CN105618130A - Preparation method and application of catalyst for phenol hydroxylation reaction - Google Patents
Preparation method and application of catalyst for phenol hydroxylation reaction Download PDFInfo
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- CN105618130A CN105618130A CN201510982619.1A CN201510982619A CN105618130A CN 105618130 A CN105618130 A CN 105618130A CN 201510982619 A CN201510982619 A CN 201510982619A CN 105618130 A CN105618130 A CN 105618130A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/041—Mesoporous materials having base exchange properties, e.g. Si/Al-MCM-41
- B01J29/042—Mesoporous materials having base exchange properties, e.g. Si/Al-MCM-41 containing iron group metals, noble metals or copper
- B01J29/044—Iron group metals or copper
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/041—Mesoporous materials having base exchange properties, e.g. Si/Al-MCM-41
- B01J29/045—Mesoporous materials having base exchange properties, e.g. Si/Al-MCM-41 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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- 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
- C07C37/60—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by oxidation reactions introducing directly hydroxy groups on a =CH-group belonging to a six-membered aromatic ring with the aid of other oxidants than molecular oxygen or their mixtures with molecular oxygen
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
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Abstract
The invention relates to a preparation method and application of a catalyst for phenol hydroxylation reaction. The preparation method comprises the following steps: dissolving transition metal nitrate in 50-80mL of deionized water, wherein the molar ratio of Fe3+ to Co2+/ Cr3+/Cu2+ in the solution is kept at 1: (1-1.5); adding 1-5g of MCM-41 molecular sieve into the solution, coprecipitating under an alkaline condition, and aging and roasting the obtained precipitate to obtain a final catalyst product. The series catalyst can be applied to the phenol hydroxylation reaction and can significantly improve the yield of paradioxybenzene. The reaction has the advantages of a mild condition, easy separation, low pollution and no corrosion.
Description
Technical field
The invention belongs to field of heterogeneous catalysis, it relates to a kind of preparations and applicatio method of metal oxide supported type molecular sieve catalyst. Specifically for taking hydrogen peroxide as the reaction of phenol hydroxylation synthesizing benzene diphenol of oxygenant. Improve the dispersity of active ingredient by carrier of MCM-41 mesopore molecular sieve, utilize the shape selective catalysis effect of this molecular sieve to improve the product rate of Resorcinol in product simultaneously. In addition, the synergy of many metals can improve transformation efficiency and the selectivity of reaction further.
Background technology
Dihydroxy-benzene (Dihydroxybenzene, DHB) is the product that two on phenyl ring hydrogen is optionally substituted by a hydroxyl group, and its isomers comprises pyrocatechol, Resorcinol and Resorcinol. Dihydroxy-benzene described herein specially refers to pyrocatechol and Resorcinol. Pyrocatechol is a kind of important fine chemistry industry intermediates, and purposes is extensive, is mainly used in agricultural chemicals, spices and pharmaceutical industries. Resorcinol is mainly used in sensitive materials, rubber industry and dye industry, and near its added value of industry, dihydroxy-benzene is higher. Compared with traditional technology, phenol and hydrogen peroxide synthesizing benzene diphenol have the advantages such as reaction conditions gentleness, equipment corrosion is little, technical process is simple. Hydrogen peroxide only generates water as oxygenant, and byproduct of reaction is few, and environmental pollution is little.
The gordian technique of phenol hydroxylation reaction is the exploitation of high activated catalyst. FrancePoulenc company is catalyzer taking perchloric acid, and phosphoric acid makes promotor, and the phenol hydroxylation achieving industrialization first produces dihydroxy-benzene. Taking the hydrogen peroxide that consumes as benchmark, the transformation efficiency of phenol is 5%, and the selectivity of dihydroxy-benzene is 90%. The Subsidiary Company Brichima of Enichem company of Italy develops the production technique utilizing Fenton (Fenton) Reactive Synthesis dihydroxy-benzene. Taking the mixture of molysite (II) and cobalt salt (II) as catalyzer, adopting 60% aqueous hydrogen peroxide solution to be oxygenant, under the temperature of reaction of 40 DEG C, phenol per pass conversion can reach 10%, and dihydroxy-benzene selectivity is about 90%. Enichem company take titanium-silicon molecular sieve TS-1 as the hydrogen peroxide phenol hydroxylation technique that catalyst development makes new advances, its condition is temperature of reaction 60-90 DEG C, and the aqueous hydrogen peroxide solution of 30% makes oxygenant, and water and acetone make solvent, phenol conversion 25%, dihydroxy-benzene selectivity 90%. Making a general survey of the catalyzer of existing phenol hydroxylation synthesizing benzene diphenol, mainly there are the following problems: (1) catalyzer is serious to equipment corrosion, separating difficulty is bigger. (2) catalyst activity is lower, it is necessary to higher temperature of reaction and the aqueous hydrogen peroxide solution of high density make oxygenant, and contraposition product proportion is lower. The preparation process of catalyzer is complicated, and needs regeneration to use, and can only adopt the mode of batch production. (3) per pass conversion of phenol is lower, and internal circulating load is big, and energy consumption is very high. The effective rate of utilization of hydrogen peroxide is lower.
