CN102886277A - Preparation method of modified catalyst for bisphenol A preparation - Google Patents
Preparation method of modified catalyst for bisphenol A preparation Download PDFInfo
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- CN102886277A CN102886277A CN2012103713001A CN201210371300A CN102886277A CN 102886277 A CN102886277 A CN 102886277A CN 2012103713001 A CN2012103713001 A CN 2012103713001A CN 201210371300 A CN201210371300 A CN 201210371300A CN 102886277 A CN102886277 A CN 102886277A
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- acid
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- amines
- bearing
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- 239000003054 catalyst Substances 0.000 title claims abstract description 48
- 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 33
- 238000002360 preparation method Methods 0.000 title claims description 71
- 239000002253 acid Substances 0.000 claims abstract description 66
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 57
- 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 56
- 239000011593 sulfur Substances 0.000 claims abstract description 56
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 56
- 239000003456 ion exchange resin Substances 0.000 claims abstract description 53
- 229920003303 ion-exchange polymer Polymers 0.000 claims abstract description 53
- 239000007864 aqueous solution Substances 0.000 claims abstract description 27
- -1 amine compound Chemical class 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 9
- 230000002378 acidificating effect Effects 0.000 claims abstract description 7
- 150000001412 amines Chemical class 0.000 claims description 52
- 238000012986 modification Methods 0.000 claims description 34
- 230000004048 modification Effects 0.000 claims description 34
- 239000007788 liquid Substances 0.000 claims description 30
- 239000011260 aqueous acid Substances 0.000 claims description 19
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 14
- 229940106691 bisphenol a Drugs 0.000 claims description 13
- BDHFUVZGWQCTTF-UHFFFAOYSA-N sulfonic acid Chemical compound OS(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-N 0.000 claims description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- 238000002347 injection Methods 0.000 claims description 9
- 239000007924 injection Substances 0.000 claims description 9
- 230000001351 cycling effect Effects 0.000 claims description 8
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 7
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 3
- 235000019253 formic acid Nutrition 0.000 claims description 3
- 150000007522 mineralic acids Chemical class 0.000 claims description 3
- 150000007524 organic acids Chemical class 0.000 claims description 3
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 2
- 239000004327 boric acid Substances 0.000 claims description 2
- 150000003548 thiazolidines Chemical class 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 125000005358 mercaptoalkyl group Chemical group 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 12
- 229910019142 PO4 Inorganic materials 0.000 description 11
- 239000010452 phosphate Substances 0.000 description 11
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 150000001335 aliphatic alkanes Chemical class 0.000 description 8
- 239000011347 resin Substances 0.000 description 8
- 229920005989 resin Polymers 0.000 description 8
- 238000011156 evaluation Methods 0.000 description 7
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 6
- 239000003729 cation exchange resin Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000006386 neutralization reaction Methods 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethanethiol Chemical compound CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 3
- 238000006073 displacement reaction Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 230000008961 swelling Effects 0.000 description 3
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 3
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- SLGWESQGEUXWJQ-UHFFFAOYSA-N formaldehyde;phenol Chemical compound O=C.OC1=CC=CC=C1 SLGWESQGEUXWJQ-UHFFFAOYSA-N 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- 229920001568 phenolic resin Polymers 0.000 description 2
- VRVRGVPWCUEOGV-UHFFFAOYSA-N 2-aminothiophenol Chemical compound NC1=CC=CC=C1S VRVRGVPWCUEOGV-UHFFFAOYSA-N 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical class C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- KLSLBUSXWBJMEC-UHFFFAOYSA-N 4-Propylphenol Chemical compound CCCC1=CC=C(O)C=C1 KLSLBUSXWBJMEC-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
