CN102698801B - 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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- CN102698801B CN102698801B CN201210178302.9A CN201210178302A CN102698801B CN 102698801 B CN102698801 B CN 102698801B CN 201210178302 A CN201210178302 A CN 201210178302A CN 102698801 B CN102698801 B CN 102698801B
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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, more than 90% phenol is produced by cumene method in the world.This method mainly comprises 3 reactions: alkylated reaction, oxidation reaction and decomposition reaction.For hydrogen phosphide cumene (CHP) decomposition reaction, mostly adopting traditional concentrated sulfuric acid catalyst. its reaction is violent, not easy to operate, accessory substance is many, separation of products difficulty, equipment corrosion is serious, with the sodium sulphate that alkali neutralisation of sulphuric acid generates, easily causes the fouling of distillation system reboiler. while processing fouling, produce again more phenol-containing wastewater. and contaminated environment.Therefore, finding better catalyst replaces sulfuric acid very necessary.At present, a lot of for the catalyst of CHP decomposition reaction both at home and abroad, mainly comprise (1) homogeneous reaction catalyst (as BF3 class, halogeno-benzene thiophenol, metal complex etc.); (2) clay catalyst; (3) zeolite catalyst; (4) acid resin catalyst.Wherein, sulfonate resin, with other catalyst ratios, has reaction condition gentleness, and side reaction is few, and selectively good, yield is high, renewable, the advantage that the life-span is long.And as solid matter, easily separated from reaction medium, corrosive equipment not, add uniform particles, be specially adapted to successive reaction, and can be according to granular size. voidage and specific area are selected specific resin, control rate of catalysis reaction, applying flexible.
Hydrogen phosphide cumene has strong oxidizing property, easily causes that resin " decortication " is damaged, number of dropouts is large, and generator nozzle easily stops up, and affects the service life of resin.So the oxidation resistance that improves resin catalyst is to produce phenol process technical barrier urgently to be resolved hurrily.
CN101343212 provides a kind of method of decomposing hydrogen phosphide cumene to prepare phynol and acetone, it is characterized in that adopting the smectites solid acid catalyst through inorganic ammonium salt modification is catalysts, make hydrogen phosphide cumene generation decomposition reaction, the inventive method makes that reaction is carried out under relatively mild condition, extent of reaction easily controlled, accessory substance is few, corrosion-free, product easily separated, catalyst is recyclable recycles.
CN101219394 provides a kind of manufacturing phynol/acetone with hydrogen phosphide cumene decomposition carried heteropoly acid catalyst.This invention has very wide acid site and acid strength, the advantage such as specific area is large, structural stability good, activity is high, corrosion-free, pollution-free, product is easily separated, reaction condition is gentle, production cost is low and can regenerate that can modulation.
But, the shortcoming such as above patent is used solid acid as catalyst, has preparation method complexity, and service life is short.
Summary of the invention
(methyl) acrylic acid fluoroalkyl esters monomer participates in fluorinated acrylamide acid polymer that reaction obtains and has 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 surface can, and C-C main chain has been played to shielding protection effect, thereby has improved weatherability, non-oxidizability and the corrosion resistance of organo-fluorine polymer.
Therefore, for a little less than being applied to the resin catalyst non-oxidizability of decomposing hydrogen phosphide cumene to prepare phynol in prior art, service life short defect, the present invention proposes a kind of described resin catalyst, described resin catalyst is that to take the formula of the conventional acid resin catalyst-macropore styrene type cation exchange resin in this area and preparation technology be basis, difference is in polymerization, add (methyl) acrylic acid fluoroalkyl esters monomer and phenol to participate in polymerization, then obtain through conventional process for sulfonation.Polymerisation equation is as follows:
After oversulfonate, end product structural formula is as follows:
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, described 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, described technique is as follows:
Adopt macropore styrene ion exchange resin polymerization process well known in the art, control the 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 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, 0.1～5% phenol participates in polymerization, then obtains finished product through conventional process for sulfonation simultaneously.Wherein, (methyl) acrylic acid fluoroalkyl esters monomer is preferably 1%, and phenol is preferably 5%.
The inventor finds on the basis of great many of experiments and research, adopt acrylic acid fluoroalkyl esters monomer and the phenol of above-mentioned percent concentration proportioning to participate in polymerization, unforeseeable technique effect described in after the resin catalyst obtaining has, reason is as follows: 1). and too much acrylic acid fluoroalkyl esters monomer participates in polymerization, can destroy the stabilising system balance of polymerization, cause sudden and violent gathering, or make polymer thickness, affect the generation of normal resin particle; 2) too much phenol participates in polymerization, due to the sterically hindered effect of phenolic hydroxyl group, can affect on sulfonic group to cinnamic phenyl ring, causes catalyst exchange capacity to reduce, thereby affects catalytic activity.And the addition of these two kinds of materials is very few, required weatherability, non-oxidizability, corrosion resistance and compatibility can cannot be reached.
