CN106061931A - Process for producing bisphenol A - Google Patents
Process for producing bisphenol A Download PDFInfo
- Publication number
- CN106061931A CN106061931A CN201580010942.0A CN201580010942A CN106061931A CN 106061931 A CN106061931 A CN 106061931A CN 201580010942 A CN201580010942 A CN 201580010942A CN 106061931 A CN106061931 A CN 106061931A
- Authority
- CN
- China
- Prior art keywords
- bisphenol
- phenol
- adduct
- concentration
- crystallize
- 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.)
- Pending
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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 363
- 238000000034 method Methods 0.000 title claims abstract description 100
- WUQYBSRMWWRFQH-UHFFFAOYSA-N 2-prop-1-en-2-ylphenol Chemical compound CC(=C)C1=CC=CC=C1O WUQYBSRMWWRFQH-UHFFFAOYSA-N 0.000 claims abstract description 63
- 229940106691 bisphenol a Drugs 0.000 claims description 165
- 238000004519 manufacturing process Methods 0.000 claims description 84
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 67
- 239000007788 liquid Substances 0.000 claims description 65
- 238000002425 crystallisation Methods 0.000 claims description 59
- 230000008025 crystallization Effects 0.000 claims description 59
- 239000000243 solution Substances 0.000 claims description 50
- 239000002253 acid Substances 0.000 claims description 48
- 238000000926 separation method Methods 0.000 claims description 42
- 238000006317 isomerization reaction Methods 0.000 claims description 38
- 239000010413 mother solution Substances 0.000 claims description 30
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 24
- 238000006482 condensation reaction Methods 0.000 claims description 22
- 239000000203 mixture Substances 0.000 claims description 21
- 239000012530 fluid Substances 0.000 claims description 12
- 239000000376 reactant Substances 0.000 claims description 11
- 239000003054 catalyst Substances 0.000 claims description 10
- 238000000354 decomposition reaction Methods 0.000 claims description 10
- 230000002378 acidificating effect Effects 0.000 claims description 7
- 239000012141 concentrate Substances 0.000 claims description 7
- 238000011084 recovery Methods 0.000 claims description 6
- HLXZNFNQKKBUJX-UHFFFAOYSA-N CC(C)C1=CC=CC(O)=C1C1=NCCS1 Chemical compound CC(C)C1=CC=CC(O)=C1C1=NCCS1 HLXZNFNQKKBUJX-UHFFFAOYSA-N 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 claims 1
- 238000005469 granulation Methods 0.000 abstract description 7
- 230000003179 granulation Effects 0.000 abstract description 7
- 239000000463 material Substances 0.000 description 23
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 19
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical class ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 18
- 239000002245 particle Substances 0.000 description 17
- 239000002994 raw material Substances 0.000 description 16
- 238000005406 washing Methods 0.000 description 16
- 238000006243 chemical reaction Methods 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- 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 12
- 239000000047 product Substances 0.000 description 12
- 241001550224 Apha Species 0.000 description 11
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 9
- 239000007864 aqueous solution Substances 0.000 description 9
- 239000003729 cation exchange resin Substances 0.000 description 9
- 238000004140 cleaning Methods 0.000 description 9
- 238000004821 distillation Methods 0.000 description 9
- 238000001953 recrystallisation Methods 0.000 description 9
- 230000006837 decompression Effects 0.000 description 8
- 238000001704 evaporation Methods 0.000 description 8
- 230000008020 evaporation Effects 0.000 description 8
- 239000011347 resin Substances 0.000 description 8
- 229920005989 resin Polymers 0.000 description 8
- 235000011121 sodium hydroxide Nutrition 0.000 description 8
- 238000004128 high performance liquid chromatography Methods 0.000 description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- 239000003957 anion exchange resin Substances 0.000 description 6
- 239000002585 base Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000004431 polycarbonate resin Substances 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 238000004040 coloring Methods 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- NUHSROFQTUXZQQ-UHFFFAOYSA-N isopentenyl diphosphate Chemical compound CC(=C)CCO[P@](O)(=O)OP(O)(O)=O NUHSROFQTUXZQQ-UHFFFAOYSA-N 0.000 description 5
- 239000004417 polycarbonate Substances 0.000 description 5
- 229920000515 polycarbonate Polymers 0.000 description 5
- 229920005668 polycarbonate resin Polymers 0.000 description 5
- -1 Thiazolinyl phenol Chemical compound 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 4
- 239000000470 constituent Substances 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 150000002989 phenols Chemical class 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- 238000007711 solidification Methods 0.000 description 4
- 230000008023 solidification Effects 0.000 description 4
- ZYUVGYBAPZYKSA-UHFFFAOYSA-N 5-(3-hydroxybutan-2-yl)-4-methylbenzene-1,3-diol Chemical compound CC(O)C(C)C1=CC(O)=CC(O)=C1C ZYUVGYBAPZYKSA-UHFFFAOYSA-N 0.000 description 3
- 229930185605 Bisphenol Natural products 0.000 description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 3
- 239000008346 aqueous phase Substances 0.000 description 3
- 230000033228 biological regulation Effects 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 3
- 238000007600 charging Methods 0.000 description 3
- 239000000112 cooling gas Substances 0.000 description 3
- NHADDZMCASKINP-HTRCEHHLSA-N decarboxydihydrocitrinin Natural products C1=C(O)C(C)=C2[C@H](C)[C@@H](C)OCC2=C1O NHADDZMCASKINP-HTRCEHHLSA-N 0.000 description 3
- 239000003925 fat Substances 0.000 description 3
- 230000002349 favourable effect Effects 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 239000003456 ion exchange resin Substances 0.000 description 3
- 229920003303 ion-exchange polymer Polymers 0.000 description 3
- 238000012544 monitoring process Methods 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 238000005292 vacuum distillation Methods 0.000 description 3
- 208000035126 Facies Diseases 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- RRTCFFFUTAGOSG-UHFFFAOYSA-N benzene;phenol Chemical compound C1=CC=CC=C1.OC1=CC=CC=C1 RRTCFFFUTAGOSG-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 125000000555 isopropenyl group Chemical group [H]\C([H])=C(\*)C([H])([H])[H] 0.000 description 2
- 239000003595 mist Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- JVBXVOWTABLYPX-UHFFFAOYSA-L sodium dithionite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])=O JVBXVOWTABLYPX-UHFFFAOYSA-L 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 238000005728 strengthening Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 238000011144 upstream manufacturing Methods 0.000 description 2
- HSAYSFNFCZEPCN-UHFFFAOYSA-N 3-(dimethylamino)propane-1-thiol Chemical compound CN(C)CCCS HSAYSFNFCZEPCN-UHFFFAOYSA-N 0.000 description 1
- IYGAMTQMILRCCI-UHFFFAOYSA-N 3-aminopropane-1-thiol Chemical compound NCCCS IYGAMTQMILRCCI-UHFFFAOYSA-N 0.000 description 1
- YLXAAHHOPYLRJV-UHFFFAOYSA-N 4-(dibutylamino)butane-1-thiol Chemical compound CCCCN(CCCC)CCCCS YLXAAHHOPYLRJV-UHFFFAOYSA-N 0.000 description 1
- JAGRUUPXPPLSRX-UHFFFAOYSA-N 4-prop-1-en-2-ylphenol Chemical class CC(=C)C1=CC=C(O)C=C1 JAGRUUPXPPLSRX-UHFFFAOYSA-N 0.000 description 1
- QHPQWRBYOIRBIT-UHFFFAOYSA-N 4-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C=C1 QHPQWRBYOIRBIT-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000004425 Makrolon Substances 0.000 description 1
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical group OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 150000001339 alkali metal compounds Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229920000402 bisphenol A polycarbonate polymer Polymers 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000005341 cation exchange Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000006166 lysate Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 235000014593 oils and fats Nutrition 0.000 description 1
- 238000005453 pelletization Methods 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical group 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-O sulfonium group Chemical group [SH3+] RWSOTUBLDIXVET-UHFFFAOYSA-O 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000003981 vehicle Substances 0.000 description 1
- 239000003643 water by type Substances 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
-
- 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
- C07C37/68—Purification; separation; Use of additives, e.g. for stabilisation
- C07C37/70—Purification; separation; Use of additives, e.g. for stabilisation by physical treatment
- C07C37/82—Purification; separation; Use of additives, e.g. for stabilisation by physical treatment by solid-liquid treatment; by chemisorption
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C39/00—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring
- C07C39/12—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring polycyclic with no unsaturation outside the aromatic rings
- C07C39/15—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring polycyclic with no unsaturation outside the aromatic rings with all hydroxy groups on non-condensed rings, e.g. phenylphenol
- C07C39/16—Bis-(hydroxyphenyl) alkanes; Tris-(hydroxyphenyl)alkanes
Abstract
A process for producing bisphenol A, wherein the concentration of isopropenylphenol under an ambient temperature condition of 10 to 50 ℃ within 1 hour after granulation of bisphenol A is monitored and controlled to 150 mass ppm or less.
