CN102029171B - Catalyst for synthesizing diphenylmethane and preparation method thereof - Google Patents

Catalyst for synthesizing diphenylmethane and preparation method thereof Download PDF

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CN102029171B
CN102029171B CN2010105471008A CN201010547100A CN102029171B CN 102029171 B CN102029171 B CN 102029171B CN 2010105471008 A CN2010105471008 A CN 2010105471008A CN 201010547100 A CN201010547100 A CN 201010547100A CN 102029171 B CN102029171 B CN 102029171B
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benzene
catalyst
methane
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benzyl chloride
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CN102029171A (en
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张昕
林涛
李蓉
张贵泉
龚婷
祁敏
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Northwest University
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Abstract

The invention discloses a catalyst for synthesizing diphenylmethane and a preparation method thereof. The catalyst is a metal phosphate catalyst system, namely MxPyO, wherein the metal M is selected from Cu, Mn, Zn, Al, Ni, V, Fe, Co, Mo, W, Cr and Zr; P is a phosphorus element; O is an oxygen element; and the molar ratio of x to y is (1:0.01)-(1:2). Through the catalyst provided by the invention, benzene and benzyl chloride are phenylated to generate diphenylmethane under a mild reaction condition, with high selectivity and high yield. The preparation method does not pollute equipment and environment; the reaction condition is mild; no toxic ion is doped in the product; and the benzene used in the reaction can be recycled, so that resources are reasonably used substantially.