This product has following beneficial effect:
Owing to having added phenol and (methyl) acrylic acid fluoroalkyl esters monomer in preparation technology, the compatibility that phenolic hydroxyl group is conducive to catalyst and phenol improves, C-F structure can improve catalyst oxidation resistent susceptibility, thereby catalyst resistance to oxidation prepared by technique of the present invention is effective, long service life.Can decompose in preparation phenol production and use at catalyzing hydrogen peroxide isopropylbenzene.There is catalyst amount few, reaction continuously, the advantage such as the reaction time is short.
The specific embodiment
Following instance is only to further illustrate the present invention, is not restriction the scope of protection of the invention.
Embodiment 1:
1). polymerisation
Select the macropore styrene ion exchange resin polymerization process of knowing altogether in the industry, control the 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%, 0.1% phenol participates in polymerization, then obtains finished product through techniques such as sulfonation simultaneously.Be numbered KRB-1
Embodiment 2
The polymerisation degree of cross linking 30%, the other the same as in Example 1.Products obtained therefrom is numbered KRB-2.
Embodiment 3
The polymerisation degree of cross linking 22.5%, the other the same as in Example 1.Products obtained therefrom is numbered KRB-3.
Embodiment 4
Polymerisation pore rate 60%, the other the same as in Example 1.Products obtained therefrom is numbered KRB-4.
Embodiment 5
Polymerisation pore rate 45%, the other the same as in Example 1.Products obtained therefrom is numbered KRB-5.
Embodiment 6
Add the acrylic acid hexafluoro butyl ester that accounts for monomer mass percentage 2%, the other the same as in Example 1.Products obtained therefrom is numbered KRB-6.
Embodiment 7
Add the acrylic acid hexafluoro butyl ester that accounts for monomer mass percentage 2%, the other the same as in Example 2.Products obtained therefrom is numbered KRB-7.
Embodiment 8
Add the acrylic acid hexafluoro butyl ester that accounts for monomer mass percentage 2%, the other the same as in Example 3.Products obtained therefrom is numbered KRB-8.
Embodiment 9
Add the acrylic acid hexafluoro butyl ester that accounts for monomer mass percentage 2%, the other the same as in Example 4.Products obtained therefrom is numbered KRB-9.
Embodiment 10.
Add the acrylic acid hexafluoro butyl ester that accounts for monomer mass percentage 2%, the other the same as in Example 5.Products obtained therefrom is numbered KRB-10.
Embodiment 11.
Add the dodecafluorhe-ptylacrylate that accounts for monomer mass percentage 1%, the other the same as in Example 1.Products obtained therefrom is numbered KRB-11.
Embodiment 12.
Add the acrylic acid hexafluoro butyl ester that accounts for monomer mass percentage 1%, the other the same as in Example 2.Products obtained therefrom is numbered KRB-12.
Embodiment 13.
Add the acrylic acid hexafluoro butyl ester that accounts for monomer mass percentage 1%, the other the same as in Example 3.Products obtained therefrom is numbered KRB-13.
Embodiment 14.
Add the acrylic acid hexafluoro butyl ester that accounts for monomer mass percentage 1%, the other the same as in Example 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%, the other the same as in Example 5.Products obtained therefrom is numbered KRB-15.
Embodiment 16.
Add the phenol that accounts for monomer mass percentage 0.1%, the other the same as in Example 1.Products obtained therefrom is numbered KRB-16.
Embodiment 17.
Add the phenol that accounts for monomer mass percentage 5%, the other the same as in Example 2.Products obtained therefrom is numbered KRB-17.
Embodiment 18.
Add the phenol that accounts for monomer mass percentage 5%, the other the same as in Example 3.Products obtained therefrom is numbered KRB-18.
Embodiment 19.
Add the phenol that accounts for monomer mass percentage 5%, the other the same as in Example 4.Products obtained therefrom is numbered KRB-19.
Embodiment 20.
Add the phenol that accounts for monomer mass percentage 5%, the other the same as in Example 5.Products obtained therefrom is numbered KRB-20.
Comparative example 1.
Adopt the macropore styrene ion exchange resin polymerization process identical with embodiment 1-20, do not add (methyl) acrylic acid fluoroalkyl esters monomer and phenol to participate in polymerization.Products obtained therefrom is comparative example-1.
Comparative example 2.
Add the acrylic acid hexafluoro butyl ester that accounts for monomer mass percentage 0.01%, 0.01% phenol participates in polymerization, the other the same as in Example 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 participates in polymerization, the other the same as in Example 1.Products obtained therefrom is numbered comparative example-3.