Description
Technical field
The present invention relates to the manufacture method for manufacturing the good bisphenol-A of the bisphenol-A of high-quality, particularly form and aspect.
Background technology
The polycarbonate resin (hereinafter sometimes referred to simply as PC resin) manufactured by bisphenol-A is due to the transparency, thermostability, low suction
Moist, mechanical property is excellent, is thus suitable for the light guide plate being mounted in mobile phone, portable game machine, vehicle mounted guidance etc.
Etc. purposes.For the makrolon material used in the purposes such as this light guide plate, it is desirable to the transparency (low YI).
When bisphenol-A is at high temperature kept molten by its manufacturing process, in several hours, generate isopropenyl phenol
(hereinafter sometimes referred to simply as IPP).Because generate isopropenyl phenol and cause the coloring of raw materials bisphenol A, form and aspect be deteriorated, using its as
The transparency decline of the Merlon that raw material manufactures.
Therefore, the Merlon high in order to obtain the transparency, need to suppress raw material by minimizing isopropenyl phenol amount
The coloring (low APHA) of bisphenol-A.
Patent documentation 1 is recorded: when at high temperature keeping bisphenol-A with molten condition, in several hours, generate 4-different
Acrylic phenol and cause raw materials bisphenol A start coloring, using its as raw material manufacture Merlon tone be deteriorated.In order to press down
Make the generation of this 4-isopropenyl phenol, Patent Document 1 discloses following manufacture method: the ratio making bisphenol a/phenol is
Specific scope the most also keeps liquid molten state.In patent documentation 1, although describe without pelletize work
Sequence and bisphenol-A is used for manufacturing under being kept molten by the manufacture method of Merlon, but about the bisphenol-A to molten condition
The situation carrying out pelletize and be granulated is silent on.
The generation of known isopropenyl phenol mainly causes because of the acid flowed out from primary response operation, therefore arranges outflow
The removing equipment (filter material/anion exchange resin etc.) of acid is effective.Patent Document 2 discloses following method: arrange
Free acid removal step thus remove causes generating the coloring material in the presence of mother solution or isomerization treatment fluid and causes product
The free acid that the form and aspect of bisphenol-A are deteriorated, bisphenol-A that thus manufacture high-quality, that particularly the transparency (form and aspect) is excellent.
Patent documentation 3 is recorded: it is known that the free acid produced in main reactor in the method manufacturing bisphenol-A becomes
Promote the decomposition and 2 of bisphenol-A, the generation of 4 '-bisphenol-A for reason, and disclose the manufacturing process at bisphenol-A and make free acid
Concentration be specific in the range of the manufacture method of bisphenol-A.
Patent documentation 4 provides following method: separated with the adduct of phenol by the bisphenol-A of crystallize by known method
After, utilize phenol purification to implement carrying out washing treatment.In this carrying out washing treatment, this phenol purification is relative to usual adduct 100 mass
Part uses with the ratio of 30～100 mass parts.
Prior art literature
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 2002-173530 publication
Patent documentation 2: Japanese Unexamined Patent Publication 2007-308408 publication
Patent documentation 3: Japanese Unexamined Patent Publication 2001-316313 publication
Patent documentation 4: Japanese Unexamined Patent Publication 6-048970 publication
Summary of the invention
The problem that invention is to be solved
As described in patent documentation etc., it is known that isopropenyl phenol is the reason material that form and aspect are deteriorated.But, isopropenyl
The reactivity of phenol is the highest, even if the most apt to deteriorate for other composition, accordingly, there exist in the manufacture of bisphenol-A
It is difficult to set the problem that concentration adjusts target.The present invention completes to solve the problems referred to above, its object is to provide logical
Cross and set the isopropenyl phenol concentration of the bisphenol-A obtained after pelletize and adjust target and control this concentration and it is possible to make continuously
Make the manufacture method of the good bisphenol-A of form and aspect.
Means for solving the above
The inventors discovered that, by after the pelletize of the bisphenol-A obtained bisphenol-A fused solution is carried out pelletize 1 hour with
In, isopropenyl phenol concentration under the ambient temperature conditions of 10～50 DEG C control below particular range, it is possible to continuously
Ground manufactures the bisphenol-A that form and aspect are good.
The i.e. present invention comprises the description below.
1. a manufacture method for bisphenol-A, wherein, after the pelletize of bisphenol-A within 1 hour, monitors the ring of 10～50 DEG C
Above-mentioned concentration is also controlled below 150 mass ppm by isopropenyl phenol concentration under the temperature conditions of border.
2. a manufacture method for bisphenol-A, the manufacture method of described bisphenol-A has:
(1) condensation reaction operation, makes the phenol of excess and acetone carry out condensation reaction in the presence of acidic catalyst；
(2) crystallize, solid-liquid separation process, by cooling down the reactant mixture obtained in operation (1), makes bis-phenol
A and the adduct crystallize of phenol, be separated into this adduct and mother solution；
(3) adduct decomposition process, removes phenol from the adduct of the bisphenol-A obtained operation (2) with phenol, is formed
Bisphenol-A fused solution；With
(4) granulating working procedure, carries out pelletize to the bisphenol-A fused solution obtained in operation (3),
Wherein,
Monitor the isopropenyl phenol concentration within 1 hour, under the ambient temperature conditions of 10～50 DEG C after the pelletize of bisphenol-A
And above-mentioned concentration is controlled below 150 mass ppm.
3. the manufacture method of the bisphenol-A as described in 2, it also has: (D) enrichment process, anti-to obtain in operation (1)
Mixture is answered to concentrate.
4. the manufacture method of the bisphenol-A as according to any one of 1～3, it also has (A) free acid removal step, passes through
Remove free acid and control above-mentioned isopropenyl phenol concentration.
5. the manufacture method of the bisphenol-A as described in 2 or 3, wherein, in above-mentioned crystallize, solid-liquid separation process (2), passes through
Change the amount of liquor that the adduct crystallization to bisphenol-A Yu phenol washs, thus control above-mentioned isopropenyl phenol concentration.
6. the manufacture method of the bisphenol-A as described in 5, wherein, above-mentioned amount of liquor is relative to the adduct of bisphenol-A Yu phenol
Crystallizing 100 mass parts is 10～100 mass parts.
7. the manufacture method of the bisphenol-A as according to any one of 2～6, also has:
(B) isomerization operation, utilizes the isomerization catalyst mother to obtaining in above-mentioned crystallize, solid-liquid separation process (2)
Total amount or the one portion of liquid carry out isomerization process, make isomerization treatment fluid be recycled to condensation reaction operation (1) and/or concentrate work
Sequence (D)；With
(C) recovery process, reclaims double from the remainder of isomerization treatment fluid treated isomerization operation (B)
Phenol A and the adduct of phenol.
The effect of invention
The manufacture method of the bisphenol-A according to the present invention, monitor bisphenol-A pelletize after within 1 hour, the environment of 10～50 DEG C
Above-mentioned concentration is also controlled below 150 mass ppm by isopropenyl phenol concentration under temperature conditions, it is possible to manufacture form and aspect
Good bisphenol-A.
