CN102698801A - Resin catalyst applied to preparation of phenol through decomposition of cumene hydroperoxide (CHP) and preparation method for resin catalyst - Google Patents
Resin catalyst applied to preparation of phenol through decomposition of cumene hydroperoxide (CHP) and preparation method for resin catalyst Download PDFInfo
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- CN102698801A CN102698801A CN2012101783029A CN201210178302A CN102698801A CN 102698801 A CN102698801 A CN 102698801A CN 2012101783029 A CN2012101783029 A CN 2012101783029A CN 201210178302 A CN201210178302 A CN 201210178302A CN 102698801 A CN102698801 A CN 102698801A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The invention discloses a resin catalyst applied to preparation of phenol through decomposition of cumene hydroperoxide (CHP) and a preparation method for the resin catalyst. The preparation method comprises the following steps of: by a macroporous styrene ion exchange resin aggregation production process, adding a (methyl) crylic acid halothane-based ester monomer and the phenol, aggregating, sulfonating, and thus obtaining the resin catalyst. The prepared catalyst is high in oxidation resistance and mechanical strength, has long service life, can be widely applied in production, and has an extremely good application prospect in the field of preparation of the phenol through a CHP decomposition reaction.
Description
Technical field
The present invention relates to a kind of resin catalyst and preparation method thereof, particularly a kind of resin catalyst that is applied to decomposing hydrogen phosphide cumene to prepare phynol and preparation method thereof.
Background technology
At present, the phenol more than 90% is produced by cumene method in the world.This method mainly comprises 3 reactions: alkylated reaction, oxidation reaction and decomposition reaction.As far as hydrogen phosphide cumene (CHP) decomposition reaction; Mostly adopt traditional concentrated sulfuric acid catalyst. its reaction is violent; Not easy to operate, accessory substance is many, the product separation difficulty; Equipment corrosion is serious, and the sodium sulphate that generates with the alkali neutralisation of sulphuric acid is prone to cause the fouling of distillation system reboiler. produce more phenol-containing wastewater when handling fouling again. and contaminated environment.Therefore, seeking better catalyst replaces sulfuric acid very necessary.At present, the catalyst that is used for the CHP decomposition reaction both at home and abroad is a lot, mainly comprises (1) homogeneous reaction catalyst (like BF3 class, halogeno-benzene thiophenol, metal complex etc.); (2) clay catalyst; (3) zeolite catalyst; (4) acid resin catalyst.Wherein, sulfonate resin has the reaction condition gentleness with other catalyst ratios, and side reaction is few, and selectivity is good, and yield is high, and is renewable, the advantage that the life-span is long.And, from reaction medium, separate corrosive equipment not easily as solid matter; Add uniform particles, be specially adapted to successive reaction, and can be according to granular size. voidage and specific area are selected specific resin; The control rate of catalysis reaction, applying flexible.
Hydrogen phosphide cumene has strong oxidizing property, is prone to cause that resin " decortication " is damaged, number of dropouts is big, and the generator nozzle easy blocking influences service life of resin.So the oxidation resistance that improves resin catalyst is to produce the technical barrier that phenol process needs to be resolved hurrily.
CN101343212 provides the method for a kind of decomposing hydrogen phosphide cumene to prepare phynol and acetone; It is characterized in that adopting the smectites solid acid catalyst through the inorganic ammonium salt modification is catalysts; Make hydrogen phosphide cumene generation decomposition reaction, the inventive method make be reflected under the relatively mild condition carry out, extent of reaction be prone to controlled, accessory substance is few, no burn into product easy separation, catalyst is recyclable recycles.
CN101219394 provides a kind of manufacturing phynol/acetone with hydrogen phosphide cumene decomposition carried heteropoly acid catalyst.But this invention has the acid site and the acid strength of very wide modulation, advantage such as specific area is big, structural stability good, activity is high, no burn into is pollution-free, product is easily separated, reaction condition is gentle, production cost is low and can regenerate.
Shortcomings such as but above patent is used the solid acid as catalyst, has the preparation method complicacy, and service life is short.
Summary of the invention
(methyl) acrylic acid fluoroalkyl esters monomer is participated in fluorinated acrylamide acid polymer that reaction obtains and is had many excellent surfaces characteristic such as low-surface-energy, low frictional properties, stain resistance, good water-oil resistance and good weatherability, chemical resistance.Reason is, fluorine-containing the side chain ((CF of polymer
2)
nCF
3, n=0 ~ 11), occupy the interface of polymer and air, not only greatly reduce polymer the surface can, and the C-C main chain played the shielding protection effect, thereby improved weatherability, non-oxidizability and the corrosion resistance of organo-fluorine polymer.
