction, use the described acid-type ion-exchange resin of wash phenol.
2. the described method for preparing dihydroxyphenyl propane of claim 1, wherein continuous washing is reduced to 0.01 to 5ppm until the nitrogen component that phenol contained that is used for washing.
3. the described method for preparing dihydroxyphenyl propane of claim 1, wherein continuous washing is reduced to 0.05 to 3ppm until the nitrogen component that phenol contained that is used for washing.
4. the described method for preparing dihydroxyphenyl propane of claim 1 is wherein used the wash phenol acid-type ion-exchange resin with the liquid hourly space velocity degree (LHSV) in 0.02 to 5 hour-1 scope.
5. the described method for preparing dihydroxyphenyl propane of claim 1 is wherein used the wash phenol acid-type ion-exchange resin with the liquid hourly space velocity degree (LHSV) in 0.05 to 2 hour-1 scope.
6. the described method for preparing dihydroxyphenyl propane of claim 1 is wherein used the wash phenol acid-type ion-exchange resin under the temperature in 45 to 110 ℃ of scopes.
7. the described method for preparing dihydroxyphenyl propane of claim 1 is wherein used the wash phenol acid-type ion-exchange resin under the temperature in 55 to 90 ℃ of scopes.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002353940A JP4338966B2 (en) | 2002-12-05 | 2002-12-05 | Method for producing bisphenol A |
| JP353940/2002 | 2002-12-05 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1717379A true CN1717379A (en) | 2006-01-04 |
Family
ID=32463318
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200380104506 Pending CN1717379A (en) | 2002-12-05 | 2003-12-01 | Process for preparing bisphenol A |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP4338966B2 (en) |
| CN (1) | CN1717379A (en) |
| TW (1) | TWI328575B (en) |
| WO (1) | WO2004050593A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1927464B (en) * | 2006-09-26 | 2010-09-29 | 蓝星化工新材料股份有限公司无锡树脂厂 | Pretreatment method for preventing deactivation of diphenol propane synthesis reaction catalyst |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4423252A (en) * | 1980-08-07 | 1983-12-27 | Mitsubishi Chemical Industries Limited | Process for preparing bisphenols |
| JPH09176069A (en) * | 1995-12-26 | 1997-07-08 | Nippon Steel Chem Co Ltd | Production of bisphenols |
| JPH11246458A (en) * | 1998-02-26 | 1999-09-14 | Mitsubishi Chemical Corp | Production of bisphenol |
| JP2000143565A (en) * | 1998-11-12 | 2000-05-23 | Idemitsu Petrochem Co Ltd | Pretreatment of catalyst for producing bisphenol a and production of bisphenol a having stable hue |
| JP2001199919A (en) * | 2000-01-18 | 2001-07-24 | Idemitsu Petrochem Co Ltd | Method for producing bisphenol a |
| JP4689059B2 (en) * | 2001-02-28 | 2011-05-25 | 出光興産株式会社 | Method for producing bisphenol A |
-
2002
- 2002-12-05 JP JP2002353940A patent/JP4338966B2/en not_active Expired - Lifetime
-
2003
- 2003-12-01 WO PCT/JP2003/015334 patent/WO2004050593A1/en active Application Filing
- 2003-12-01 CN CN 200380104506 patent/CN1717379A/en active Pending
- 2003-12-03 TW TW92134079A patent/TWI328575B/en not_active IP Right Cessation
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1927464B (en) * | 2006-09-26 | 2010-09-29 | 蓝星化工新材料股份有限公司无锡树脂厂 | Pretreatment method for preventing deactivation of diphenol propane synthesis reaction catalyst |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2004182682A (en) | 2004-07-02 |
| TW200412338A (en) | 2004-07-16 |
| JP4338966B2 (en) | 2009-10-07 |
| TWI328575B (en) | 2010-08-11 |
| WO2004050593A1 (en) | 2004-06-17 |
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