Detailed description of the invention
The manufacture method of the bisphenol-A of the present invention need monitor bisphenol-A pelletize after within 1 hour, the environment of 10～50 DEG C
Above-mentioned concentration is also controlled below 150 mass ppm by isopropenyl phenol concentration under temperature conditions.Isopropenyl phenol concentration
Such as can be measured monitoring by utilizing high performance liquid chromatography (hereinafter sometimes referred to simply as HPLC).Isopropenyl phenol is dense
When degree is more than 150 mass ppm, the form and aspect of obtained bisphenol-A are deteriorated, and quality comes into question.By dense for above-mentioned isopropenyl phenol
Degree controls below preferably 100 mass ppm, below more preferably 50 mass ppm.Here, " after pelletize " refers to molten condition
Moment of contacting with cooling ways such as cooling gases of bisphenol-A.
Isopropenyl phenol represents with following formula (1).
In the present invention, the isopropenyl phenol concentration of bisphenol-A after the pelletizing within 1 hour, 10～50 DEG C, more preferably
Monitor under the ambient temperature conditions of 15～40 DEG C, more preferably 20～30 DEG C.Isopropenyl phenol concentration in time and temperature
Degree significantly changes, therefore, in order to monitor isopropenyl phenol concentration, it is also desirable to by time and temperature treatment specifically
Scope.More specifically, in the present invention, the condition monitored isopropenyl phenol concentration is after pelletize 1 hour, 30 DEG C
Ambient temperature.
For the increase and decrease of the isopropenyl phenol concentration of bisphenol-A, the free acid concentration in adduct decomposition process is close
Cut is closed.In order to reduce isopropenyl phenol concentration, as an example, can enumerate: remove the free acid in technique so that double
Phenol A declines with the free acid concentration in the adduct crystallization (hereinafter sometimes referred to adduct crystallization (ア ダ Network Bu Jing)) of phenol
Method and/or in crystallize, solid-liquid separation process, bisphenol-A and the adduct crystallization of phenol are washed thus remove attached
The method of free acid in crystallization.By fully reducing the dense of free acid contained and/or accompanying in adduct crystallization
Degree, it is possible to this adduct crystallization will be made to decompose and the isopropenyl phenol concentration of bisphenol-A that obtains control 150 mass ppm with
Under.
As the method for the free acid removed in technique, it is arranged as required to free acid removal step (A) described later, thus
Isopropenyl phenol concentration can be controlled.
The washing of the adduct crystallization in crystallize, solid-liquid separation process can proceed as described below control.That is, set in manufacture
Standby identical and volume of production one timing, after pelletize within 1 hour, under the ambient temperature conditions of 10～50 DEG C in the isopropyl of bisphenol-A
Thiazolinyl phenol concentration dependant is in the particle diameter of the adduct crystallization obtained in the crystallize operation of condensation reaction mixture.Adduct is tied
When brilliant particle diameter reduces, specific surface area increases, impurity level accompanying in the crystallization obtained in crystallize, solid-liquid separation process
(free acid, isomer etc.) increases, and free acid accompanying in crystallization increases, and thus isopropenyl phenol concentration also raises.Separately
On the one hand, when the particle diameter of adduct crystallization increases, specific surface area reduces, in the crystallization obtained in crystallize, solid-liquid separation process
Accompanying impurity level reduces, and isopropenyl phenol concentration reduces.That is, isopropenyl phenol concentration dependant is in adduct crystallization
Particle diameter.
Herein, the particle diameter of adduct crystallization is imported the impurity in liquid by the kind of crystallize equipment and operating condition, crystallize
The biggest impact of concentration.It addition, in industrialness manufactures, even if manufacturing under the same conditions, strict for adduct crystallization
Particle diameter the most periodically change.Accordingly, it is difficult to directly control the particle diameter of adduct crystallization.
The particle diameter depending on adduct crystallization or the isopropenyl phenol concentration that periodically changes are supervised
In the manufacturing process of apparent bisphenol-A extremely important.Manufacturing method according to the invention, in predefined conditions to bisphenol-A after pelletize
Isopropenyl phenol concentration be measured, thus, isopropenyl phenol concentration raise (that is, the particle diameter of adduct crystallization subtracts
Little) in the case of, change fabrication process condition and isopropenyl phenol concentration is reduced, it is possible to keep well bisphenol-A
The quality of product.It addition, in the case of isopropenyl phenol concentration reduces (that is, the particle diameter of adduct crystallization increases), permissible
Stop unwanted manufacturing process etc., be industrially favourable.
In the manufacture of bisphenol-A, in order to prevent the heat deterioration of product, coloring, use at the purifiable crystallize of low temperature more, consolidate
Liquid separation circuit.In crystallize, solid-liquid separation process, mostly wash on the basis of crystallize, solid-liquid separation.Particularly exist
In washing operation, product quality is brought the biggest impact by its clean result.This clean result not only with amount of liquor and also with analysis
The crystal form obtained in brilliant operation also has much relations.But, in common manufacture device, the particle diameter of crystallization confirms very
Difficulty.In addition, grain size number distribution depends on mixing speed, manufactures device volume.Additionally, the particle diameter of crystallization can be periodically
Change.For above-mentioned situation, obtain the product quality of excellence to realize optimal clean result, in a manufacturing process
Confirm target bisphenol-A product character while regulation amount of liquor becomes critically important at any time.
In the manufacture method of the present invention, when bisphenol-A is carried out pelletize, it is possible to use the general fused solution to bisphenol-A
Carry out the prilling granulator of pelletize.It is, for example possible to use make bisphenol-A fused solution become drop, tower top arrange there is large number of orifices
Nozzle plate and at the granulation tower of conduit possessing winding-up cooling gas at the bottom of tower.By bisphenol-A fused solution liquor charging to granulation tower
Tower top, bisphenol-A fused solution large number of orifices set by the nozzle plate being arranged at tower top is sprayed out with shape spray.That sprays out is molten
Melt liquid to pass through to be cooled from the recyclegas risen at the bottom of the tower of granulation tower, from forming the emboliform solid being referred to as grain at the bottom of tower
Send mouth from pelletize after (bisphenol-A sometimes obtained carrying out pelletize is referred to as " granular bisphenol A ") to discharge, form product bisphenol-A.Make
For said nozzle plate, use the metallic plate etc. being provided with large number of orifices, in order to prevent the solidification of bisphenol-A, it is possible to use electric heater
Or steam etc. heats.
The temperature of above-mentioned bisphenol-A fused solution is preferably 157～200 DEG C.When the temperature of bisphenol-A fused solution is less than 157 DEG C, have
Solidification may be occurred to block in pipe arrangement by fused solution when bisphenol-A fused solution is imported granulating working procedure.It addition, during more than 200 DEG C,
Likely promote that the decomposition of bisphenol-A colours.The temperature of above-mentioned bisphenol-A fused solution is more preferably 160～180 DEG C.
Prilling nozzle is provided with the structure of nozzle the most onboard.In the present invention, the aperture (diameter) of nozzle is preferred
It is set as 0.3～1.0mm, is more preferably set as 0.4～0.7mm, is further preferably set as 0.5～0.6mm, thus can obtain
To the granular bisphenol A that mean diameter is 0.5～about 1.5mm.
In the present invention, it is preferred to the rate of outflow of the bisphenol-A fused solution flowed out from above-mentioned prilling nozzle is set as 0.5～
1.8m/ the second.When the rate of outflow of bisphenol-A fused solution is the 0.5m/ second more than, the drop of bisphenol-A fused solution is fusion together and obtains
Granular bisphenol A be formed as above-mentioned particle size range.When the rate of outflow of bisphenol-A fused solution is the 1.8m/ second below, obtained bis-phenol
The size of A grain becomes uniform.The rate of outflow of above-mentioned bisphenol-A fused solution be preferably 1.0～1.8m/ seconds, more preferably 1.4～
1.8m/ the second.
It is usually tens seconds～1 minute degree the cool time of the drop of bisphenol-A fused solution.The tower height of granulation tower is by bis-phenol
The cool time of the drop of A fused solution determines, typically about 10～50m.
