CN1039707C - Preparation method of p-nonyl phenol - Google Patents
Preparation method of p-nonyl phenol Download PDFInfo
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- CN1039707C CN1039707C CN92109000A CN92109000A CN1039707C CN 1039707 C CN1039707 C CN 1039707C CN 92109000 A CN92109000 A CN 92109000A CN 92109000 A CN92109000 A CN 92109000A CN 1039707 C CN1039707 C CN 1039707C
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- IGFHQQFPSIBGKE-UHFFFAOYSA-N 4-nonylphenol Chemical compound CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 title claims description 30
- 238000002360 preparation method Methods 0.000 title abstract description 7
- 238000000034 method Methods 0.000 claims abstract description 34
- JRZJOMJEPLMPRA-UHFFFAOYSA-N 1-nonene Chemical compound CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 30
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical class CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 claims abstract description 30
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000000203 mixture Substances 0.000 claims abstract description 26
- 150000001768 cations Chemical class 0.000 claims abstract description 7
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims abstract description 3
- 230000002378 acidificating effect Effects 0.000 claims abstract description 3
- 239000003456 ion exchange resin Substances 0.000 claims abstract description 3
- 229920003303 ion-exchange polymer Polymers 0.000 claims abstract description 3
- 150000001875 compounds Chemical class 0.000 claims description 19
- 238000006243 chemical reaction Methods 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 239000000047 product Substances 0.000 claims description 11
- 239000006227 byproduct Substances 0.000 claims description 9
- 238000004821 distillation Methods 0.000 claims description 6
- JKTAIYGNOFSMCE-UHFFFAOYSA-N 2,3-di(nonyl)phenol Chemical compound CCCCCCCCCC1=CC=CC(O)=C1CCCCCCCCC JKTAIYGNOFSMCE-UHFFFAOYSA-N 0.000 claims 2
- 230000029936 alkylation Effects 0.000 abstract description 3
- 238000005804 alkylation reaction Methods 0.000 abstract description 3
- 239000011541 reaction mixture Substances 0.000 description 13
- 239000003054 catalyst Substances 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- YZUPZGFPHUVJKC-UHFFFAOYSA-N 1-bromo-2-methoxyethane Chemical compound COCCBr YZUPZGFPHUVJKC-UHFFFAOYSA-N 0.000 description 1
- 241001550224 Apha Species 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 239000008246 gaseous mixture Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- GJRQTCIYDGXPES-UHFFFAOYSA-N iso-butyl acetate Natural products CC(C)COC(C)=O GJRQTCIYDGXPES-UHFFFAOYSA-N 0.000 description 1
- FGKJLKRYENPLQH-UHFFFAOYSA-M isocaproate Chemical compound CC(C)CCC([O-])=O FGKJLKRYENPLQH-UHFFFAOYSA-M 0.000 description 1
- JMMWKPVZQRWMSS-UHFFFAOYSA-N isopropanol acetate Natural products CC(C)OC(C)=O JMMWKPVZQRWMSS-UHFFFAOYSA-N 0.000 description 1
- 229940011051 isopropyl acetate Drugs 0.000 description 1
- GWYFCOCPABKNJV-UHFFFAOYSA-N isovaleric acid Chemical compound CC(C)CC(O)=O GWYFCOCPABKNJV-UHFFFAOYSA-N 0.000 description 1
- OQAGVSWESNCJJT-UHFFFAOYSA-N isovaleric acid methyl ester Natural products COC(=O)CC(C)C OQAGVSWESNCJJT-UHFFFAOYSA-N 0.000 description 1
- 238000006384 oligomerization reaction Methods 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 230000005180 public health Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to a process for the preparation of nonylphenols by reacting phenol with nonene in the presence of an acidic ion exchange resin. The process is carried out in two steps. A first step of contacting a mixture of phenol and tripropylene with a gel-type and/or macroporous cation exchanger in the presence of an alkylation product; in the second step, the mixture containing phenol, nonene and the like is contacted with a macroporous cation exchanger.