- 229930185605 Bisphenol Natural products 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- 229940092714 benzenesulfonic acid Drugs 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000000354 decomposition reaction 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
- 239000003822 epoxy resin Substances 0.000 description 1
- CCIVGXIOQKPBKL-UHFFFAOYSA-N ethanesulfonic acid Chemical compound CCS(O)(=O)=O CCIVGXIOQKPBKL-UHFFFAOYSA-N 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 229920001230 polyarylate Polymers 0.000 description 1
- 229920005668 polycarbonate resin Polymers 0.000 description 1
- 239000004431 polycarbonate resin Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- WHMDPDGBKYUEMW-UHFFFAOYSA-N pyridine-2-thiol Chemical class SC1=CC=CC=N1 WHMDPDGBKYUEMW-UHFFFAOYSA-N 0.000 description 1
- FFWJHVGUAKWTKW-UHFFFAOYSA-N pyridine-3-thiol Chemical compound SC1=CC=CN=C1 FFWJHVGUAKWTKW-UHFFFAOYSA-N 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006277 sulfonation reaction Methods 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
- B01J31/08—Ion-exchange resins
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
- B01J31/08—Ion-exchange resins
- B01J31/10—Ion-exchange resins sulfonated
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
- B01J2231/34—Other additions, e.g. Monsanto-type carbonylations, addition to 1,2-C=X or 1,2-C-X triplebonds, additions to 1,4-C=C-C=X or 1,4-C=-C-X triple bonds with X, e.g. O, S, NH/N
- B01J2231/341—1,2-additions, e.g. aldol or Knoevenagel condensations
- B01J2231/347—1,2-additions, e.g. aldol or Knoevenagel condensations via cationic intermediates, e.g. bisphenol A type processes
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A process for producing a modified catalyst for bisphenol A production, which comprises partially modifying a strongly acidic ion exchange resin with a sulfur-containing amine compound, characterized by charging the strongly acidic ion exchange resin in a fixed bed reactor, injecting an acid aqueous solution and a sulfur-containing amine compound in an amount at which the acid aqueous solution is in equilibrium with the acid aqueous solution to modify the strongly acidic ion exchange resin, and thereby producing a modified catalyst for bisphenol A production, which does not damage the strongly acidic ion exchange resin, is uniformly modified with the strongly acidic ion exchange resin, and has excellent catalytic performance.
Description
The application be based on the applying date be that August 30, application number in 2004 are 200480025087.2, denomination of invention is dividing an application that the application of " bisphenol-A preparation with the preparation method of modified catalyst " is submitted to.
Technical field
The present invention relates to for bisphenol-A [2, two (4-hydroxyphenyl) propane of 2-] preparation method of catalyst of preparation, in detail, relate to the preparation method that modified catalyst is used in the amines bisphenol-A preparation that strong-acid ion exchange resin is partially modified that comprises the usefulness sulfur-bearing.
Background technology
Known bisphenol-A is that its demand has increasing trend in recent years as the important compound of the raw material of the engineering plastics such as polycarbonate resin or polyarylate resin or epoxy resin etc.
When this bisphenol-A of preparation, to use as catalyst with the partially modified strong-acid ion exchange resin of the amines of sulfur-bearing, as the preparation method of this catalyst, adopt the amines of disposable interpolation sulfur-bearing in fixed bed reactors, with the sulfonic acid ion exchange resin modification.
Usually, the amines of disposable interpolation sulfur-bearing in fixed bed reactors, during with the sulfonic acid ion exchange resin modification, the amines of sulfur-bearing mobile under the effect of acid (to sulfonic absorption, disengaging and movement from sulfonic group) is as the sulfonic group the resin of fixed bed.At this moment, the amines of sulfur-bearing is mobile to outlet from the entrance of fixed bed reactors, can not be with equably modification of sulfonic acid ion exchange resin but only move 1 time.Namely, when the amines of sulfur-bearing moves, because the concentration of the amines of sulfur-bearing is high concentration (degree of modification is about 30～80% high degree of modification) in the outlet of fixed bed reactors, be low concentration (degree of modification is about 5～30% low degree of modification) at the entrance of fixed bed reactors, therefore only mobile have for 1 time the sulfonic acid ion exchange resin can not be by the problem of modification equably.