The manufacture method of the bisphenol-A of the present invention can have in its a kind of mode: (1) condensation reaction operation, makes excess
Phenol and acetone in the presence of acidic catalyst, carry out condensation reaction；(2) crystallize, solid-liquid separation process, by work
The reactant mixture obtained in sequence (1) cools down, and makes the adduct crystallize of bisphenol-A and phenol, is separated into this adduct and mother
Liquid；(3) adduct decomposition process, removes phenol from the adduct of the bisphenol-A obtained operation (2) with phenol, forms bisphenol-A
Fused solution；(4) granulating working procedure, carries out pelletize to the bisphenol-A fused solution obtained in operation (3).
It addition, can also have (D) between (1) condensation reaction operation and (2) crystallize, solid-liquid separation process to concentrate work
Sequence, concentrates the reactant mixture obtained in operation (1).
Hereinafter each operation is illustrated.
(1) condensation reaction operation
In this operation, the phenol of raw material and acetone stoichiometrically react under phenol surplus.Phenol and acetone
Mol ratio be usually phynol/acetone=3～the scope of 30, be preferably 5～20 scope.As reaction temperature, generally use
50～100 DEG C, as reaction pressure, generally use normal pressure～1.5MPa, normal pressure～0.6MPa are preferably used.As catalyst,
Generally use storng-acid cation exchange resin.As storng-acid cation exchange resin, it is known to have sulphur in functional group
Acidic group (RSO3 -H+) material, as weak-acid cation-exchange resin, it is known to have carboxylic acid group (R-COO in functional group-
H+), phosphonate group (R-P (O) (O-H+)2), phosphinic acid base (R-PH (O) (O-H+)), arsenous acidic group (R-OAsO-H+), phenoxy group (R-
C6H4O-H+) material etc., can use in the present invention.Generally preferably there is in functional group sulfonic sulfonic acid type strong
Acid cation exchange resin.
As the commercially available product of ion exchange resin, the ダ イ ヤ イ オ ソ that Mitsubishi chemical Co., Ltd manufactures can be enumerated
The ァ ソ バ mono-リ ス ト A26 etc. that SK104H, the レ バ チ Star ト MP-62 of Beyer Co., Ltd's manufacture and R&H company manufacture, at this
Can use in bright.
Utilize the promoters such as alkyl mercaptoamine to strong acid cation exchange resin catalyst in addition it is also possible to use
A part be neutralized after catalyst.Such as can enumerate: utilize 2-MEA, 3-mercaptopropylamine, N, N-dimethyl-3-
Mercaptopropylamine, N, N-di-n-butyl-4-sulfydryl butylamine, 2,2-dimethylthiazole alkane etc. make sulfonic 5～30 moles of % by
Material after with.
Phenol can circulate to be utilized as the fixed bed of continuation mode and baric flow mode with the condensation reaction of the material liquid of acetone
Mode or suspension bed intermittent mode are carried out.In the case of fixed bed circulation style, to the liquid of the material liquid of reactor supply
Air speed (LHSV) is 0.1～50hr-1Left and right.It addition, in the case of utilizing suspension bed intermittent mode to carry out, although because of reaction temperature
Degree, reaction pressure are the most different, but generally, use relative to the scope that this material liquid is 20～100 mass %
Resin catalysis dosage, is all about 0.5～5 hour during reaction.
(D) enrichment process
The manufacture method of the present invention can also be according to circumstances at (1) condensation reaction operation and (2) crystallize, solid-liquid separation process
Between there is enrichment process (D).Reactant mixture from above-mentioned (1) condensation reaction operation generally can be by two stage work
Sequence concentrates.In the first enrichment process, remove unreacted acetone, water generation reaction etc. by methods such as decompression distillations.Subtract
Pressure distillation is generally about 30～180 DEG C and pressure is to implement under 13～about 67kPa in temperature.
Then, in the second enrichment process, remove phenol, adjust the concentration of bisphenol-A.The concentration of bisphenol-A now is preferred
It is set as about 20～60 mass %.When the concentration of bisphenol-A is less than 20 mass %, productivity reduces.It addition, higher than 60 mass %
Time, the solidification temperature of bisphenol-A raises, easily solidifies, can cause the problem that can not carry.Therefore, generally at the first enrichment process
Middle concentration in advance by reaction mixture is thus adjusted to above-mentioned concentration.This second enrichment process generally preferably temperature be 70～
About 140 DEG C and pressure are to implement under conditions of 4～about 40kPa.
(2) crystallize, solid-liquid separation process
Carry out the reactant mixture of self-condensation reaction operation (1) or from the concentrated solution of enrichment process (D) generally from 70～140
Being cooled to about 35～60 DEG C about DEG C, there is crystallize with the adduct (adduct) of phenol in bisphenol-A, is formed as pulp-like.
The cooling of concentrated solution carries out heat extraction by external heat exchanger, the latent heat that caused by evaporation of water added in crystallize tank.
Then, the liquid of pulp-like carries out solid-liquid separation.The composition of the mother solution obtained in this crystallize, solid-liquid separation process is typically benzene
Phenol be 65～85 mass %, bisphenol-A be 10～20 mass %, 2, the by-product such as 4 '-isomer is 5～15 mass %.
By the reactant mixture of pulp-like being carried out solid-liquid separation and the adduct crystallization of isolated bisphenol-A and phenol
It is ready to proceed to adduct decomposition process and removes phenol, thus can get highly purified bisphenol-A.
The solid constituent using adduct crystallization as main component piled up through the surface of filter medium filtration of solid-liquid separating machine
It is supplied to the washing utilizing cleaning mixture to carry out.As cleaning mixture, except the phenol reclaimed after evaporation, raw material phenol, water, water-phenol mix
Close and can also use the liquid identical with the saturated phenol solution of bisphenol-A beyond liquid.About the amount of cleaning mixture, it is to control the present invention
A kind of means of isopropenyl phenol concentration, illustrate afterwards.
It should be noted that the mother solution obtained in crystallize, solid-liquid separation process (2) is recirculated to condensation reaction operation
(1) and/or enrichment process (D) or in the case of isomerization operation (B) described later is set further the total amount of mother solution or its
A part is supplied to isomerization operation (B).
After crystallize solid-liquid separation can by adduct crystallization re-dissolved, crystallize and solid-liquid separation are repeated again.Logical
Crossing multistage and this crystallize and solid-liquid separation are repeated, the impurity being thus mixed in adduct crystallization gradually decreases.This situation
Under, as the lysate to re-dissolved and the solid constituent using adduct crystallization as main component that obtained by solid-liquid separation
Cleaning mixture when washing, the phenol reclaimed after evaporation, raw material phenol, water, can also each section in addition to water-phenol mixed liquor
The liquid that middle use is identical with the saturated phenol solution of bisphenol-A.About the amount of cleaning mixture during this recrystallization, also it is to control this
A kind of means of bright isopropenyl phenol concentration, illustrate afterwards.It addition, the mother obtained by crystallize again and solid-liquid separation
Liquid can also be recycled to above-mentioned crystallize operation.
(3) adduct decomposition process
In crystallize, solid-liquid separation process (2), the adduct crystallization reclaimed by solid-liquid separation is at adduct decomposition process
Middle removing phenol and be formed as bisphenol A with high purity.Such as, this adduct crystallization is heated by ordinary circumstance at about 100～160 DEG C
Melt and be thus decomposed into bisphenol-A and phenol, utilize evaporator etc. to remove major part phenol from this fused solution, pass through vapour further
Carry the phenol removing residual, thus obtain bisphenol-A fused mass.
(4) granulating working procedure
The bisphenol-A fused mass obtained by above-mentioned adduct decomposition process (3) by above-mentioned prilling process in this operation
Carry out pelletize.I.e., it is possible to use bisphenol-A fused solution made drop tower top be provided with have large number of orifices nozzle plate and
The prilling granulator of the such general fused solution manufacturing bisphenol-A of granulation tower of the conduit possessing winding-up cooling gas at the bottom of tower enters
Row pelletize.The temperature of bisphenol-A fused solution is preferably set to 157～200 DEG C, the aperture (diameter) of nozzle be preferably set to 0.3～
1.0mm, was preferably set to for 0.5～1.8m/ second from the rate of outflow of the bisphenol-A fused solution of prilling nozzle outflow.The tower of granulation tower
Height is usually 10～about 50m.Preferably reason and preferred scope etc. is described above.