Therefore; To a little less than the resin catalyst non-oxidizability that is applied to decomposing hydrogen phosphide cumene to prepare phynol in the prior art, service life short defective; The present invention proposes a kind of said resin catalyst; Said resin catalyst is that prescription and the preparation technology with this area acid resin catalyst-macropore styrene type cation exchange resin commonly used is the basis; Difference is in polymerization, adds (methyl) acrylic acid fluoroalkyl esters monomer and phenol and participates in polymerization, obtains through conventional process for sulfonation again.The polymerisation equation is following:
Behind oversulfonate, the end product structural formula is following:
Wherein, (methyl) acrylic acid fluoroalkyl esters monomer, its general formula is: R
1(CH
2) mCOOCR
1=CH
2(R
1=H, CH
2Or CF
2; M>=1), typical, said monomer is acrylic acid hexafluoro butyl ester, dodecafluorhe-ptylacrylate and/or acrylic acid ten trifluoro monooctyl esters etc.
On the other hand, the invention provides a kind of resin catalyst and preparation technology thereof who is applied to decomposing hydrogen phosphide cumene to prepare phynol, said technology is following:
Adopt macropore styrene ion exchange resin polymerization process well known in the art; The control degree of cross linking 15～30%; Pore rate 30～60%, the higher degree of cross linking and pore rate make resin matrix have higher specific surface area, are beneficial to the ability that improves resin adsorption phenol; In addition, add (methyl) acrylic acid fluoroalkyl esters monomer of the whole monomer mass percentages 0.1～2% that account for polymerisation simultaneously, 0.1～5% phenol is participated in polymerization, obtains finished product through conventional process for sulfonation again.Wherein, (methyl) acrylic acid fluoroalkyl esters monomer is preferably 1%, and phenol is preferably 5%.
The inventor finds on the basis of a large amount of experiments and research; Adopt the acrylic acid fluoroalkyl esters monomer and the phenol of above-mentioned percent concentration proportioning to participate in polymerization, described unforeseeable technique effect after the resin catalyst that obtains has, reason is following: 1). and too much acrylic acid fluoroalkyl esters monomer is participated in polymerization; Can destroy the stabilising system balance of polymerization; Cause cruelly and gather, or make the polymer thickness, influence the generation of normal resin particle; 2) too much phenol is participated in polymerization, because the sterically hindered effect of phenolic hydroxyl group, can influence on the sulfonic group to cinnamic phenyl ring, causes the catalyst exchange capacity to reduce, thereby influences catalytic activity.And the addition of these two kinds of materials is very few, can can't reach required weatherability, non-oxidizability, corrosion resistance and compatibility.
This product has following beneficial effect:
Owing in preparation technology, added phenol and (methyl) acrylic acid fluoroalkyl esters monomer; The compatibility that phenolic hydroxyl group helps catalyst and phenol improves; The C-F structure can improve the catalyst tolerates oxidation susceptibility, thereby makes the catalyst tolerates oxidation effectiveness of prepared of the present invention good, long service life.Can decompose in the preparation phenol production at the catalyzing hydrogen peroxide isopropylbenzene and use.Advantages such as it is few to have catalyst amount, and reaction is continuous, and the reaction time is short.
The specific embodiment
Following instance only is to further specify the present invention, is not the scope of restriction the present invention protection.
Embodiment 1:
1). polymerisation
Select the macropore styrene ion exchange resin polymerization process of knowing altogether in the industry for use, the control degree of cross linking 15%, pore rate 30%; In addition; Add the acrylic acid hexafluoro butyl ester that accounts for monomer mass percentage 0.1% simultaneously, 0.1% phenol is participated in polymerization, obtains finished product through technologies such as sulfonation again.Be numbered KRB-1
Embodiment 2
The polymerisation degree of cross linking 30%, other is with embodiment 1.Products obtained therefrom is numbered KRB-2.
Embodiment 3
The polymerisation degree of cross linking 22.5%, other is with embodiment 1.Products obtained therefrom is numbered KRB-3.
Embodiment 4
Polymerisation pore rate 60%, other is with embodiment 1.Products obtained therefrom is numbered KRB-4.
Embodiment 5
Polymerisation pore rate 45%, other is with embodiment 1.Products obtained therefrom is numbered KRB-5.
Embodiment 6
Add the acrylic acid hexafluoro butyl ester that accounts for monomer mass percentage 2%, other is with embodiment 1.Products obtained therefrom is numbered KRB-6.
Embodiment 7
Add the acrylic acid hexafluoro butyl ester that accounts for monomer mass percentage 2%, other is with embodiment 2.Products obtained therefrom is numbered KRB-7.
Embodiment 8
Add the acrylic acid hexafluoro butyl ester that accounts for monomer mass percentage 2%, other is with embodiment 3.Products obtained therefrom is numbered KRB-8.
