CN103801393A - Preparation method of catalyst for phenol preparation by benzene hydroxylation - Google Patents
Preparation method of catalyst for phenol preparation by benzene hydroxylation Download PDFInfo
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- CN103801393A CN103801393A CN201210439833.9A CN201210439833A CN103801393A CN 103801393 A CN103801393 A CN 103801393A CN 201210439833 A CN201210439833 A CN 201210439833A CN 103801393 A CN103801393 A CN 103801393A
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- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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Abstract
The invention discloses a preparation method of a catalyst for phenol preparation by benzene hydroxylation, which comprises the following steps: (1) adding a TS-1 molecular sieve into an ammonium salt solution, performing stirring, drying and roasting to obtain the ammonium-treated TS-1molecular sieve; (2) adding the ammonium-treated TS-1molecular sieve prepared in step (1) into a tin-containing acetone solution, performing dipping, drying and roasting to obtain the catalyst for phenol preparation by benzene hydroxylation. The catalyst of the invention is simple in preparation process, high in phenol selectivity, and green and environment-friendly in reaction process. When the catalyst of the invention is used in phenol preparation reaction by benzene hydroxylation, the phenol selectivity is up to 99.6% when the benzene conversion rate is 16.4%.
Description
Technical field
The present invention relates to the preparation method of a kind of benzene hydroxylation phenol catalyst processed.
Background technology
phenol (Phenol) is commonly called as carbolic acid, is a kind of important large Organic Chemicals, mainly for the production of resin, medicine intermediate, agricultural chemicals, spices, dyestuff and auxiliary agent etc.At present main production method both domestic and external is production phenols, but the problem such as this method exists that reactions steps is many, complex process, environmental pollution are serious.Therefore, people to begin one's study by benzene be the production method that phenol is produced in raw material direct oxidation.And the catalytic oxidation system that TS-1 molecular sieve and hydrogen peroxide form, due to features such as reaction condition gentleness, environmental protections, gets the attention in the direct hydroxylating of benzene is prepared the new technology of phenol.
In CN101733098A, introduced a kind of benzene hydroxylation phenol catalyst processed, it is carrier that this catalyst adopts clay, by drip copper aluminum crosslinker and copper metal oxide in its suspension, then obtains this catalyst by exchange, dry and grinding.Under the condition that adds acetonitrile solvent, employing hydrogen peroxide is oxidant, and maximum conversion has reached 64.2%, and phenol has selectively been up to 85.1%.With respect to HTS, conversion ratio is greatly improved, but has reduced selectively, and under dicyandiamide solution, exists the problem of rear separation, greatly reduces the advantage of this course of reaction.
In CN101973852A, introduce a kind of take TS-1 molecular sieve as main benzene hydroxylation phenol catalyst processed.In this patent, be mainly by optimizing reaction system, improved the conversion ratio of benzene, thereby improved the yield of phenol, and phenol be selectively still not high.In this reaction system, adopt excessive hydrogen peroxide, reduce the utilization rate of hydrogen peroxide, and widely distributed phenol, the benzenediol of both having contained of product, also contain a large amount of aniline and nitrobenzene and isomers thereof simultaneously.Course of reaction control difficulty is large, is very easily aniline and nitrobenzene by benzene direct oxidation.
TS-1 molecular sieve has represented excellent catalytic performance with its distinctive structure and activity position.Although conversion ratio can be lower with respect to other catalyst, phenol is selectively very high, even can reach 100%.But in the situation of this high selectivity, conversion ratio does not reach 5%.Therefore,, in the situation that keeping high selectivity, the conversion ratio that as far as possible improves benzene becomes the key problem of this course of reaction research.
Summary of the invention
For the deficiencies in the prior art, the invention provides the preparation method of a kind of benzene hydroxylation phenol catalyst processed.Catalyst preparation process of the present invention is simple, and phenol is selectively high, course of reaction environmental protection.
The preparation method of benzene hydroxylation of the present invention phenol catalyst processed, comprises following content:
(1) TS-1 molecular sieve is joined in ammonium salt solution, stirring, dry, roasting, obtain ammonium and process TS-1 molecular sieve;
(2) the ammonium processing TS-1 molecular sieve of being prepared by step (1) joins in stanniferous acetone soln and floods, and then dry, roasting, obtains benzene hydroxylation phenol catalyst processed.
In the inventive method step (1), preferably carry out following process: before dry processing, carry out Separation of Solid and Liquid, isolated TS-1 molecular sieve again joins in ammonium salt solution and stirs.