In the present invention, need to monitor after the pelletize of bisphenol-A within 1 hour, under the ambient temperature conditions of 10～50 DEG C
Isopropenyl phenol concentration also controls manufacturing process in the way of above-mentioned concentration is below 150 mass ppm.
As dense with the isopropenyl phenol within after the pelletize of bisphenol-A 1 hour, under the ambient temperature conditions of 10～50 DEG C
Degree is a kind of means that the mode of below 150 mass ppm controls the method for manufacturing process, can be set forth in the bisphenol-A of the present invention
Manufacture method in arrange remove free acid free acid removal step (A).Therefore, the manufacture method of the bisphenol-A of the present invention can
To have following free acid removal step (A).
(A) free acid removal step
The position that arranges of free acid removal step (A) is not particularly limited, preferably by raw material phenol, condensation reaction operation
(1) (enter oral fluid) before, obtain after (going out oral fluid) and crystallize mother solution separation circuit (2) after condensation reaction operation (1)
Crystallize mother solution etc. is set as object, more preferably the crystallize mother solution obtained after crystallize, solid-liquid separation process (2) is set as object.
In the free acid removal step of the present invention, remove means as acid, it is possible to use acid adsorbent, anion exchange
Resin.As acid adsorbent, such as shown in Japanese Unexamined Patent Publication 11-152240 publication, it is possible to use alkali metal compound/alkali
Earth metal compound.As anion exchange resin, it is possible to use strong basic ion exchange resin and weakbase ion exchange tree
Fat.
It addition, as strong-base anion-exchange resin, it is possible to use there is quaternary ammonium salt base (R-N+R1R2R3) or tertiary sulfonium base
(R-S+R1R2) as the material of functional group.
As the commercially available product of anion exchange resin, the ダ イ ヤ イ オ Application that Mitsubishi chemical Co., Ltd manufactures can be enumerated
WA-20,21,30, R&H company manufacture ァ Application バ mono-リ ス ト A21, can use in the present invention.
In the manufacture method of the present invention, can monitor after the pelletize of bisphenol-A within 1 hour, the ring of 10～50 DEG C
Isopropenyl phenol concentration under the temperature conditions of border, decides whether to above-mentioned free acid removal step (A) base feed benzene
Phenol, mother solution etc..That is, the bisphenol-A obtained after pelletize above-mentioned under the conditions of isopropenyl phenol concentration begin to exceed 150 mass
During ppm, carry out making raw material phenol, mother solution etc. remove free acid by free acid removal step (A) and thus reduce isopropenyl
The operation of phenol concentration.It addition, by the particle diameter increase etc. of adduct crystallization make above-mentioned under the conditions of isopropenyl phenol dense
When degree is below 150 mass ppm, can make in the case of not making raw material phenol, mother solution etc. by free acid removal step (A)
Manufacturing process is carried out.
So, monitor that isopropenyl phenol concentration decides whether to carry out free acid removal step in predefined conditions, by
This can obtain the bisphenol-A that isopropenyl phenol concentration is low, quality is good.Isopropenyl phenol concentration is below 150 mass ppm
Time, it is convenient to omit free acid removal step, the volume of production in the unit interval can be improved when being continuously manufactured by bisphenol-A, industrial
It is favourable.
As dense with the isopropenyl phenol within after the pelletize of bisphenol-A 1 hour, under the ambient temperature conditions of 10～50 DEG C
Degree is the another kind of means that the mode of below 150 mass ppm controls the method for manufacturing process, can enumerate and make at crystallize, solid
In liquid separation circuit (2) through above-mentioned solid-liquid separating machine surface of filter medium filter and pile up using adduct crystallization as main component
Solid constituent when washing and time solid constituent when this adduct crystallization is carried out recrystallization is washed
The amount change of cleaning mixture.As cleaning mixture, as it has been described above, except the phenol reclaimed after phenol purification, evaporation, raw material phenol, water,
The liquid etc. identical with the saturated phenol solution of bisphenol-A can also be used beyond water-phenol mixed liquor.
As above-mentioned amount of liquor, generally, obtain relative in this crystallize, solid-liquid separation process (2) in terms of quality criteria
To adduct crystallization 100 mass parts be preferably 10～100 mass parts, more preferably 15～85 mass parts, more preferably
20～75 mass parts.Relative to adduct crystallization 100 mass parts, when amount of liquor is less than 10 mass parts, detersive efficiency declines, because of
This is the most preferred.When amount of liquor is more than 100 mass parts, the re-dissolved loss of adduct crystallization tends to increasing, it addition, from cleaning mixture
Circulation, reclaim, re-use from the viewpoint of the most preferred.
In the manufacture method of the bisphenol-A of the present invention, as the means of technology controlling and process, make crystallize, solid-liquid separation process
(2), in the case of the amount of liquor change in, the amount of cleaning mixture is as described below to be determined.
In the manufacture method of the present invention, monitor bisphenol-A pelletize after within 1 hour, the environment temperature of 10～50 DEG C
Isopropenyl phenol concentration under the conditions of degree, makes amount of liquor change within the above range.That is, the bis-phenol obtained after pelletize
A above-mentioned under the conditions of isopropenyl phenol concentration when beginning to exceed 150 mass ppm, increase washing within the above range
Liquid measure, strengthening washing thus reduce the operation of isopropenyl phenol concentration.It addition, because the particle diameter increase etc. of adduct crystallization makes
When isopropenyl phenol concentration under the conditions of above-mentioned is below 150 mass ppm, amount of liquor is made to decline within the above range.
So, the isopropyl alkene by monitoring after the pelletize of bisphenol-A within 1 hour, under the ambient temperature conditions of 10～50 DEG C
Base phenol concentration and control washing, the bisphenol-A that isopropenyl phenol concentration is low, quality is good can be obtained.Isopropenyl phenol
When concentration is below 150 mass ppm, can stop unnecessary washing, industrial when being continuously manufactured by bisphenol-A is favourable.
It addition, the manufacture method of the bisphenol-A of the present invention can also have isomerization operation (B) in other scheme, utilize
Total amount or the one part of the isomerization catalyst mother solution to obtaining in crystallize, solid-liquid separation process (2) are carried out at isomerization
Reason, makes isomerization treatment fluid be recycled to condensation reaction operation (1) and/or enrichment process (D).
(B) isomerization operation
The total amount in the liquid phase portion (mother solution) that will obtain in crystallize, solid-liquid separation process (2) or one part supply are to different
Structure chemical industry sequence (B), can carry out isomerization process to the byproduct of reaction (2,4 '-isomer etc.) in mother solution.Need explanation
It is that the mother solution obtained in crystallize, solid-liquid separation process (2) not supplied to isomerization operation (B) is recycled to as mentioned above
Condensation reaction operation (1) and/or enrichment process (D).
Isomerization processes preferably by mother solution supply being handed over to being filled with highly acidic cation with continuous way and baric flow mode
The fixed bed circulation style of the fixed bed reactors (isomerization vessel) changing resin is carried out.As strongly acidic cation exchange tree
Fat, such as, can use sulfonic acid ion exchange resin.Isomerization reaction temperature is preferably 50 DEG C～the scope of 100 DEG C, more
It is preferably 70～80 DEG C.By being set as more than 50 DEG C, the solidification of bisphenol-A in mother solution can be avoided, by being set as 100 DEG C
Hereinafter, de-from catalyst and bisphenol-A the acid of sulfonic acid can be avoided to decompose the problem that the product quality caused is deteriorated.
In the case of fixed bed isomerization reactor, liquid air speed (LHSV) is preferably generally 0.1～50hr-1, more preferably
It is 0.15～25hr-1, more preferably 0.2～0.4hr-1.By LHSV is set as 0.1hr-1Above, amount of by-products subtracts
Few, by being set as 50hr-1Hereinafter, high conversion can be obtained.
Above-mentioned isomerization process after the major part of isomerization treatment fluid be recirculated to condensation reaction operation (1) and/or
Enrichment process (D), is preferably recirculated to enrichment process (D).It addition, as required, in order to prevent the accumulation of impurity, isomerization
A part for treatment fluid is discharged in the way of discharging liquid delivers to following recovery process (C).