Cationic ion-exchange resin fixed bed by the neutralization of the amines of sulfur-bearing can utilize the whole bag of tricks to be prepared, and for example discloses acid cation exchange resin by preparation method's (for example with reference to Unexamined Patent 6-296871 communique, JP 2001-286770 communique, Unexamined Patent 8-40961 communique and JP 2001-288132 communique) of the acid cation exchange resin fixed bed of the aminate of sulfur-bearing neutralization.The method (for example with reference to JP 53-14680 communique) that the amine compound aqueous solution that makes the sulfur-bearing that has added hydrochloric acid circulates in the resin fixed bed is disclosed in addition, if but use a large amount of hydrochloric acid, then might etching apparatus.
As the preparation method for the preparation of the catalyst of bisphenols, disclose following several: on one side on one side the ion exchange resin in the stirring reaction container inject sulfur-bearing amines weak solution method (for example with reference to Unexamined Patent 9-24279 communique), in reactor, fill acid cation exchange resin, in the amine compound aqueous solution of sulfur-bearing of packing into or after packing into, pass into the method (for example with reference to JP 2000-254523 communique) that bubble neutralizes acid cation exchange resin equably from reactor lower part.But the former situation need to be stored the equipment of extensive weak solution, and owing to be the batch (-type) preparation of stirring by impeller, therefore not only the ion exchange resin generation is damaged, and needs again filling ion-exchange resin owing to formed fixed bed.In the latter's the situation, carry out more than pH6 owing to prepare, thus the homogenization of the amines of sulfur-bearing difficulty, owing to this reason has formed inhomogenous modified catalyst, the problem that therefore has catalytic performance to descend.
Summary of the invention
The present invention finishes in view of the above fact, its purpose is to provide that strong-acid ion exchange resin is not damaged, strong-acid ion exchange resin equably the bisphenol-A preparation of modification and catalytic performance excellence with the preparation method of modified catalyst.
The inventor has carried out repeatedly in depth research in order to solve above-mentioned problem, found that, by in fixed bed reactors, filling strong-acid ion exchange resin, inject aqueous acid and reach the amines of sulfur-bearing of the concentration amount of balance at this aqueous acid, carry out the modification of strong-acid ion exchange resin, can achieve the above object.The present invention is found to be the basis with these and finishes.
Namely, the invention provides the bisphenol-A preparation preparation method of modified catalyst, it comprises with the amines of sulfur-bearing strong-acid ion exchange resin is partially modified, it is characterized in that, in fixed bed reactors, fill strong-acid ion exchange resin, to injected water solution wherein with in this aqueous acid, reach the amines of sulfur-bearing of the concentration amount of balance, with the strong-acid ion exchange resin modification.
The specific embodiment
As the strong-acid ion exchange resin that uses among the present invention, can enumerate the sulfonic acid ion exchange resins such as sulfonated phenylethylene-divinyl benzene copolymer, sulfonation crosslinked styrene polymers, phenol formaldehyde (PF)-sulfonate resin, benzaldehyde-sulfonate resin etc.Strong-acid ion exchange resin is filled in the fixed bed reactors.Since directly ion exchange resin is packed into fixed bed, therefore not damaged at the modified process intermediate ion exchanger resin of ion exchange resin, and owing to also need not transfer from batch reactor or modified catalyst preparation vessel, therefore favourable on preparation cost.
Among the present invention, amines as the sulfur-bearing that is used for the strong-acid ion exchange resin modification, can enumerate the mercaptoalkyl amines, 2 such as mercaptopyridine class, 2-MEA such as 3-mercaptopyridine, the pyridine alkanethiol classes such as the aminothiophenol classes such as the thiazolidines such as 2-dimethylthiazole alkane, 4-aminothiophenol, 4-pyridine ethyl mercaptan etc.Wherein, preferred 4-pyridine ethyl mercaptan, 2,2-dimethylthiazole alkane and 2-MEA.Can use separately a kind or will be used in combination more than 2 kinds.