In the inventive method, the silicon titanium of this molecular sieve of TS-1 molecular sieve is 30 ~ 120 than (mol ratio of silica and titanium oxide), preferably 60 ~ 90, and can be commercially available prod, also can prepare according to this area conventional method.
In the inventive method, ammonium salt used is one or more in ammonium nitrate, ammonium chloride, ammonium sulfate or ammonium acetate, preferably ammonium acetate; The mass ratio of ammonium salt solution and TS-1 molecular sieve is 5 ~ 20; The concentration range of ammonium salt solution is 0.5 ~ 2mol/L.
In the inventive method, Xi Yuan used is dibutyl tin dilaurate.
In the inventive method step (1), whipping temp is 20 ~ 90 ℃, preferably 50 ~ 80 ℃; Baking temperature is 70 ~ 120 ℃; Be 12 ~ 24 hours drying time; Sintering temperature is 450 ~ 650 ℃, preferably 500 ~ 550 ℃; Roasting time is 4 ~ 8 hours.
In the inventive method step (2), in stanniferous acetone soln, the content of element tin is 0.5wt% ~ 20wt%, and the mass ratio of the acetone soln of TS-1 molecular sieve and tin is 0.5 ~ 2; Preferably 1 ~ 1.5.
In the inventive method step (2), dip time is 6 ~ 48 hours, preferably 18 ~ 24 hours; Baking temperature is 70 ~ 120 ℃; Be 12 ~ 24 hours drying time; Sintering temperature is 450 ~ 650 ℃, preferably 500 ~ 550 ℃; Roasting time is 4 ~ 8 hours.
The catalyst that the inventive method obtains is for benzene hydroxylation phenol reactant processed, under atmospheric pressure state, and 40 ~ 80 ℃ of reaction temperatures, the reaction time is 2 ~ 8 hours, benzene/H
2o
2(mol/mol) be 1 ~ 5, the volume ratio of water/benzene is 2 ~ 10, and catalyst/benzene (g/mol) is 0.05 ~ 0.5; Hydrogen peroxide adopts the mode dripping, and dropwises at 30 ~ 240 minutes, and the speed of agitator that reaction adopts is 400 ~ 800r/min.
The present invention has adopted tin to having carried out modification, the activated centre Ti-O-SiO on tin and molecular sieve surface through the TS-1 molecular sieve of ammonium processing
2there is synergy, optimized the catalytic performance of catalyst, suppressed to know clearly the generation of benzenediol and benzoquinones, greatly improved the selective of phenol.
The specific embodiment
Below by embodiment, the present invention is further described, it does not limit the scope of application of the present invention.Silicon titanium described in embodiment is than the mol ratio for silica and titanium oxide.
Reaction evaluating condition: benzene/H
2o
2(mol/mol)=2:1; V
water/ V
benzene=5:1; Catalyst/benzene (g/mol)=25; Rise to 60 ℃ by room temperature, 60 ℃ of reactions of constant temperature 6 hours, mixing speed is 500r/min.React the complete room temperature that is cooled to, centrifugation, leaves standstill separatory by the liquid obtaining, and obtains oil phase and water, analyzes by chromatogram.Product adopts Agilent 6890N gas chromatograph to analyze; Analytical column is DB-5ms type capillary chromatographic column (30m*0.32mm*0.25 um); Employing fid detector detects; Adopt external standard method to process experimental data.
Embodiment 1
The ammonium processing of molecular sieve: with the ammonium salt solution of deionized water and ammonium acetate configuration 1mol/L, taking 100g TS-1 molecular screen primary powder (silicon titanium ratio is 38.7) joins in the ammonium acetate solution that 1L prepares, under 60 ℃ of water bath with thermostatic control conditions, stir 6 hours, filter, repeat aforesaid operations, then at 120 ℃, be dried 12 hours, then 6 hours deaminations of roasting at 550 ℃, obtain the TS-1 molecular sieve of ammonium processing.
The load of tin metal: with 30ml acetone solution 1.1g dibutyl tin laurate (containing 18-20 wt%Sn), take 40g ammonium salt TS-1 molecular sieve after treatment, join in solution and flood 24 hours, then sample is put into 120 ℃, baking oven dry, final sample roasting at 550 ℃ obtains the catalyst C1 of load 0.5wt%Sn for 6 hours.Its composition is in table 1, and evaluation result is in table 2.