Description
The present invention relates in the presence of acidic ion exchange resin reaction by phenol and nonene with the method for preparation to nonyl phenol.Nonyl phenol, particularly its para-isomeride are the important intermediate in the tensio-active agent production process.
Poland Patent the 93812nd and disclosed a kind of method that in the presence of cationite, prepares nonyl phenol for No. 97840, its principle is to carry out the alkylation of phenol under heating condition with tripropylene, temperature improves gradually in the reaction process.Take out a certain proportion of reaction mixture in a continuous manner after reaching outlet temperature from reaction system, the weight concentration of nonyl phenol is 40% to 75% in this mixture, and nonyl phenol coarse products wherein and the unconverted part that remains to be recycled are separated.
Till above-mentioned preparation process was performed until and is no more than 15 parts of weight with respect to the prepared nonyl phenol of the dry catalyst of every part of weight, with the equipment turned letter, another took turns preparation with new reinforced beginning more then.A shortcoming of this method is that byproducts build-up is arranged in the reaction mixture.
Belgian patent has disclosed a kind of method for preparing alkylphenol by alkene and phenol reactant No. 860268, unconverted phenol be separating of alkylate in 80 ℃ to 250 ℃ temperature range, to carry out the way that gas is put forward with rare gas element, to be that the initial phenol of every part of weight is reinforced per hour use 0.3 to 6 part of volume to the rare gas element consumption, subsequently gaseous mixture cooled-40 ℃ to 100 ℃ to reclaim phenol with a step or two steps.This method also generates the dialkyl phenol and the trialkyl phenol (surpassing 5% parts by weight) of larger amt except that generating monoalkyl phenol, these dialkyl phenols can separate with primary product by distillation with trialkyl phenol, but the efficient of entire method can be affected.
In these methods of above disclosure, the inert compound in the alkene is not discharged from system, and this just causes them to be accumulated in preparation process in the system, and consequently the production efficiency of final nonyl phenol product descends gradually.
The objective of the invention is to develop and a kind ofly make the method for alkylation of phenol with nonene, the efficient of this method and selectivity are enough high, and the weight percentage that the nonyl phenol that is generated contains para-isomeride is not less than 90%.By discovering, prepare nonyl phenol with two-step approach and can avoid generating the increasing by product of quantity: in the first step conversion of nonene not too complete, the generation of binonylphenol then is subject to significant restrictions.
Very unexpected is also to find simultaneously, in the presence of the mixture of phenol that definite composition is arranged and alkylate, in the presence of macroporous catalyst, the nonene of remainder in the first step is joined the growing amount that goes to make nonene be converted into nonyl phenol fully in second step and can not increase by product.
According to the present invention, in the first step of described method, have alkylate in the presence of, phenol contacts under 70 ℃ to 140 ℃ temperature with gel-type and/or macroporous type cationite with the mixture (containing the inert compound that is no more than 2% (weight)) of tripropylene.In second step of described method, contain 30% to 80% (weight) phenol, 1% to 25% (weight) nonene, 0.1% to 10% (weight) inert compound, 0.01% to 1% (weight) water, 3% to 60% (weight) nonyl phenol, the mixture that is no more than 5% (weight) binonylphenol and is no more than other alkylate by-products (total amount is equivalent to 1% to 50% (weight) of mixture stream passes gross weight after the reaction that this method the first step taken out) of 5% (weight) contacts under 80 ℃ to 150 ℃ temperature with the macroporous cation exchanger.The cut that contains inert compound and water is isolated in the mixture redistillation after the reaction of gained.Mixture merges after the reaction of the distillation residue and the first step, and final nonyl phenol product is isolated in redistillation.The volume ratio of used cationite was 30: 1 to 2: 1 during the first step and second went on foot.Used tripropylene is the oligomerization product of propylene in present method, contain the inert compound that is no more than 2% (weight), for example boiling point be 120 ℃ to the stable hydrocarbon of 150 ℃ of scopes and the carboxylicesters of isopropyl acetate or isobutyl acetate one class, these inert compounds are not easy to remove or can not remove on very economical ground, thereby cause it to accumulate in the reaction mixture of system's internal recycle.