Utilize the degree of modification of strong-acid ion exchange resin of the amines of sulfur-bearing to be generally about 5～45%, be preferably 8～35%, more preferably 10～30%.Be located at about 45% by the upper limit with this degree of modification, catalyst activity can not reduce; By lower limit is located at about 5%, does not have catalyst life and shorten, perhaps the situation of catalyst activity or selection rate step-down.Here, " degree of modification " of strong-acid ion exchange resin refer to utilize the amines that closes sulphur strong-acid ion exchange resin the highly acid ion-exchange group the mole degree of modification.
As acid, can use organic acid or inorganic acid.Can enumerate the aromatic sulphonic acid classes such as benzene sulfonic acid, p-methyl benzenesulfonic acid, xylene monosulfonic acid as organic acid, the alkyl sulfonic acid classes such as methanesulfonic acid, ethyl sulfonic acid, acetic acid and formic acid etc.Wherein optimization aromatic sulphonic acids, more preferably p-methyl benzenesulfonic acid.In addition, the acidic aqueous solution that also preferably in the washing of sulfonic acid ion exchange resin is processed, obtains.As inorganic acid, can enumerate phosphoric acid, boric acid and sulfuric acid etc., preferably phosphoric acid.Use aromatic sulphonic acid or phosphoric acid, have the hardly advantage of etching apparatus.
The concentration of aqueous acid when the strong acid such as use aromatic sulphonic acid class, alkyl sulfonic acid class and sulfuric acid, is generally about 0.01～5 quality %, is preferably 0.03～2 quality %.When the weak acid such as use acetic acid, formic acid and phosphoric acid, be generally about 0.01～8 quality %, be preferably 0.05～3 quality %.By the upper limit with acid concentration, be located at about 8 quality % when being located at about 5 quality %, for weak acid during for strong acid, in aqueous acid, reach balance sulfur-bearing amines concentration (below, be called " equilibrium concentration of the amines of sulfur-bearing ") can not increase, therefore the loss of the amines of the use amount of acid and sulfur-bearing is all lacked, and is preferred economically.In addition, be located at about 0.01 quality % by the lower limit with acid concentration, it is low that the equilibrium concentration of the amines of sulfur-bearing can not become, so the used time of modification can not become long.
Here, the equilibrium concentration of the amines of sulfur-bearing is following in the aqueous acid obtains.For example, repeatedly add acid solution in the strong-acid ion exchange resin after the water swelling, stir, filter, with acid solution water is replaced, while then stir the 10 quality % aqueous solution that ion exchange resin slowly adds the amines of sulfur-bearing.So far the catalyst preparation for carrying out with batch (-type)., the part of this aqueous solution as sample, carried out total nitrogen analysis, try to achieve the concentration of the amines of sulfur-bearing from nitrogen pool concentration thereafter.
Among the present invention, preferably before the modification of strong-acid ion exchange resin, first with the water displacement that contains in the fixed bed (strong-acid ion exchange resin) of aqueous acid with fixed bed reactors.Its reason is, the water swelling type of the gel-type ion-exchange resin that uses as strong-acid ion exchange resin contains the water about 50 quality %.By carrying out this displacement, in the time of will carrying out cycling and reutilization from the aqueous acid that the outlet of reactor is flowed out, can reach acid concentration and keep certain effect.
The temperature of catalyst preparation (utilizing the modification of strong-acid ion exchange resin of the amines of sulfur-bearing) normally about 0～120 ℃, is preferably 20～100 ℃.Be located at about 120 ℃ by the upper limit with the catalyst preparation temperature, can not produce the decomposition of ion exchange resin; By lower limit being located at about 0 ℃, can not produce the problem that aqueous acid solidifies in addition.