Embodiment 9
Add the acrylic acid hexafluoro butyl ester that accounts for monomer mass percentage 2%, other is with embodiment 4.Products obtained therefrom is numbered KRB-9.
Embodiment 10.
Add the acrylic acid hexafluoro butyl ester that accounts for monomer mass percentage 2%, other is with embodiment 5.Products obtained therefrom is numbered KRB-10.
Embodiment 11.
Add the dodecafluorhe-ptylacrylate that accounts for monomer mass percentage 1%, other is with embodiment 1.Products obtained therefrom is numbered KRB-11.
Embodiment 12.
Add the acrylic acid hexafluoro butyl ester that accounts for monomer mass percentage 1%, other is with embodiment 2.Products obtained therefrom is numbered KRB-12.
Embodiment 13.
Add the acrylic acid hexafluoro butyl ester that accounts for monomer mass percentage 1%, other is with embodiment 3.Products obtained therefrom is numbered KRB-13.
Embodiment 14.
Add the acrylic acid hexafluoro butyl ester that accounts for monomer mass percentage 1%, other is with embodiment 4.Products obtained therefrom is numbered KRB-14.
Embodiment 15.
Add the acrylic acid ten trifluoro monooctyl esters that account for monomer mass percentage 1%, other is with embodiment 5.Products obtained therefrom is numbered KRB-15.
Embodiment 16.
Add the phenol that accounts for monomer mass percentage 0.1%, other is with embodiment 1.Products obtained therefrom is numbered KRB-16.
Embodiment 17.
Add the phenol that accounts for monomer mass percentage 5%, other is with embodiment 2.Products obtained therefrom is numbered KRB-17.
Embodiment 18.
Add the phenol that accounts for monomer mass percentage 5%, other is with embodiment 3.Products obtained therefrom is numbered KRB-18.
Embodiment 19.
Add the phenol that accounts for monomer mass percentage 5%, other is with embodiment 4.Products obtained therefrom is numbered KRB-19.
Embodiment 20.
Add the phenol that accounts for monomer mass percentage 5%, other is with embodiment 5.Products obtained therefrom is numbered KRB-20.
Comparative example 1.
Adopt the macropore styrene ion exchange resin polymerization process identical, do not add (methyl) acrylic acid fluoroalkyl esters monomer and phenol and participate in polymerization with embodiment 1-20.Products obtained therefrom is a comparative example-1.
Comparative example 2.
Add the acrylic acid hexafluoro butyl ester that accounts for monomer mass percentage 0.01%, 0.01% phenol is participated in polymerization, and other is with embodiment 1.Products obtained therefrom is numbered comparative example-2.
Comparative example 3.
Add the acrylic acid hexafluoro butyl ester that accounts for monomer mass percentage 5%, 10% phenol is participated in polymerization, and other is with embodiment 1.Products obtained therefrom is numbered comparative example-3.
Embodiment 21. catalyst are used for the evaluation 1 of hydrogen phosphide cumene (CHP) decomposition reaction experimental implementation reaction). test method:
In the 2L there-necked flask, squeeze into the pure water of 1L, be reflected to be with in the batch reactor that stirs and carry out, reaction condition is: 60～100 ℃ of temperature, the pressure normal pressure is squeezed into N
2Air is isolated, and raw material CHP molar fraction 20%. is a solvent with the mixed liquor of phenol-acetone, and its volume ratio is 1:5.The mass percentage content that resin accounts for raw material CHP is 15%, and insulation 300h takes out the survey physical and chemical index with resin catalyst.2). the mensuration of mill back rate of small round spheres
Method by stipulating among the GB/T12598 is measured.
Mill back rate of small round spheres rate of change %=(mill back rate of small round spheres behind the rate of small round spheres-nitric acid dousing of the preceding mill of nitric acid dousing the back)/preceding mill of nitric acid dousing back rate of small round spheres; Mill back rate of small round spheres rate of change is more little; Mechanical strength of resin is good more, and oxidation resistent susceptibility is high more, is also just representing longer service life.
Table: the comparison of the test specimen oxidation resistent susceptibility that different process is made
| Numbering | Mill back rate of small round spheres rate of change % |
| KRB－1 | 3.15 |
| KRB－2 | 3.45 |
| KRB－3 | 5.61 |
| KRB－4 | 5.26 |
| KRB－5 | 6.18 |
| KRB－6 | 3.42 |
| KRB－7 | 4.10 |
| KRB－8 | 4.65 |
| KRB－9 | 4.39 |
| KRB－10 | 18.15 |
| KRB－11 | 5.41 |
| KRB－12 | 3.52 |
| KRB－13 | 4.12 |
| KRB－14 | 8.95 |
| KRB－15 | 15.52 |
| KRB－16 | 10.13 |
| KRB－17 | 3.15 |
| KRB－18 | 1.25 |
| KRB-19 | 3.69 |
| KRB-20 | 2.89 |
| Comparative example-1 | 35.42 |
| Comparative example-2 | 39.45 |
| Comparative example-3 | 27.15 |
Can find out from the data of last table; The resin catalyst oxidation resistent susceptibility for preparing according to the method for the invention far is better than the known acid resin catalyst that in polymerization, does not add acrylic acid fluoroalkyl esters monomer and phenol, and the resin catalyst that in polymerization, does not add acrylic acid fluoroalkyl esters monomer and phenol according to ratio according to the invention.Therefore, the resin catalyst oxidative resistance that the method for the invention prepares is better, longer service life.