Except inert compound, mainly be also to need from reaction system, to remove with the reinforced moisture that enters system, otherwise when the concentration of water surpasses 1% (weight), thereby it will influence the formation efficiency that activity of such catalysts also influences the nonyl phenol final product.Prepare in the process of nonyl phenol in two-step approach, be easy to from the reaction mixture (wherein not conforming to nonene) in this second step of method, remove inert substance and water with distillation method.
Because charging almost is a Quantitative yield, the inventive method provides very high selectivity, and compares with currently known methods, and the formation efficiency of nonyl phenol will exceed 5% to 20%.In addition, the color of the nonyl phenol product that method of the present invention provided is 5 to 10APHA (American Public Health Association (APHA)) standard units, and contained nonyl phenol para-isomeride is higher than 90% (weight) in the product, and binonylphenol content is no more than 1% (weight).Because adding compound of reaction with tripropylene and water makes them keep constant concentration to avoid the loss of charging in the round-robin reaction mixture, entire method can be carried out continuously, and this just makes that the efficient of process is high and stable.
Embodiment 1.
In vertical and cylindrical reactor (D=1800 millimeter, h=9 rice), pack into 22 cubic metres the gel type cation exchanger of the Wofatit KPS trade mark.Mix resulting reaction mixture with 18 cubic metres/hour the flow above-mentioned reactor of flowing through by following three bursts of streams, first burst of logistics is phenol and tripropylene, wherein contains the inert compound of 7.6 kilograms of/hour flows and the water of 0.3 kilogram of/hour flow; Second burst of logistics comes the unconverted raw material of mixture predistillation operation behind the autoreaction, wherein contains the inert compound of 43.3 kilograms of/hour flows and the water of 1.6 kilograms of/hour flows, the first step of its circulation return course; The 3rd burst of logistics is the collected partial reaction mixture of reactor bottom.Temperature at reactor inlet place reaction mixture is 100 ℃.From the alkylate logistics that reactor takes out, contain 654.5 kilograms/hour phenol, 147.7 kilogram/hour nonene, 50.6 kilogram/hour inert compound, 1.9 kilogram/hour water, 612.5 kilogram/hour nonyl phenol, 8.6 kilogram/hour binonylphenol and other by product of 5.9 kilograms/hour.
Mix the mixture that obtains with phenol with a part of alkylate logistics and add to second step of present method as charging, the phenol that contains 57.28% (weight) in this mixture, the nonene of 7.62% (weight), the inert compound of 2.61% (weight), the water of 0.12% (weight), the nonyl phenol of 31.61% (weight), other by product of the binonylphenol of 0.44% (weight) and 0.31% (weight).
In second step of present method, a part of reaction mixture that said mixture stream and reactor bottom are collected merges and volume of the reaction mixture logistics warp let-off of obtaining is 5 cubic metres a reactor, logistics flux is 4 cubic metres/hour, is filled with the macroporous cation exchanger of Am-berlyst-16 model in the reactor.The reactor inlet place, the temperature in second step of process is 110 ℃.After the reaction that second stage reactor takes out, do not conform to nonene the mixture stream passes, contained is the phenol of 51.64% (weight), the inert compound of 2.62% (weight), the water of 0.12% (weight), the nonyl phenol of 44.67% (weight), other alkylate by-product of the binonylphenol of 0.66% (weight) and 0.31% (weight).
Mixture distills after the reaction in second step of present method, separate and obtain 7.5 kilograms/hour inert compound and 0.3 kilogram/hour water, the alkylate stream of distillation residuum and present method the first step merges the nonyl phenol final product to reclaim 650 kilograms/hour, wherein contain the binonylphenol of the para-isomeride and 0.88% (weight) of 92% (weight), the color of the finished product is 10APHA.