The injection of the amines of aqueous acid and sulfur-bearing normally is dissolved in by injecting amines with sulfur-bearing that preparation liquid that aqueous acid forms carries out.The injection rate of this aqueous solution is considered from the viewpoint of acid concentration or preparation time, is generally 0.1～20h in LHSV (liquid hourly space velocity (LHSV))
-1About, be preferably 0.2～10h
-1, 0.4～5h more preferably
-1The linear velocity of this preparation liquid is generally about 0.1～100m/h, is preferably 0.2～50m/h, more preferably 0.5～20m/h.
Catalyst prepares the needed time by decisions such as the equilibrium concentration of the amines of kind, the sulfur-bearing of the concentration of acid in the aqueous acid or acid, the degree of modification of strong-acid ion exchange resin of amines that utilizes sulfur-bearing and LHSV.The amount of the amines of the sulfur-bearing that consumes in the catalyst preparation is determined by degree of modification.The concentration of the amines of the sulfur-bearing that injects in the fixed bed reactors is the equilibrium concentration of the amines of sulfur-bearing.
In the catalyst preparation, the preparation liquid of a certain amount of amines that is dissolved with sulfur-bearing in the aqueous acid entrance from fixed bed reactors is injected, and the preparation liquid that has passed through to be filled in the strong-acid ion exchange resin in this reactor flows out from the outlet of fixed bed reactors.The processing method of this preparation liquid has the method for discarded or cycling and reutilization, but considers the method for preferred cycle recycling from the viewpoint that reduces waste liquid amount, reduces the use amount of the amines of sulfur-bearing and acid.When carrying out cycling and reutilization, measure the concentration of the amines of the sulfur-bearing from the preparation liquid that the outlet of fixed bed reactors is flowed out, append the amines of sulfur-bearing that the amines that makes sulfur-bearing reaches the amount of equilibrium concentration.The concentration of the amines of sulfur-bearing can by mensuration contain sulfur-bearing amines and acid preparation liquid in nitrogen concentration obtain.Because total injection length is roughly determined by the equilibrium concentration of the amines of the sulfur-bearing that injects or the degree of modification of ion exchange resin, so the measuring interval of the amines concentration of sulfur-bearing can be 2～20 hours usually.When circulation contains the preparation liquid of the amines of sulfur-bearing and acid, can be made as LHSV same as described above and linear velocity to the injection rate (internal circulating load) of fixed bed reactors.
In the catalyst preparation, the liquid stream of the preparation liquid of the amines that contains acid and sulfur-bearing in fixed bed reactors can be flow downward and make progress and flow any.But the injection rate for preparing liquid when flowing owing to making progress increases, the expansion of ion exchange resin (floating, mobile etc.) uprise, so preferably flow downward among the present invention.
Use the as above modified catalyst of preparation, prepare bisphenol-A take phenol and acetone as raw material.In fixed bed reactors, in raw material, add modified catalyst, can the roughly the same condition of condition (LHSV and linear velocity) when preparing with catalyst add.Usage ratio for phenol and acetone is not particularly limited, but considers that from being easy to the aspects such as bisphenol-A that purifying generates or economy the amount of preferred unreacted acetone is as far as possible little, and therefore to use phenol be favourable to be in excess in stoichiometric amount.Usually, per 1 mole of acetone is used about 3～30 moles, preferred 5～15 moles phenol.Reaction temperature is generally about 40～150 ℃, is preferably 60～110 ℃ scope.
The condensation reaction of phenol and acetone can be any of batch-type and continous way, but in being filled with the reaction tower of modified catalyst, preferred continuous supplying makes the continuous fixed bed reaction or continuous mode of their reactions to phenol and acetone.
By the present invention, can prepare that strong-acid ion exchange resin is not damaged, the time of equably modification of strong-acid ion exchange resin, homogeneous modification is short and the modified catalyst that is used for the bisphenol-A preparation of catalytic performance excellence.