Claims (6)
1. resin catalyst that is applied to decomposing hydrogen phosphide cumene to prepare phynol; Said catalyst adopts macropore styrene ion exchange resin polymerization process; Add (methyl) acrylic acid fluoroalkyl esters monomer and phenol and participate in polymerization; Obtain described resin catalyst through sulfonation again, its structural formula is:
R wherein
1Be H, CH
2Or CF
2; M>=1.
2. the described resin catalyst of claim 1, wherein (methyl) acrylic acid fluoroalkyl esters monomer is acrylic acid hexafluoro butyl ester, dodecafluorhe-ptylacrylate and/or acrylic acid ten trifluoro monooctyl esters.
3. the preparation technology of the said resin catalyst of claim 1; Said technology comprises: adopt macropore styrene ion exchange resin polymerization process, it is characterized in that, the control degree of cross linking 15～30% in the polymerization process; Pore rate 30～60%; Add (methyl) acrylic acid fluoroalkyl esters monomer of the whole monomer mass percentages 0.1～2% that account for polymerisation simultaneously, 0.1～5% phenol is participated in polymerization, obtains described resin catalyst through sulfonation again.
4. the preparation technology of claim 3, wherein, (methyl) acrylic acid fluoroalkyl esters monomer is acrylic acid hexafluoro butyl ester, dodecafluorhe-ptylacrylate and/or acrylic acid ten trifluoro monooctyl esters.
5. claim 3 or 4 preparation technology, wherein, the mass percent of (methyl) acrylic acid fluoroalkyl esters monomer is 1%, the mass percent of phenol is 5%.
6. claim 1 or 2 application of described resin catalyst in decomposing hydrogen phosphide cumene to prepare phynol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210178302.9A CN102698801B (en) | 2012-06-01 | 2012-06-01 | Resin catalyst applied to preparation of phenol through decomposition of cumene hydroperoxide (CHP) and preparation method for resin catalyst |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210178302.9A CN102698801B (en) | 2012-06-01 | 2012-06-01 | Resin catalyst applied to preparation of phenol through decomposition of cumene hydroperoxide (CHP) and preparation method for resin catalyst |
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| Publication Number | Publication Date |
|---|---|
| CN102698801A true CN102698801A (en) | 2012-10-03 |
| CN102698801B CN102698801B (en) | 2014-02-19 |
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|---|---|---|---|
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Cited By (4)
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|---|---|---|---|---|
| CN105218304A (en) * | 2015-10-12 | 2016-01-06 | 中石化上海工程有限公司 | Moving-burden bed reactor is adopted to prepare the method for phenol-acetone |
| CN105688994A (en) * | 2016-01-18 | 2016-06-22 | 张玲 | Preparation method of phenol catalyst |
| CN106866379A (en) * | 2017-03-23 | 2017-06-20 | 中石化上海工程有限公司 | Reactive distillation decomposes the method that CHP prepares phenol-acetone |
| CN113083363A (en) * | 2019-12-23 | 2021-07-09 | 万华化学集团股份有限公司 | Resin catalyst and preparation method and application thereof |
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| CN102319585A (en) * | 2011-05-18 | 2012-01-18 | 凯瑞化工股份有限公司 | High-temperature-resistant maleic anhydride (MAH) resin catalyst and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105218304A (en) * | 2015-10-12 | 2016-01-06 | 中石化上海工程有限公司 | Moving-burden bed reactor is adopted to prepare the method for phenol-acetone |
| CN105218304B (en) * | 2015-10-12 | 2018-07-06 | 中石化上海工程有限公司 | The method that phenol-acetone is prepared using moving-burden bed reactor |
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| CN106866379B (en) * | 2017-03-23 | 2020-11-10 | 中石化上海工程有限公司 | Method for preparing phenol acetone by CHP (CHP) through reactive distillation decomposition |
| CN113083363A (en) * | 2019-12-23 | 2021-07-09 | 万华化学集团股份有限公司 | Resin catalyst and preparation method and application thereof |
| CN113083363B (en) * | 2019-12-23 | 2022-09-16 | 万华化学集团股份有限公司 | Resin catalyst and preparation method and application thereof |
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