Embodiment 2
The preparation method of catalyst C2 of the present invention is as follows:
Method for preparing catalyst is with embodiment 1, and difference is that the silicon titanium ratio of TS-1 molecular screen primary powder used is 85.8; The dibutyl tin laurate (containing 18-20 wt%Sn) that the acetone soln of preparation tin is used is 2.2g.Its composition is in table 1, and evaluation result is in table 2.
Embodiment 3
The preparation method of catalyst C3 of the present invention is as follows:
Method for preparing catalyst is with embodiment 1, and difference is that the silicon titanium ratio of TS-1 molecular screen primary powder used is 85.8; The dibutyl tin laurate (containing 18-20 wt%Sn) that the acetone soln of preparation tin is used is 4.5g.Its composition is in table 1, and evaluation result is in table 2.
Embodiment 4
The preparation method of catalyst C4 of the present invention is as follows:
Method for preparing catalyst is with embodiment 1, and difference is that the silicon titanium ratio of TS-1 molecular screen primary powder used is 85.8; The dibutyl tin laurate (containing 18-20 wt%Sn) that the acetone soln of preparation tin is used is 8.8g.Its composition is in table 1, and evaluation result is in table 2.
Embodiment 5
The preparation method of catalyst C5 of the present invention is as follows:
Method for preparing catalyst is with embodiment 1, and difference is that ammonium salt used is ammonium chloride; The dibutyl tin laurate (containing 18-20 wt%Sn) that the acetone soln of preparation tin is used is for its composition of 2.2g. is in table 1, and evaluation result is in table 2.
Embodiment 6
The preparation method of catalyst C6 of the present invention is as follows:
Method for preparing catalyst is with embodiment 1, and difference is that ammonium salt used is ammonium nitrate; The dibutyl tin laurate (containing 18-20 wt%Sn) that the acetone soln of preparation tin is used is for its composition of 2.2g. is in table 1, and evaluation result is in table 2.
Comparative example 1
Method for preparing catalyst, with embodiment 1, obtains comparative catalyst BC1.Difference is only to carry out ammonium salt processing, does not carry out the load of tin metal.Its composition is in table 1, and evaluation result is in table 2.
Comparative example 2
Method for preparing catalyst, with embodiment 1, obtains comparative catalyst BC2.Difference is that the silicon titanium ratio of TS-1 molecular screen primary powder used is 85.8; And only carry out ammonium salt processing, do not carry out the load of tin metal.Its composition is in table 1, and evaluation result is in table 2.
Table 1 catalyst composition.
| Embodiment | Catalyst numbering | Metal Sn content (wt%) in catalyst |
| Embodiment 1 | C1 | 0.5 |
| Embodiment 2 | C2 | 1.0 |
| Embodiment 3 | C3 | 2.0 |
| Embodiment 4 | C4 | 4.0 |
| Embodiment 5 | C5 | 1.0 |
| Embodiment 6 | C6 | 1.0 |
| Comparative example 1 | BC1 | --- |
| Comparative example 2 | BC2 | --- |
Table 2 evaluation result.
| Catalyst numbering | C1 | C2 | C3 | C4 | C5 | C6 | BC1 | BC2 |
| Benzene conversion ratio % | 14.1 | 15.2 | 16.4 | 16.1 | 15.0 | 14.5 | 13.1 | 12.4 |
| The selective % of phenol | 94.3 | 95.5 | 99.6 | 97.5 | 94.3 | 96.7 | 72.2 | 79.3 |
From upper table, in data, can find out, adopt benzene hydroxylation phenol catalyst processed prepared of this method, through ammonium process and tin modification after, catalyst selectivity has obtained raising greatly, the high selectivity of phenol has reached 99.6%.
Claims (12)
1. a preparation method for benzene hydroxylation phenol catalyst processed, is characterized in that comprising following content: (1) joins TS-1 molecular sieve in ammonium salt solution, and stirring, dry, roasting, obtain ammonium and process TS-1 molecular sieve; (2) the ammonium processing TS-1 molecular sieve of being prepared by step (1) joins in stanniferous acetone soln and floods, and then dry, roasting, obtains benzene hydroxylation phenol catalyst processed.
2. in accordance with the method for claim 1, it is characterized in that: in step (1), carry out following process: before dry processing, carry out Separation of Solid and Liquid, isolated TS-1 molecular sieve again joins in ammonium salt solution and stirs.
3. according to the method described in claim 1 or 2, it is characterized in that: the silica of TS-1 molecular sieve and the mol ratio of titanium oxide are 30 ~ 120.