Then, more specifically describe the present invention by embodiment, but the present invention is not subjected to any restriction of these embodiment.
Embodiment 1
As reactor, use the reactor series connection with 4 internal diameter 10mm, long 1200mm, outlet side is linked to each other with pipe arrangement with entrance side, make the reactor that is circulated to entrance side from the preparation liquid of reactor outlet discharge.In this reactor, fill sulfonic acid ion exchange resin (Mitsubishi Chemical Ind's system, the trade name: Diaion SK-104), wash in the mode that flows downward with 1500ml distilled water of 300ml water swelling state.Then, with 0.3 quality % phosphate aqueous solution with in the reactor and the water displacement in the pipe arrangement.To add 2,2-dimethylthiazole alkane in 0.3 quality % phosphate aqueous solution, to make the concentration of 2,2-dimethylthiazole alkane be the preparation liquid that 117 quality ppm form, with 300ml/h (LHSV=1h
-1, in the injecting reactor of linear velocity=3.8m/h).The target degree of modification that utilizes 2,2-dimethylthiazole alkane is 23%, injects continuously above-mentioned preparation liquid 298 hours, carries out the modification of above-mentioned ion exchange resin under 25 ℃.The above-mentioned preparation liquid that flows out from the 4th reactor is circulated in the 1st reactor to be recycled.At this moment, utilize per 20 hours of total blood urea/nitrogen analyzer measure 1 time from the preparation liquid that the 4th reactor outlet flows out 2,2-dimethylthiazole alkane content appends 2 of the amount that keeps 117 quality ppm, 2-dimethylthiazole alkane.
After the preparation liquid injection end that forms in 2, the 2-dimethylthiazole alkane adding phosphate aqueous solution, from reactor, take out modified catalyst, phosphate aqueous solution is removed with distilled water.Make this modified catalyst dry, carry out the mensuration of degree of modification with following method.The results are shown in table 1.
The mensuration of＜degree of modification 〉
Use sodium hydrate aqueous solution by the titration measuring acid equivalent, utilize following formula to calculate neutralization ratio, with this neutralization ratio as degree of modification.
Neutralization ratio (%)=100 * acid equivalent (meq./g) of the acid equivalent of 1-[modified resin (meq./g)/unmodified resin] }
Embodiment 2
In embodiment 1, except injected in continuous 79 hours with 1.0 quality % phosphate aqueous solutions replace that 0.3 quality % phosphate aqueous solution prepares, contain 2, outside the preparation liquid of 2-dimethylthiazole alkane 440 quality ppm, all the other operate similarly to Example 1, obtain modified catalyst.The modified catalyst that obtains is carried out the evaluation identical with embodiment 1.The results are shown in table 1.
Embodiment 3
In embodiment 1, except use contains the preparation liquid of the 2-MEA 52 quality ppm that substitute 2,2-dimethylthiazole alkane, the target degree of modification is made as 15%, injects outside this preparation liquid in continuous 280 hours, and all the other and embodiment 1 same operation obtain modified catalyst.The modified catalyst that obtains is carried out the evaluation identical with embodiment 1.The results are shown in table 1.
Embodiment 4
In embodiment 1, except injected in continuous 266 hours with the 0.3 quality % p-methyl benzenesulfonic acid aqueous solution replace that 0.3 quality % phosphate aqueous solution prepares, contain 2, outside the preparation liquid of 2-dimethylthiazole alkane 131 quality ppm, all the other operate similarly to Example 1, obtain modified catalyst.The modified catalyst that obtains is carried out the evaluation identical with embodiment 1.The results are shown in table 1.
Comparative example 1
In embodiment 1, except injecting 2 of total consumption 10.1g with 0.5 hour, 2-dimethylthiazole alkane, outside time cycling and reutilization 0.3 quality % phosphate aqueous solution similarly to Example 1, all the other operate similarly to Example 1, obtain modified catalyst.The modified catalyst that obtains is carried out the evaluation identical with embodiment 1.The results are shown in table 1.