Embodiment 2
Part in the logistics of the unconverted raw material of embodiment 1 (contains 73.39% (weight) phenol, 15.20% (weight) nonene, 5.15% (weight) inert compound, 0.20% (weight) water and 6.15% (weight) nonyl phenol) as charging add to present method second the step, the reaction mixture in this step is that the part of the reaction mixture collected by said mixture logistics and reactor bottom merges and forms, merge the reaction mixture obtain and flow through one with 2 cubic metres/hour flow and be filled with Amberlyst-15 type macroporous cation exchanger, volume is 2 cubic metres a reactor.This reactor inlet place, the temperature in second step of present method is 120 ℃.After present method reaction in second step, isolate 7.35 kilograms/hour inert compound and 0.29 kilogram/hour water the mixture, separate in the residuum and contain 88.49 kilograms of/hour phenol, 46.22 kilogram/hour nonyl phenol and 0.35 kilogram of/hour binonylphenol, the alkylate logistics of this residuum and this law the first step is merged, reclaim the nonyl phenol product then, its product flow and quality are as described in the embodiment 1.
Claims (2)
- In the presence of acidic ion exchange resin, make phenol and nonene prepared in reaction method to nonylphenol, wherein, this method was carried out with two steps, in the first step, in the presence of the product of using tripropylene alkanisation base phenol, make and contain the phenol that is no more than 2% weight inert compound and 0.1% weight water and contact with gel-type and/or macroporous type cationite in 70 ℃-140 ℃ temperature range with the mixture of tripropylene, described alkylate mainly contains nonylphenol and dinonyl phenol and by product; In second step, make contain 30%-80% weight phenol, 1%-25% weight nonene, 0.1%-10% weight inert compound, 0.01%-1% weight water, 3%-60% weight nonylphenol, 5% weight dinonyl phenol contacts with the macroporous cation exchanger in 80 ℃-150 ℃ temperature range with the mixture of 5% other by product of weight at the most at the most, the amount of described mixture is the 1%-50% of mixture flow weight after the first step reaction of taking out; To separate inert compound and water, mixture merges mixture after the reaction of the distillation residue and the first step through distillation after the reaction of the second step gained, by distilling to reclaim nonyl phenol.
- 2. the process of claim 1 wherein that the cationite that is used for the first step is 30 with the volume ratio that is used for second cationite that goes on foot: 1-2: 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN92109000A CN1039707C (en) | 1992-08-01 | 1992-08-01 | Preparation method of p-nonyl phenol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN92109000A CN1039707C (en) | 1992-08-01 | 1992-08-01 | Preparation method of p-nonyl phenol |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1082530A CN1082530A (en) | 1994-02-23 |
| CN1039707C true CN1039707C (en) | 1998-09-09 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN92109000A Expired - Fee Related CN1039707C (en) | 1992-08-01 | 1992-08-01 | Preparation method of p-nonyl phenol |
Country Status (1)
| Country | Link |
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| CN (1) | CN1039707C (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103265408B (en) * | 2013-05-31 | 2016-01-20 | 滁州市润达溶剂有限公司 | A kind of process for purification of nonyl phenol |
| CN103483489B (en) * | 2013-09-27 | 2015-12-09 | 凯瑞环保科技股份有限公司 | A kind of preparation method of catalytic resin for nonyl phenol |
| CN107162878A (en) * | 2017-06-06 | 2017-09-15 | 常州大学 | A kind of acidic ion liquid is used for the method for being catalyzed nonene and phenol synthesis nonyl phenol |
| CN107162879B (en) * | 2017-06-06 | 2020-05-26 | 常州大学 | Method for synthesizing nonyl phenol by catalyzing nonene and phenol with alkaline ionic liquid |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4168390A (en) * | 1973-09-14 | 1979-09-18 | Chemische Werke Huls A.G. | Process for continuous alkylation of phenol using ion exchange resins |
-
1992
- 1992-08-01 CN CN92109000A patent/CN1039707C/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4168390A (en) * | 1973-09-14 | 1979-09-18 | Chemische Werke Huls A.G. | Process for continuous alkylation of phenol using ion exchange resins |
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| Publication number | Publication date |
|---|---|
| CN1082530A (en) | 1994-02-23 |
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