(C) recovery process
Double containing about 15～20 mass % in the isomerization treatment fluid of the part sent here from isomerization operation (B)
Phenol A, 5～10 about mass % 2, the by-product such as 4 '-isomer.After this isomerization treatment fluid is concentrated, in the existence of phenol
Under cool down, thus make the adduct crystallization crystallize of bisphenol-A and phenol.After solid-liquid separation, this adduct crystallization is melted, so
After be recycled to enrichment process (D) and/or crystallize, solid-liquid separation process (2).After disposing mother liquor phenol after above-mentioned solid-liquid separation
Process.
As other the method controlling isopropenyl phenol concentration, such as, can also enumerate following method.
As it has been described above, isopropenyl phenol concentration can the grain of adduct crystallization because obtaining in crystallize, solid-liquid separation process
Footpath and change.Speculate that generally generating oversaturated increase in crystalline growth contributes to crystallizing the increase of average diameter.Cause
This, as in order to reduce isopropenyl phenol concentration and one of method of particle diameter increasing adduct crystallization, can enumerate regulation
The operation degree of supersaturation (Δ C=P (crystallization volume of production)/G (circulating load in groove)) that manufacturing process makes bisphenol-A manufacture in device subtracts
Little.
Above, manufacturing method according to the invention, monitor bisphenol-A pelletize after within 1 hour, the environment temperature of 10～50 DEG C
Above-mentioned concentration is also controlled below 150 mass ppm by isopropenyl phenol concentration under the conditions of degree, it is possible to manufacture form and aspect good
The bisphenol-A of good (low APHA).APHA used in the evaluation of form and aspect such as can pass through JIS K-4101 or ASTM D-
1686 (the benchmark oils and fats analysis test method(s) (Standard of oiling association of Japan (Japan Oil Chemist ｀ s Society)
Methods for the Analysis of Fats, Oils and Related Materials)) it is measured.APHA is excellent
Elect less than 50, more preferably less than 40, more preferably less than 30 as.
Embodiment
Hereinafter, by embodiment, the present invention is more specifically illustrated, but the present invention is not by any limit of these examples
Fixed.In embodiment and comparative example, different to by within after the pelletize of bisphenol-A 1 hour, under the ambient temperature conditions of 10～50 DEG C
The method that acrylic phenol concentration controls below 150 mass ppm is studied.
Embodiment 1
Utilize 2-MEA by cation exchange resin [Mitsubishi chemical Co., Ltd's manufacture, " ダ イ ヤ イ to being filled with
オ ソ SK104H "] 20 moles of % parts neutralize after material fixed bed reaction tower in continuously with LHSV3hr-1Logical liquid mole
Phenol than 10: 1 and acetone, carry out reacting (condensation reaction operation (1)) at 75 DEG C.The reaction mixture obtained is imported decompression
In distillation column, column bottom temperature be 170 DEG C, pressure be 67kPa under conditions of carry out decompression distillation, remove unreacted acetone, anti-
Should generate water etc., the most further temperature be 130 DEG C, pressure be 14kPa under conditions of carry out decompression distillation, evaporate phenol,
Carrying out being concentrated into bisphenol A concentration is 40 mass %, obtains the concentrated solution (enrichment process (D)) of phenol/bisphenol-A.
Then, in the concentrated solution obtained add water, decompression for 2kPa (15 torr) crystallize groove in be held in 45 DEG C by
This carries out crystallize, utilizes horizontal belt filter material to filter the pulp solution obtained, then relative to the adduct knot obtained
Brilliant 100 mass parts use raw material phenol to wash with the ratio of 40 mass parts.Obtained adduct crystallization carries out described later
Recrystallization operation (crystallize, solid-liquid separation process (2)).
Liquid (crystallize mother solution) after utilizing horizontal belt filter material to filter exists the moisture of 5 mass %, hence with
Moisture concentration in mother solution is adjusted to 0.5 mass % by distillation column.Before mother solution after this adjustment is carried out isomerization process, send
Tower is removed, in reaction to the free acid being filled with weak-base anion-exchange resin (" the ァ Application バ mono-リ ス ト A21 " of R&H company)
Temperature is 75 DEG C, LHSV=1hr-1Under carry out processing (free acid removal step (A)).By remove the whole mother solutions after free acid with
Reaction temperature is 75 DEG C, LHSV=1hr-1Supply to being filled with cation exchange resin (Mitsubishi chemical Co., Ltd's manufacture, " ダ
イ ヤ イ オ Application SK104H ") isomerization reactor in (isomerization treatment process (B)).It should be noted that in order to by bis-phenol
A concentration is adjusted to 40 mass %, and 8 one-tenth of the mother solution after being processed by isomerization are recycled to the vacuum distillation tower of enrichment process (D)
Upstream, by 2 one-tenth liquor chargings to recovery process (C).
In the adduct crystallization utilizing above-mentioned horizontal belt filter material to filter and to obtain, add evaporation reclaim phenol and tie again
Mother solution in brilliant operation, is heated to 90 DEG C and prepares the solution of the bisphenol-A containing 45 mass %, utilize the filter of 10 micron-scales
Material filters.Add water again to the crystallization obtained, under conditions of 5.33kPa (40 torr) and 50 DEG C, carry out recrystallization.Will
The pulp solution arrived supplies to two sections of extrusion type centrifugal separators (400G), relative to adduct crystallization 100 mass parts, utilizes 40
The raw material phenol of the ratio of mass parts washs, and obtains moistening adduct crystallization.By the moistening adduct crystallization that obtains 130
DEG C carry out adding heat fusing, de-phenol, then utilize mist projection granulating tower to carry out pelletize, obtain bisphenol-A (grain) as product.
Will after pelletize obtained by bisphenol-A (30 DEG C) at ambient temperature under keeping, to after pelletize through 1 hour, 2 little
Time, 8 hours, 24 hours, bisphenol-A after 48 hours utilize high performance liquid chromatography to be analyzed.In the present embodiment, by bisphenol-A
Fused solution after the moment that prilling nozzle flows out is set as pelletize 0 hour.In analysis, (Waters is public to use high-speed liquid chromatography
Department manufactures, model: 2695, post: Inertsil (registered trade mark) ODS-3V GL science Co., Ltd. system).As mobile phase
25 mass % acetonitrile solutions kept after 45 minutes, utilize 3.5 mass %/minute gradient be analyzed.Arrive 100 matter
Keep 5 minutes after amount % acetonitrile.The injection rate of sample be set as 5.0 μ L, column temperature be set as 40 DEG C, flow set be 1.0mL/
Minute, analyze wavelength be set as 277nm.
HPLC measure result in, IPP concentration be respectively 40 ((following identical) 1 hours after pelletize), 36 (2 hours), 32
(8 hours), 26 (24 hours), 23 (48 hours) quality ppm.Show the result in table 1.
It addition, commented the form and aspect evaluation carrying out bisphenol-A by APHA.APHA is carried out by the method for regulation in JIS K-4101
Measure.Specifically, granular bisphenol A is heated 40 minutes in 220 DEG C in air atmosphere, use APHA reference colour, by visually
Evaluate form and aspect.The all APHA10 of result.Show the result in table 1.
It addition, the bisphenol-A obtained in use the present embodiment, manufacture polycarbonate resin according to following manufacture example, measure YI.
Manufacture example: the manufacture of bisphenol A polycarbonate resin
1. polycarbonate oligomer synthesis procedure
In 5.6 mass % sodium hydrate aqueous solutions, relative to the bisphenol-A (being the most sometimes abbreviated as BPA) dissolved afterwards
Add the sodium dithionite of 2000 mass ppm, dissolve in the present embodiment in the way of BPA concentration is 13.5 mass % wherein
The BPA obtained, prepares the sodium hydrate aqueous solution of BPA.To internal diameter be 6mm, pipe range be 30m tube-type reactor in continuously
It is passed through sodium hydrate aqueous solution 40L/ hour of this BPA, dichloromethane 15L/ hour and phosgene 4.0kg/ hour.Tube-type reactor
There is jacket portion, be connected with cooling water so that the temperature of reactant liquor is held in less than 40 DEG C at chuck.