Comparative example 2
In embodiment 2, except injecting 2 of total consumption 10.1g with 0.5 hour, 2-dimethylthiazole alkane, outside time cycling and reutilization 1.0 quality % phosphate aqueous solutions similarly to Example 2, all the other operate similarly to Example 2, obtain modified catalyst.The modified catalyst that obtains is carried out the evaluation identical with embodiment 1.The results are shown in table 1.
Comparative example 3
In embodiment 3, except injecting 2 of total consumption 4.2g with 0.5 hour, 2-MEA, outside time cycling and reutilization 0.3 quality % phosphate aqueous solution similarly to Example 1, all the other operate similarly to Example 3, obtain modified catalyst.The modified catalyst that obtains is carried out the evaluation identical with embodiment 1.The results are shown in table 1.
Comparative example 4
In embodiment 4, except injecting 2 of total consumption 10.1g with 0.5 hour, 2-dimethylthiazole alkane, outside time cycling and reutilization 0.3 quality % phosphate aqueous solution similarly to Example 4, all the other operate similarly to Example 4, obtain modified catalyst.The modified catalyst that obtains is carried out the evaluation identical with embodiment 1.The results are shown in table 1.
Table 1
Industrial applicability
By the present invention, can provide the modified catalyst that is used for the bisphenol-A preparation of catalytic performance excellence.
Claims (14)
1. bisphenol-A prepares the preparation method with modified catalyst, it is characterized in that, strong-acid ion exchange resin being carried out the partially modified bisphenol-A that forms with the amines of sulfur-bearing in preparation prepares in the usefulness method of modified catalyst, in fixed bed reactors, fill strong-acid ion exchange resin, to wherein injecting aqueous acid, amines with the sulfur-bearing of the concentration amount that in this aqueous acid, reaches balance, the amines that appends the sulfur-bearing from the preparation liquid that reactor outlet flows out reaches the amines of the sulfur-bearing of equilibrium concentration amount, make preparation liquid cycling and reutilization, with the strong-acid ion exchange resin modification.
2. preparation method as claimed in claim 1, aforementioned equilibrium concentration is the equilibrium concentration of the target degree of modification that reaches strong-acid ion exchange resin in aqueous acid.
3. preparation method as claimed in claim 2, wherein aforementioned target degree of modification is 5～45 % by mole
4. preparation method as claimed in claim 1, wherein the amines of sulfur-bearing is more than one in selected from mercapto alkyl amine, thiazolidines and the mercaptoalkylpyridin class.
5. preparation method as claimed in claim 1 is wherein, sour for being selected from the organic acid of aromatic sulphonic acid class, alkyl sulfonic acid class, acetic acid and formic acid.
6. preparation method as claimed in claim 5, wherein acid is 0.01～5 quality % aqueous solution of aromatic sulphonic acid class.
7. preparation method as claimed in claim 6, wherein acid is 0.03～2 quality % aqueous solution of aromatic sulphonic acid class.
8. preparation method as claimed in claim 1 is wherein sour for being selected from the inorganic acid of phosphoric acid, boric acid and sulfuric acid.
9. preparation method as claimed in claim 8, wherein acid is 0.01～8 quality % aqueous solution of phosphoric acid.
10. preparation method as claimed in claim 9, wherein acid is 0.05～3 quality % aqueous solution of phosphoric acid.
11. preparation method as claimed in claim 1, the wherein acidic aqueous solution of acid in the washing of sulfonic acid ion exchange resin is processed, obtaining.
12. preparation method as claimed in claim 1 wherein utilizes the modification of strong-acid ion exchange resin of the amines of sulfur-bearing under 0～120 ℃.