Summary of the invention:
Technical problem: it is an object of the invention to provide a kind of preparation method of catalyzer for phenol hydroxylation reaction and the application of this catalyzer, it has the advantage that easy preparation, reaction conditions are gentle, can improve Resorcinol product rate.
Summary of the invention: for solving the problems of the technologies described above, the present invention provides the preparation method of a kind of catalyzer for phenol hydroxylation reaction, and the method comprises the steps: to be dissolved in transition metal nitrate 50-80mL deionized water, keeps Fe in solution3+With Co2+/Cr3+/Cu2+Mol ratio be 1:1-1.5; 1-5gMCM-41 molecular sieve is joined above-mentioned solution, stirs and start heating; Slowly adding NaOH solution after rising to 40-80 DEG C in solution and carry out co-precipitation, control pH is 7-12 and aging 60-120min; Then filtration, washing, drying, then through 350-550 DEG C of roasting 5-8h, grind, sieve and obtain catalyzer finished product.
Preferably, in transition metal nitrate mixing solutions, transition metal nitrate is that one or both in iron nitrate and cupric nitrate, chromium nitrate, Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES are composite.
Present invention also offers a kind of application by the above-mentioned catalyzer obtained for the preparation method of the catalyzer of phenol hydroxylation reaction, this catalyzer is used for phenol hydroxylation reaction, keeping the mol ratio that temperature of reaction is 40-60 DEG C, the reaction times is 30-40min, reactant phenol and hydrogen peroxide to be 1:1-1.3, catalyzer add-on at ambient pressure is 0.02-0.04wt%, and gained primary product is Resorcinol.
Useful effect:
(1) catalytic activity height, the product rate of dihydroxy-benzene can reach 47.86%.
(2) in product, the content of Resorcinol promotes greatly, and the ratio at contraposition and ortho position can reach 2:1.
(3) catalyst preparing is simple, cheap and can recycle, remarkable in economical benefits.
(4) phenol hydroxylation process is simple, and reaction conditions is gentle, and catalyzer is easily separated.
Embodiment
Having the present invention relates to a kind of preparations and applicatio method for improving the metal oxide supported MCM-41 molecular sieve of Resorcinol product rate in phenol hydroxylation, its composition can represent for Fe2O3-CoO/MCM-41��Fe2O3-Cr2O3/ MCM-41 and Fe2O3-CuO/MCM-41��
Its preparation method is as follows: the preparation method of a kind of catalyzer for phenol hydroxylation reaction, the method comprises the steps: to be dissolved in transition metal nitrate 50-80mL deionized water, keeps Fe in solution3+With Co2+/Cr3+/Cu2+Mol ratio be 1:1-1.5; 1-5gMCM-41 molecular sieve is joined above-mentioned solution, stirs and start heating; Slowly adding NaOH solution after rising to 40-80 DEG C in solution and carry out co-precipitation, control pH is 7-12 and aging 60-120min; Then filtration, washing, drying, then through 350-550 DEG C of roasting 5-8h, grind, sieve and obtain catalyzer finished product.
In transition metal nitrate mixing solutions, transition metal nitrate is that one or both in iron nitrate and cupric nitrate, chromium nitrate, Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES are composite.
Present invention also offers a kind of application by the above-mentioned catalyzer obtained for the preparation method of the catalyzer of phenol hydroxylation reaction, this catalyzer is used for phenol hydroxylation reaction, keeping the mol ratio that temperature of reaction is 40-60 DEG C, the reaction times is 30-40min, reactant phenol and hydrogen peroxide to be 1:1-1.3, catalyzer add-on at ambient pressure is 0.02-0.04wt%, and gained primary product is Resorcinol.
It is characteristic of the invention that and utilize cheap cost and simple method to prepare the molecular sieve catalytic with greater activity. This catalyst series can be used for the hydroxylating of phenol, and can significantly improve the product rate of Resorcinol, and this reaction has product and catalyzer is easily separated, it is little to pollute, reaction conditions is gentle, free from corrosion advantage.
Embodiment 1
The preparation of catalyzer: by 4.62gFe (NO3)3��9H2O and 3.34gCo (NO3)2��6H2O joins in 50ml deionized water, 1.0gMCM-41 carrier is joined above-mentioned solution, heated and stirred. After rising to 40 DEG C, in solution, slowly add NaOH solution, control pH at 7-8 and aging 60min; Throw out is washed, filters, dry, then through 350 DEG C of roasting 5h, then grind, sieve, namely obtain Fe2O3The catalyzer of-CoO/MCM-41 bimetal load.