The band baffling that internal volume is 40L possessing retreating blade it is directed into continuously from tube-type reactor reactant liquor out
In the tank reactor of plate, add the most further 2.8L/ hour the sodium hydrate aqueous solution of BPA, 0.07L/ hour
1 mass % triethylamine aqueous solution of 25 mass % sodium hydrate aqueous solutions, the water of 17L/ hour and 0.64L/ hour is carried out instead
Should.
Discharge the reactant liquor overflowed from tank reactor continuously, stand, be thus separated off aqueous phase, gather dichloro
Methane phase.The concentration of obtained polycarbonate oligomer is 325g/L, chloro-carbonic acid ester group concentration is 0.77mol/L.
2. the polymerization process of Merlon
The temperature of the cooling solvent possessing the 50L tank reactor of baffle plate, paddle agitator and cooling chuck reaches 20
After below DEG C, add oligomer solution 15L, dichloromethane 8.9L, p-t-butyl phenol 192g, the hydrogen of triethylamine 0.7mL and BPA
Aqueous solution of sodium oxide (by the NaOH of 647g with molten relative to the sodium dithionite that the BPA dissolved afterwards is 2000 mass ppm
Solution dissolves material obtained by the BPA of 1185g in aqueous solution obtained by 9.5L water), implement 30 minutes polyreactions.Add afterwards
The triethylamine adding 0.8mL stirs 30 minutes further.
Add after the dichloromethane 15L of dilution, be separated into the organic facies comprising polycarbonate resin and comprise surplus
The aqueous phase of BPA and NaOH, isolate organic facies.The dichloromethane solution of the polycarbonate resin obtained is utilized successively relatively
Wash, followed by pure water in the 0.03mol/L NaOH aqueous solution that its solution is 15 capacity % and 0.2mol/L hydrochloric acid
Washing is repeated until the electrical conductivity in aqueous phase after Xi Di is 0.05 below μ S/m.The Merlon that will be obtained by washing
The dichloromethane solution of resin concentrates, pulverizes, by the thin slice obtained under reduced pressure, 100 DEG C be dried, obtain polymer with bis phenol A carbon
Acid ester resin.
Manufacture polycarbonate resin YI value be determined as follows described carrying out.
To be granulated by resin flake obtained above, after being dried 5 hours at 110 DEG C by this resin particle, use injection
Forming machine (Nissei Plastic Industrial Co., Ltd manufactures, ProductName FS80S-12ASE) plastifies at 300 DEG C, then at cylinder body
Interior delay 15 seconds, shaping thickness is the square molded body of 3.2mm, 60mm, and this test film uses Japan's electricity color industry manufacture
Light splitting colour difference meter SE-2000 utilize and be measured according to the method for JIS K-7105.Show the result in table 2.
Embodiment 2
Relative to adduct crystallization 100 mass parts obtained in crystallize, solid-liquid separation process (2), use with 5 mass parts
Ratio evaporation reclaim after phenol wash, and when carrying out the recrystallization of above-mentioned adduct crystallization relative to adduct
Crystallizing 100 mass parts utilizes the raw material phenol of 5 mass parts to wash, and carries out operation similarly to Example 1 in addition, system
Make bisphenol-A.
Will obtain after pelletize bisphenol-A (30 DEG C) at ambient temperature keeping, for after pelletize through 1 hour, 2 hours, 8
Hour, 24 hours, the bisphenol-A of 48 hours, utilize high performance liquid chromatography to be analyzed similarly to Example 1.The result measured
Be, IPP concentration be respectively 99 ((following identical) 1 hours after pelletize), 92 (2 hours), 81 (8 hours), 63 (24 hours), 56
(48 hours) quality ppm.Show the result in table 1.
APHA is utilized to carry out form and aspect evaluation the most similarly to Example 1 for obtained bisphenol-A.Result is all
APHA20.Show the result in table 1.
It addition, similarly to Example 1 according to manufacturing the example poly-carbonic acid of manufacture in addition to using the bisphenol-A obtained in this example
Ester resin, measures YI value by method similarly to Example 1.Show the result in table 2.
Embodiment 3
In addition to not carrying out free acid removing, carry out operation similarly to Example 1, produce bisphenol-A.By obtained
Bisphenol-A (30 DEG C) at ambient temperature under keeping, for after pelletize through 1 hour, 2 hours, 8 hours, 24 hours, 48 hours
After bisphenol-A, utilize high performance liquid chromatography to be analyzed similarly to Example 1.The result measured is, IPP concentration is respectively
150 ((following identical) 1 hours after pelletize), 133 (2 hours), 121 (8 hours), 94 (24 hours), 84 (48 hours) quality
ppm.Show the result in table 1.
For obtained bisphenol-A, APHA is utilized to carry out form and aspect evaluation the most similarly to Example 1.Result is all
APHA35.Show the result in table 1.
It addition, similarly to Example 1 according to manufacturing the example poly-carbonic acid of manufacture in addition to using the bisphenol-A obtained in this example
Ester, produces molded body by method similarly to Example 1, measures YI value.Show the result in table 2.
Comparative example 1
Utilize 2-MEA by cation exchange resin [Mitsubishi chemical Co., Ltd's manufacture, " ダ イ ヤ イ to being filled with
オ Application SK104H "] 20 moles of % parts neutralize after material fixed bed reaction tower in continuously with LHSV3hr-1Logical liquid mole
Ratio is phenol and the acetone of 10: 1, reacts at 75 DEG C.The reaction mixture obtained is imported in vacuum distillation tower, at the bottom of tower
Temperature is 170 DEG C, pressure is to carry out decompression distillation under conditions of 67kPa, removes unreacted acetone, water generation reaction etc., then
Further temperature be 130 DEG C, pressure be 14kPa under conditions of carry out decompression distillation, evaporate phenol, be concentrated into bisphenol A concentration
It is 40 mass %, obtains the concentrated solution of phenol/bisphenol-A.
Then, in the concentrated solution obtained, add water, the crystallize groove that decompression is 2kPa (15 torr) keeps 45 DEG C thus
Carry out crystallize, utilize horizontal belt filter material to filter the pulp solution obtained, then relative to adduct 100 mass parts with
The adduct crystallization obtained is washed by the phenol after the ratio of 5 mass parts uses evaporation to reclaim.Obtained adduct knot
Crystalline substance carries out recrystallization operation described later.
Liquid (crystallize mother solution) after utilizing horizontal belt filter material to filter exists the moisture of 5 mass %, hence with
Moisture concentration in mother solution is adjusted to 0.5 mass % by distillation column.By even for the whole mother solutions after this adjustment moisture concentration reaction temperature
Degree is 75 DEG C, LHSV=1hr-1Supply to being filled with cation exchange resin (Mitsubishi chemical Co., Ltd's manufacture, " ダ イ ヤ イ
オ Application SK104H ") isomerization reactor in.
It should be noted that in order to bisphenol A concentration being adjusted to 40 mass %, eighty per cant of the mother solution after isomerization is processed
It is recycled to the upstream of the vacuum distillation tower of enrichment process (D), by twenty percent liquor charging to recovery process (C).
In the adduct crystallization utilizing above-mentioned horizontal belt filter material to filter and to obtain, add evaporation reclaim phenol and tie again
Mother solution in brilliant operation, is heated to 90 DEG C and prepares the solution of the bisphenol-A containing 45 mass %, utilize the filter of 10 micron-scales
Material filters.Add water again to the crystallization obtained, under conditions of 5.33kPa (40 torr) and 50 DEG C, carry out recrystallization.Will
The pulp solution arrived supplies to two sections of extrusion type centrifugal separators (400G), relative to adduct crystallization 100 mass parts, utilizes 5
The raw material phenol of the ratio of mass parts washs, and obtains moistening adduct crystallization.By the moistening adduct crystallization that obtains 130
DEG C carry out adding heat fusing, de-phenol, then utilize mist projection granulating tower to carry out pelletize, obtain bisphenol-A as product.
Will after pelletize obtained by bisphenol-A (30 DEG C) at ambient temperature under keeping, for after pelletize through 1 hour, 2 little
Time, 8 hours, 24 hours, bisphenol-A after 48 hours, utilize high performance liquid chromatography to be analyzed similarly to Example 1.Measure
Result be, IPP concentration be respectively 202 ((following identical) 1 hours after pelletize), 178 (2 hours), 162 (8 hours), 132 (24
Hour), 98 (48 hours) quality ppm.