4. according to the method described in claim 1 or 2, it is characterized in that: ammonium salt used is one or more in ammonium nitrate, ammonium chloride, ammonium sulfate or ammonium acetate.
5. according to the method described in claim 1 or 2, it is characterized in that: the mass ratio of ammonium salt solution and TS-1 molecular sieve is 5 ~ 20, the concentration range of ammonium salt solution is 0.5 ~ 2mol/L.
6. according to the method described in claim 1 or 2, it is characterized in that: Xi Yuan used is dibutyl tin dilaurate.
7. according to the method described in claim 1 or 2, it is characterized in that: in step (1), whipping temp is 20 ~ 90 ℃, and baking temperature is 70 ~ 120 ℃, and be 12 ~ 24 hours drying time.
8. according to the method described in claim 1 or 2, it is characterized in that: in step (1), sintering temperature is 450 ~ 650 ℃, and roasting time is 4 ~ 8 hours.
9. according to the method described in claim 1 or 2, it is characterized in that: in step (2), in stanniferous acetone soln, the content of element tin is 0.5wt% ~ 20wt%, and the mass ratio of the acetone soln of TS-1 molecular sieve and tin is 0.5 ~ 2.
10. according to the method described in claim 1 or 2, it is characterized in that: in step (2), dip time is 6 ~ 48 hours, and baking temperature is 70 ~ 120 ℃, and be 12 ~ 24 hours drying time.
11. according to the method described in claim 1 or 2, it is characterized in that: in step (2), sintering temperature is 450 ~ 650 ℃, and roasting time is 4 ~ 8 hours.
The catalyst that 12. 1 kinds of methods claimed in claim 1 obtain is for benzene hydroxylation phenol reactant processed, 40 ~ 80 ℃ of reaction temperatures, and the reaction time is 2 ~ 8 hours, benzene/H
2o
2(mol/mol) be 1 ~ 5, the volume ratio of water/benzene is 2 ~ 10, and catalyst/benzene (g/mol) is 0.05 ~ 0.5.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106588577A (en) * | 2015-10-19 | 2017-04-26 | 江苏福瑞生物医药有限公司 | Pentafluorophenol synthesis method |
| CN106607090A (en) * | 2015-10-21 | 2017-05-03 | 中国石油化工股份有限公司 | Green oxidation bifunctional catalyst, preparation method and applications thereof |
| CN113457654A (en) * | 2021-06-02 | 2021-10-01 | 江西省科学院应用化学研究所 | Carbon-based solid acid catalyst, and preparation method and use method thereof |
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| US5780654A (en) * | 1997-04-22 | 1998-07-14 | Uop Llc | Titanostannosilicalites: epoxidation of olefins |
| CN1412178A (en) * | 2002-08-28 | 2003-04-23 | 天津大学 | Preparation method of methyl phenyl oxalate and phenostal |
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2012
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5780654A (en) * | 1997-04-22 | 1998-07-14 | Uop Llc | Titanostannosilicalites: epoxidation of olefins |
| CN1412178A (en) * | 2002-08-28 | 2003-04-23 | 天津大学 | Preparation method of methyl phenyl oxalate and phenostal |
Non-Patent Citations (2)
| Title |
|---|
| RAWEEWAN KLAEWKLA等: "Phenol hydroxylation using Ti- and Sn-containing silicalites", 《CHEM.COMMUN》, 20 May 2003 (2003-05-20), pages 1500 - 1501 * |
| 徐亚荣等: "TS-1分子筛在过氧化氢氧化苯制苯酚反应中的催化性能研究", 《化工科技》, vol. 15, no. 6, 31 December 2007 (2007-12-31) * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106588577A (en) * | 2015-10-19 | 2017-04-26 | 江苏福瑞生物医药有限公司 | Pentafluorophenol synthesis method |
| CN106588577B (en) * | 2015-10-19 | 2019-08-06 | 江苏福瑞康泰药业有限公司 | The synthetic method of Pentafluorophenol |
| CN106607090A (en) * | 2015-10-21 | 2017-05-03 | 中国石油化工股份有限公司 | Green oxidation bifunctional catalyst, preparation method and applications thereof |
| CN106607090B (en) * | 2015-10-21 | 2019-08-06 | 中国石油化工股份有限公司 | Green oxidation bifunctional catalyst and the preparation method and application thereof |
| CN113457654A (en) * | 2021-06-02 | 2021-10-01 | 江西省科学院应用化学研究所 | Carbon-based solid acid catalyst, and preparation method and use method thereof |
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