The synthesis of dihydroxy-benzene: at 40 DEG C, keeping the mol ratio of reactant phenol and hydrogen peroxide to be 1:1, catalyzer add-on is 0.02wt%, reaction times 30min. Under this condition, the product rate of dihydroxy-benzene is 34.86%, to neighbour than being 1.5:1.
Embodiment 2
The preparation of catalyzer: by 4.16gFe (NO3)3��9H2O and 2.87gCu (NO3)2��3H2O joins in 60ml deionized water, 2gMCM-41 carrier is joined above-mentioned solution, heated and stirred. After rising to 50 DEG C, in solution, slowly add NaOH solution, control pH at 8-9 and aging 80min; Throw out is washed, filters, dry, then through 400 DEG C of roasting 6h, then grind, sieve, namely obtain Fe2O3The catalyzer of-CuO/MCM-4 bimetal load.
The synthesis of dihydroxy-benzene: at 50 DEG C, keeping the mol ratio of reactant phenol and hydrogen peroxide to be 1:1.1, catalyzer add-on is 0.03wt%, reaction times 35min. Under this condition, the product rate of dihydroxy-benzene is 47.86%, to neighbour than being 2:1.
Embodiment 3
The preparation of catalyzer: by 3.69gFe (NO3)3��9H2O and 2.71gCr (NO3)3��9H2O joins in 70ml deionized water, 3.0gMCM-41 carrier is joined above-mentioned solution, heated and stirred. After rising to 60 DEG C, in solution, slowly add NaOH solution, control pH at 9-10 and aging 90min; Throw out is washed, filters, dry, then through 450 DEG C of roasting 7h, then grind, sieve, namely obtain Fe2O3-Cr2O3The catalyzer of/MCM-41 bimetal load.
The synthesis of dihydroxy-benzene: at 60 DEG C, keeping the mol ratio of reactant phenol and hydrogen peroxide to be 1:1.2, catalyzer add-on is 0.04wt%, reaction times 40min. Under this condition, the product rate of dihydroxy-benzene is 37.89%, to neighbour than being 1.5:1.
Embodiment 4
The preparation of catalyzer: take 3.23gFe (NO3)3��9H2O��1.16gCu(NO3)2��3H2O and 1.69gCr (NO3)3��9H2O joins in 80mL deionized water, 4.0gMCM-41 carrier is joined above-mentioned solution, heated and stirred. After rising to 70 DEG C, in solution, slowly add NaOH solution, control pH at 10-11 and aging 100min; Throw out is washed, filters, dry, then through 500 DEG C of roasting 8h, then grind, sieve, namely obtain Fe2O3-CuO-Cr2O3The catalyzer of/MCM-4 metal load.
The synthesis of dihydroxy-benzene: at 60 DEG C, keeping the mol ratio of reactant phenol and hydrogen peroxide to be 1:1.3, catalyzer add-on is 0.03wt%, reaction times 40min. Under this condition, the product rate of dihydroxy-benzene is 43.86%, to neighbour than being 1.8:1.
Embodiment 5
The preparation of catalyzer: by 3.23gFe (NO3)3��9H2O and 2.91gCu (NO3)2��3H2O joins in 80ml deionized water, 5.0gMCM-41 carrier is joined above-mentioned solution, heated and stirred. After rising to 80 DEG C, in solution, slowly add NaOH solution, control pH at 10-11 and aging 110min; Throw out is washed, filters, dry, then through 550 DEG C of roasting 7h, then grind, sieve, namely obtain Fe2O3The catalyzer of-CuO/MCM-4 bimetal load.
The synthesis of dihydroxy-benzene: at 50 DEG C, keeping the mol ratio of reactant phenol and hydrogen peroxide to be 1:1.2, catalyzer add-on is 0.02wt%, reaction times 35min. Under this condition, the product rate of dihydroxy-benzene is 40.57%, to neighbour than being 1.7:1.
Embodiment 6
The preparation of catalyzer: take 4.62gFe (NO3)3��9H2O��1.82gCo(NO3)2��6H2O and 1.52gCr (NO3)3��9H2O joins in 80ml deionized water, 5.0gMCM-41 carrier is joined above-mentioned solution, heated and stirred. After rising to 80 DEG C, in solution, slowly add NaOH solution, control pH at 10-11 and aging 120min; Throw out is washed, filters, dry, then through 400 DEG C of roasting 6h, then grind, sieve, namely obtain Fe2O3-CoO-Cr2O3The catalyzer of/MCM-4 metal load.