APHA is utilized to carry out form and aspect evaluation the most similarly to Example 1 for obtained bisphenol-A.Result is all
APHA60。
It addition, similarly to Example 1 according to manufacturing the example poly-carbonic acid of manufacture in addition to using the bisphenol-A obtained in this example
Ester, produces molded body by method similarly to Example 1, measures YI value.Show the result in table 2.
[table 1]
Table 1
[table 2]
Table 2
| YI value | |
| Embodiment 1 | 1.3 |
| Embodiment 2 | 1.4 |
| Embodiment 3 | 1.5 |
| Comparative example 1 | 2.0 |
Embodiment 1 is that the amount of liquor of the removing to free acid and washing adduct crystallization (containing during recrystallization) is carried out
The example of strengthening, embodiment 2 has been by the example of the removing of free acid, and embodiment 3 is to washing adduct crystallization (recrystallization
The example that amount of liquor Shi Hanyou) is strengthened.On the other hand, comparative example 1 be do not include free acid removal step and
The amount of liquor washing adduct crystallization is less than the example of embodiment.
According to table 1,1 hour, isopropenyl phenol concentration under the ambient temperature conditions of 30 DEG C after the pelletize of bisphenol-A
Control to be 150 matter compared to isopropenyl phenol concentration under these conditions more than the APHA value of the comparative example 1 of 150 mass ppm
Measuring ppm below example 1～3 and significantly raise, form and aspect significantly deteriorate.It addition, use the form and aspect excellence of embodiment 1～3
The polycarbonate molding body that bisphenol-A makes has the YI value of excellence.On the other hand, the bisphenol-A system of the comparative example 1 of hue difference is used
The polycarbonate molding body result made is YI value difference, it is known that the transparency is not improved.
Isopropenyl phenol concentration changed along with the elapsed time summed up in table 1, but according to embodiment 1～3 and ratio
Relatively example 1 it will be apparent that, by the isopropenyl phenol concentration in moment of after the pelletize of bisphenol-A 1 hour is controlled in 150 mass
Below ppm, it is possible to manufacture the bisphenol-A that form and aspect are excellent.
Industrial applicability
According to the present invention, by monitoring after the pelletize of bisphenol-A within 1 hour, under the ambient temperature conditions of 10～50 DEG C
Above-mentioned concentration is also controlled below 150 mass ppm by isopropenyl phenol concentration, it is possible to manufacture the bisphenol-A that form and aspect are good.
Claims (7)
1. a manufacture method for bisphenol-A, wherein, after the pelletize of bisphenol-A within 1 hour, monitors the environment at 10～50 DEG C
Described concentration is also controlled below 150 mass ppm by isopropenyl phenol concentration under temperature conditions.
2. a manufacture method for bisphenol-A, the manufacture method of described bisphenol-A has:
(1) condensation reaction operation, makes the phenol of excess and acetone carry out condensation reaction in the presence of acidic catalyst；
(2) crystallize, solid-liquid separation process, by the reactant mixture obtained in operation (1) is cooled down, make bisphenol-A with
The adduct crystallize of phenol, is separated into this adduct and mother solution；
(3) adduct decomposition process, removes phenol from the adduct of the bisphenol-A obtained operation (2) with phenol, forms bis-phenol
A fused solution；With
(4) granulating working procedure, carries out pelletize to the bisphenol-A fused solution obtained in operation (3),
Wherein,
After the pelletize of bisphenol-A within 1 hour, monitor the isopropenyl phenol concentration under the ambient temperature conditions of 10～50 DEG C
And described concentration is controlled below 150 mass ppm.
3. the manufacture method of bisphenol-A as claimed in claim 2, it also has:
(D) enrichment process, concentrates the reactant mixture obtained in operation (1).
4. the manufacture method of the bisphenol-A as according to any one of claims 1 to 3, it also has (A) free acid removal step,
Described isopropenyl phenol concentration is controlled by removing free acid.
5. the manufacture method of the bisphenol-A as according to any one of claim 2～4, wherein, in described crystallize, solid-liquid separation work
In sequence (2), by changing the amount of liquor that the adduct crystallization to bisphenol-A Yu phenol washs, thus control described isopropyl
Thiazolinyl phenol concentration.
6. the manufacture method of bisphenol-A as claimed in claim 5, wherein, described amount of liquor adds relative to bisphenol-A and phenol
It is 10～100 mass parts that compound crystallizes 100 mass parts.
7. the manufacture method of the bisphenol-A as according to any one of claim 2～6, also has:
(B) isomerization operation, utilizes the isomerization catalyst mother solution to obtaining in described crystallize, solid-liquid separation process (2)
Total amount or one part carry out isomerization process, make isomerization treatment fluid be recycled to condensation reaction operation (1) and/or enrichment process
(D)；With
(C) recovery process, reclaims bisphenol-A from the remainder of isomerization treatment fluid treated isomerization operation (B)
Adduct with phenol.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2014039482 | 2014-02-28 | ||
| JP2014-039482 | 2014-02-28 | ||
| PCT/JP2015/055092 WO2015129640A1 (en) | 2014-02-28 | 2015-02-23 | Bisphenol a production method |
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| JP (1) | JPWO2015129640A1 (en) |
| KR (1) | KR20160127002A (en) |
| CN (1) | CN106061931A (en) |
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| US11312822B2 (en) | 2017-01-17 | 2022-04-26 | Sabic Global Technologies B.V. | Reduced color polycarbonate compositions, methods of manufacture, and articles thereof |
| JP7087848B2 (en) * | 2018-09-04 | 2022-06-21 | 三菱ケミカル株式会社 | Method for producing bisphenol and method for producing polycarbonate resin |
| CN113166011A (en) * | 2018-09-05 | 2021-07-23 | 巴杰许可有限责任公司 | Process for producing bisphenol A |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005075736A (en) * | 2003-08-28 | 2005-03-24 | Mitsubishi Chemicals Corp | Method for producing aromatic dihydroxy compound and method for producing polycarbonate |
| CN1646458A (en) * | 2002-03-29 | 2005-07-27 | 出光兴产株式会社 | Process for producing bisphenol A |
| CN101443301A (en) * | 2006-05-17 | 2009-05-27 | 出光兴产株式会社 | Process and apparatus for producing high-purity bisphenol A |
| WO2014002787A1 (en) * | 2012-06-28 | 2014-01-03 | 出光興産株式会社 | Bisphenol-a production method |
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| JPH0648970A (en) | 1992-07-31 | 1994-02-22 | Idemitsu Petrochem Co Ltd | Production of 2,2-bis@(3754/24)4-hydroxyphenyl) propane |
| JP4140171B2 (en) | 2000-05-02 | 2008-08-27 | 三菱化学株式会社 | Method for producing crystalline adduct of bisphenol A and phenol for the production of high quality bisphenol A |
| JP4080710B2 (en) | 2000-09-26 | 2008-04-23 | 三菱化学株式会社 | Method for producing aromatic polycarbonate |
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2015
- 2015-02-23 CN CN201580010942.0A patent/CN106061931A/en active Pending
- 2015-02-23 WO PCT/JP2015/055092 patent/WO2015129640A1/en active Application Filing
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| CN1646458A (en) * | 2002-03-29 | 2005-07-27 | 出光兴产株式会社 | Process for producing bisphenol A |
| JP2005075736A (en) * | 2003-08-28 | 2005-03-24 | Mitsubishi Chemicals Corp | Method for producing aromatic dihydroxy compound and method for producing polycarbonate |
| CN101443301A (en) * | 2006-05-17 | 2009-05-27 | 出光兴产株式会社 | Process and apparatus for producing high-purity bisphenol A |
| WO2014002787A1 (en) * | 2012-06-28 | 2014-01-03 | 出光興産株式会社 | Bisphenol-a production method |
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| WO2015129640A1 (en) | 2015-09-03 |
| KR20160127002A (en) | 2016-11-02 |
| RU2016134753A (en) | 2018-03-29 |
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