Embodiment 21. catalyst are for the evaluation 1 of hydrogen phosphide cumene (CHP) decomposition reaction experimental implementation reaction). test method:
In 2L there-necked flask, squeeze into the pure water of 1L, in the batch reactor that reaction is stirred at band, carry out, reaction condition is: 60～100 ℃ of temperature, pressure normal pressure, squeezes into N
2air is isolated, and it is solvent that raw material CHP molar fraction 20%. be take 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 resin catalyst to survey physical and chemical index.2). the mensuration of rate of small round spheres after mill
By the method for stipulating in GB/T12598, measure.
The rear rate of small round spheres of mill after the rear rate of small round spheres-nitric acid dousing of the front mill of the rear rate of small round spheres rate of change %=(nitric acid dousing of mill) the rear rate of small round spheres of the front mill of/nitric acid dousing, after mill, rate of small round spheres rate of change is less, mechanical strength of resin is better, and oxidation resistent susceptibility is higher, is also just representing longer service life.
Table: the comparison of the test specimen oxidation resistent susceptibility that different process is made
| Numbering | Rate of small round spheres rate of change % after mill |
| 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 |
As can be seen from the above table data, the resin catalyst oxidation resistent susceptibility preparing according to the method for the invention is far better than the known acid resin catalyst that does not add acrylic acid fluoroalkyl esters monomer and phenol in polymerization, and the resin catalyst that does not add acrylic acid fluoroalkyl esters monomer and phenol according to ratio of the present invention in polymerization.Therefore, the resin catalyst oxidative resistance that the method for the invention prepares is better, longer service life.
Claims (6)
1. a resin catalyst that is applied to decomposing hydrogen phosphide cumene to prepare phynol, described catalyst adopts macropore styrene ion exchange resin polymerization process, add (methyl) acrylic acid fluoroalkyl esters monomer and phenol to participate in polymerization, through sulfonation, obtain described resin catalyst again, its structural formula is:
Wherein R1 is H, CH2 or CF2; M >=1; Wherein, (methyl) acrylic acid fluoroalkyl esters monomer accounts for whole monomer mass percentages 0.1～2% of polymerisation, and phenol is 0.1～5%.
2. resin catalyst claimed in 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 resin catalyst described in claim 1, described technique comprises: adopt macropore styrene ion exchange resin polymerization process, it is characterized in that, in polymerization process, control the degree of cross linking 15～30%, pore rate 30～60%, (methyl) acrylic acid fluoroalkyl esters monomer that simultaneously adds the whole monomer mass percentages 0.1～2% that account for polymerisation, 0.1～5% phenol participates in polymerization, then obtains described resin catalyst through sulfonation.
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. the application of the resin catalyst described in claim 1 or 2 in decomposing hydrogen phosphide cumene to prepare phynol.
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|---|---|---|---|
| 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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|---|---|---|---|
| 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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| CN102698801B true CN102698801B (en) | 2014-02-19 |
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| 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 |
| CN105688994A (en) * | 2016-01-18 | 2016-06-22 | 张玲 | Preparation method of phenol catalyst |
| 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 |
| 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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|---|---|---|---|---|
| WO2003076376A3 (en) * | 2002-03-14 | 2003-11-13 | Eurotecnica Dev & Licensing S | Process for the synthesis of phenol and acetone |
| CN1524067A (en) * | 2001-06-26 | 2004-08-25 | 杜邦公司 | Decomposition of organic hydroperoxides in the presence of a particulate catalyst containing highly fluorinated polymer having sulfonic acid groups and process for the manufacture of bisphenol a |
| CN1649811A (en) * | 2002-03-06 | 2005-08-03 | 通用电气公司 | Production and purification of phenol |
| CN102186799A (en) * | 2008-10-16 | 2011-09-14 | 沙伯基础创新塑料知识产权有限公司 | Method for producing phenol and acetone |
| 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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- 2012-06-01 CN CN201210178302.9A patent/CN102698801B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1524067A (en) * | 2001-06-26 | 2004-08-25 | 杜邦公司 | Decomposition of organic hydroperoxides in the presence of a particulate catalyst containing highly fluorinated polymer having sulfonic acid groups and process for the manufacture of bisphenol a |
| CN1649811A (en) * | 2002-03-06 | 2005-08-03 | 通用电气公司 | Production and purification of phenol |
| WO2003076376A3 (en) * | 2002-03-14 | 2003-11-13 | Eurotecnica Dev & Licensing S | Process for the synthesis of phenol and acetone |
| CN102186799A (en) * | 2008-10-16 | 2011-09-14 | 沙伯基础创新塑料知识产权有限公司 | Method for producing phenol and acetone |
| 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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