The synthesis of dihydroxy-benzene: at 40 DEG C, keeping the mol ratio of reactant phenol and hydrogen peroxide to be 1:1.1, catalyzer add-on is 0.03wt%, reaction times 30min. Under this condition, the product rate of dihydroxy-benzene is 38.61%, to neighbour than being 1.6:1.
Claims (3)
1. the preparation method for the catalyzer of phenol hydroxylation reaction, it is characterised in that, the method comprises the steps: to be dissolved in transition metal nitrate 50-80mL deionized water, keeps Fe in solution3+With Co2+/Cr3+/Cu2+Mol ratio be 1:1-1.5; 1-5gMCM-41 molecular sieve is joined above-mentioned solution, stirs and start heating; Slowly adding NaOH solution after rising to 40-80 DEG C in solution and carry out co-precipitation, control pH is 7-12 and aging 60-120min; Then filtration, washing, drying, then through 350-550 DEG C of roasting 5-8h, grind, sieve and obtain catalyzer finished product.
2. the preparation method of catalyzer for phenol hydroxylation reaction according to claim 1, it is characterised in that: in transition metal nitrate mixing solutions, transition metal nitrate is that one or both in iron nitrate and cupric nitrate, chromium nitrate, Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES are composite.
3. one kind by the application of the catalyzer obtained for the preparation method of catalyzer of phenol hydroxylation reaction described in claim 1 or 2, it is characterized in that: this catalyzer is used for phenol hydroxylation reaction, keeping the mol ratio that temperature of reaction is 40-60 DEG C, the reaction times is 30-40min, reactant phenol and hydrogen peroxide to be 1:1-1.3, catalyzer add-on at ambient pressure is 0.02-0.04wt%, and gained primary product is Resorcinol.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107051579A (en) * | 2017-06-06 | 2017-08-18 | 江西师范大学 | A kind of method that use Ti MWW molecular screen membranes prepare benzenediol |
| CN107597173A (en) * | 2017-10-11 | 2018-01-19 | 中国天辰工程有限公司 | A kind of catalyst of phenol hydroxylation synthesizing benzene diphenol and preparation method thereof |
| CN109651090A (en) * | 2019-01-26 | 2019-04-19 | 福州大学 | A kind of method that Bi-MWW catalysis paraxylene hydroxylating prepares 2,5- xylenol |
| CN111085265A (en) * | 2019-12-27 | 2020-05-01 | 中国科学院大连化学物理研究所 | Catalyst for improving para-selectivity of phenol hydroxylation reaction product and preparation method and application thereof |
| CN113308703A (en) * | 2021-04-09 | 2021-08-27 | 桂林理工大学 | Preparation of ultrathin nickel-vanadium layered double hydroxide nanosheet and electrocatalysis phenol hydroxylation performance of ultrathin nickel-vanadium layered double hydroxide nanosheet |
| CN114192153A (en) * | 2021-12-14 | 2022-03-18 | 江苏三吉利化工股份有限公司 | Catalyst for synthesizing benzenediol and application thereof |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107051579A (en) * | 2017-06-06 | 2017-08-18 | 江西师范大学 | A kind of method that use Ti MWW molecular screen membranes prepare benzenediol |
| CN107597173A (en) * | 2017-10-11 | 2018-01-19 | 中国天辰工程有限公司 | A kind of catalyst of phenol hydroxylation synthesizing benzene diphenol and preparation method thereof |
| CN107597173B (en) * | 2017-10-11 | 2020-07-21 | 中国天辰工程有限公司 | Catalyst for synthesizing benzenediol by phenol hydroxylation and preparation method thereof |
| CN109651090A (en) * | 2019-01-26 | 2019-04-19 | 福州大学 | A kind of method that Bi-MWW catalysis paraxylene hydroxylating prepares 2,5- xylenol |
| CN109651090B (en) * | 2019-01-26 | 2021-12-03 | 福州大学 | Method for preparing 2, 5-dimethylphenol by catalyzing hydroxylation of p-xylene with Bi-MWW |
| CN111085265A (en) * | 2019-12-27 | 2020-05-01 | 中国科学院大连化学物理研究所 | Catalyst for improving para-selectivity of phenol hydroxylation reaction product and preparation method and application thereof |
| CN113308703A (en) * | 2021-04-09 | 2021-08-27 | 桂林理工大学 | Preparation of ultrathin nickel-vanadium layered double hydroxide nanosheet and electrocatalysis phenol hydroxylation performance of ultrathin nickel-vanadium layered double hydroxide nanosheet |
| CN113308703B (en) * | 2021-04-09 | 2023-05-05 | 桂林理工大学 | Preparation of ultrathin nickel-vanadium layered double hydroxide nanosheets and electrocatalytic phenol hydroxylation performance thereof |
| CN114192153A (en) * | 2021-12-14 | 2022-03-18 | 江苏三吉利化工股份有限公司 | Catalyst for synthesizing benzenediol and application thereof |
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