13. such as each described preparation method in the claim 1～12, wherein the amines of aqueous acid and sulfur-bearing be injected to the injection that the amines of sulfur-bearing is dissolved in the preparation liquid that forms in the aqueous acid, the injection rate of this preparation liquid is counted 0.1～20h with LHSV (reciprocal of duty cycle during liquid)
-1
14. preparation method as claimed in claim 13 wherein is dissolved in the amines of sulfur-bearing the injection rate of the preparation liquid that forms in the aqueous acid, counts 0.2～10h with LHSV (liquid hourly space velocity (LHSV))
-1
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003-308990 | 2003-09-01 | ||
| JP2003308990A JP4298438B2 (en) | 2003-09-01 | 2003-09-01 | Method for preparing modified catalyst for production of bisphenol A |
| CNA2004800250872A CN1845790A (en) | 2003-09-01 | 2004-08-30 | Preparation method of modified catalyst for bisphenol A preparation |
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| CNA2004800250872A Division CN1845790A (en) | 2003-09-01 | 2004-08-30 | Preparation method of modified catalyst for bisphenol A preparation |
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| JP (1) | JP4298438B2 (en) |
| KR (1) | KR101083168B1 (en) |
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| JP4971663B2 (en) * | 2006-03-31 | 2012-07-11 | 三井化学株式会社 | Method for preparing catalyst for production of bisphenols |
| EP2158040B1 (en) * | 2007-06-14 | 2011-02-16 | Dow Global Technologies Inc. | Preparation of catalyst for bisphenols production |
| JP5189439B2 (en) * | 2008-09-02 | 2013-04-24 | トヨタ自動車株式会社 | Cloth detection apparatus and cloth detection method |
| US8293137B2 (en) * | 2009-12-30 | 2012-10-23 | Jiangsu Sinorgchem Technology Co., Ltd. | Solid acid catalyst and method for preparing and using the same |
| US9718767B2 (en) * | 2015-12-04 | 2017-08-01 | Chevron Phillips Chemical Company Lp | Beta-mercaptoethanol synthesis |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1059480A (en) * | 1991-09-16 | 1992-03-18 | 天津大学 | The reparation technology of exchange resin catalyst used in bisphenol synthesis and device thereof |
| CN1343188A (en) * | 2000-01-07 | 2002-04-03 | 出光石油化学株式会社 | Process for producing bisphenol A |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1539463A (en) * | 1976-07-26 | 1979-01-31 | Shell Int Research | Preparation of a fixed bed catalyst |
| JP2001286770A (en) * | 2000-04-04 | 2001-10-16 | Idemitsu Petrochem Co Ltd | Preparation method of fixed bed of acidic cation exchange resin for bisphenol production |
| JP2001348350A (en) * | 2000-06-07 | 2001-12-18 | Idemitsu Petrochem Co Ltd | Method for preparing fixed bed of acidic cation exchange resin for producing bisphenols |
-
2003
- 2003-09-01 JP JP2003308990A patent/JP4298438B2/en not_active Expired - Fee Related
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2004
- 2004-08-30 WO PCT/JP2004/012861 patent/WO2005021155A1/en active Application Filing
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- 2004-08-30 KR KR1020067004242A patent/KR101083168B1/en active IP Right Grant
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1059480A (en) * | 1991-09-16 | 1992-03-18 | 天津大学 | The reparation technology of exchange resin catalyst used in bisphenol synthesis and device thereof |
| CN1343188A (en) * | 2000-01-07 | 2002-04-03 | 出光石油化学株式会社 | Process for producing bisphenol A |
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| JP4298438B2 (en) | 2009-07-22 |
| JP2005074332A (en) | 2005-03-24 |
| CN102886277B (en) | 2016-04-27 |
| TW200510064A (en) | 2005-03-16 |
| KR101083168B1 (en) | 2011-11-11 |
| TWI370017B (en) | 2012-08-11 |
| WO2005021155A1 (en) | 2005-03-10 |
| KR20060117905A (en) | 2006-11-17 |
| CN1845790A (en) | 2006-10-11 |
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