Description

A kind of Catalysts and its preparation method of synthesizing diphenyl methane
Technical field
The present invention relates to be used for the Catalysts and its preparation method of synthesizing diphenyl methane, be specifically related to the metal phosphate Catalysts and its preparation method, belong to Preparation of Catalyst and applied technical field.
Background technology
All produce a large amount of benzene in petrochemical industry and the Coal Chemical Industry process.Benzene has become one of important channel of benzene deep processing and utilization through the diphenyl-methane (reaction equation is following) of Friedel-Crafts phenylating reaction generation high added value.
Figure 782184DEST_PATH_IMAGE001
Diphenyl-methane is commonly called as artificial musk's leaf oil, is a kind of important fine-chemical intermediate, is mainly used in that spices and medicine are synthetic, DYE PRODUCTION etc.Diphenyl-methane has good market prospects, remarkable in economical benefits.In recent years, because the driving that diphenyl-methane downstream product demand increases fast, China's diphenyl-methane market demand is increasing, and most of diphenyl-methane needs import.In addition, the price of benzene and benzyl chloride is about 0.7 ten thousand yuan/ton and 0.9 ten thousand yuan/ton respectively, and the price of diphenyl-methane is about 30,000 yuan/ton; This shows that benzene and benzyl chloride reacted diphenyl-methane have bigger profit margin.
At present, reaction generates diphenyl-methane through the Friedel-Crafts phenylating under suitable reaction condition and catalyst action for industrial employing benzene and benzyl chloride.Main liquid acid and the strong solid acid catalyst of using is like sulfuric acid (H 2SO 4), hydrofluoric acid (HF), alchlor (AlCl 3) and zinc chloride (ZnCl 2) etc.But above-mentioned catalyst is unsatisfactory to the selectivity of diphenyl-methane, and easy etching apparatus, contaminated environment in the use make the aftertreatment technology of product become complicated.Therefore, the approach and the catalyst of efficient " green " synthesizing diphenyl methane all explored always by researcher and enterprise.In recent years, the catalyst of developing mainly contains zeolite molecular sieve catalyst and heteropolyacid catalyst of ionic-liquid catalyst, load type metal chloride catalyst, modification etc.
Chinese patent 200510010070.6 has been reported a kind of ionic-liquid catalyst that is used for benzene and benzyl chloride reacted diphenyl-methane.The general formula of catalyst is R 1R 2R 3NHX-M aX b, R 1R 2IMX-M aX bOr RPy-M aX bIonic liquid; Wherein, R 1, R 2, R 3, R is respectively C 1-C 20Alkyl or aromatic radical, HX are inorganic acid or organic acid, M aX bBe inorganic acid salt or acylate, IM is an imidazoles, and Py is a pyridine.At 0.5 gram (CH 3CH 2) 3NHCl-AlCl 3Catalyst, 50 milliliters of benzene, 8.2 milliliters of benzyl chlorides, 90 oReaction is after 3 hours under the condition of C, and the productive rate of diphenyl-methane is 100%.But, be to contain inorganic/organic acid (salt) catalyst in this catalyst, poor stability, cost is higher, and has certain environment harm.
Chinese patent 200310109813.6 reports are with No. 2 clay-SA of Hanggin of modification 01The ZnCl of composite carrier load 2For catalyst is used for benzene and the reaction of benzyl chloride phenylating, has higher diphenyl-methane yield.In reactor, add 1135 gram catalyst and 28375 milliliters of benzene, slowly be heated to 40 oC stirred 10 minutes, added 2951 milliliters of benzyl chlorides at a slow speed, made temperature rise to 70 oC reacted 4 hours, after stopping to heat, made Separation of Solid and Liquid behind the cool to room temperature, reclaimed catalyst, and the distillation mixed liquor makes benzene separate with diphenyl-methane, obtained 2883 gram diphenyl-methanes.This catalyst maybe be with Cl -Be incorporated in the product diphenyl-methane, thereby reduced the product hierarchy and the scope of application.
Arafat etc. (Journal of Porous Materials, 2009,16:565-572) develop a kind of Fe-MCM-41 (Si/Fe=10) catalyst and be used for benzene and benzyl chloride reaction generation diphenyl-methane.At 10 milliliters of benzene, 1.0 gram diphenyl-methanes, 60 oUnder the condition of C, the conversion ratio of benzene is 90%, and the selectivity of diphenyl-methane is 95%.Catalysis journal (2008. 29 (5): 468-472.) reported a kind of Fe-SBA-15 catalyst; In reaction temperature is that 70 ℃ and benzene/benzyl chloride are under 14.4 the condition than (mol ratio); It is 20-70 minute that the catalyst benzyl chloride transforms the required time fully, and the selectivity of diphenyl-methane is 97.8%-100%.Applied Catalysis A:General. (2006,300:1-7.) reported that a kind of FeSBA-15 mesoporous molecular sieve catalyst still has higher benzene under the low temperature of 313K and the benzyl chloride reaction generates the diphenyl-methane catalytic activity.Catalysis Letters (1999; 59:217-219) report in benzene and benzyl chloride reaction, is a catalyst with FeHZSM-5; The conversion ratio of 25 minutes afterchlorinate benzyls can be up to 90%, is that catalyst reaches on the identical benzyl chloride conversion ratio and then need react 107 minutes with GaHZSM-5.Although on the iron content molecular sieve catalyst, obtain diphenyl-methane yield preferably,, the cost of molecular sieve catalyst is higher.
Summary of the invention
The metal tripolyphosphate salt catalyst that the purpose of this invention is to provide the synthesizing diphenyl methane of a kind of high selectivity, high yield;
Another object of the present invention provides above-mentioned Preparation of catalysts method.
Implementation procedure of the present invention is following:
A kind of catalyst of synthesizing diphenyl methane is characterized in that: catalyst is metal phosphate catalyst system and catalyzing M xP yO, metal M is selected from Cu, Mn, Zn, Al, Ni, V, Fe, Co, Mo, W, Cr, Zr, and P is a P elements; O is an oxygen element; Wherein the mol ratio of x and y is (1: 0.01) ~ (1: 2), is preferably (1: 0.05) ~ (1: 1), most preferably is (1: 0.1) ~ (1: 1).
Form M xP yAmong the O, the letter of metal, phosphorus and oxygen is than being to get 1 and the mol ratio that draws metal and phosphorus is (1: 0.01) ~ (1: 2) with oxygen, and can prepare x/y is 1: 0.01,1: 0.5, and 1: 1,1: 2 catalyst.
One of above-mentioned Preparation of catalysts method comprises the steps:
(1) soluble phosphate or phosphoric acid and soluble metallic salt aqueous solution is even, keeping the mol ratio of metal M and P is (1: 0.01) ~ (1: 2), M and H 2The O mol ratio is 1: (1 ~ 10), said soluble metallic salt are nitrate, sulfate, halide, carbonate, the acetate of Cu, Mn, Zn, Al, Ni, V, Fe, Co, Mo, W, Cr or Zr; Soluble phosphate is ammonium phosphate or ammonium hydrogen phosphate;
(2) in above-mentioned mixed liquor, add alkaline precipitating agent fully until deposition;
(3) be ageing 24 hours under 6.5 ~ 7.5 the condition in the pH value, through filtering, obtaining solids after the washing;
(4) solids in air in 100 ~ 150 oDry 6 ~ 12 hours of C, 400 ~ 700 oThe C roasting made catalyst in 4 ~ 8 hours.
Described alkaline precipitating agent is inorganic base or organic base, and inorganic base is ammoniacal liquor, sodium hydrate aqueous solution or potassium hydroxide aqueous solution, and organic base is ethamine, propylamine or ethylenediamine; Alkaline precipitating agent is preferably ammoniacal liquor.
Two of above-mentioned Preparation of catalysts method comprises the steps:
(1) soluble metallic salt or metal oxide are mixed with organic alcohol, 50 ~ 80 oC kept 4 ~ 8 hours, and said soluble metallic salt is nitrate, sulfate, halide, carbonate, the acetate of Cu, Mn, Zn, Al, Ni, V, Fe, Co, Mo, W, Cr or Zr;
(2) in mixture, add soluble phosphate or phosphoric acid; Continued heated and stirred 4 ~ 8 hours; Keeping the mol ratio of metal M and P is (1: 0.01) ~ (1: 2), and M and pure mol ratio are 1: (0.1 ~ 2), soluble phosphate are ammonium phosphate or ammonium hydrogen phosphate;
(3) 50 ~ 150 oThe slow evaporate to dryness said mixture of C obtains solids, in 400 ~ 700 oThe C roasting made catalyst in 4 ~ 8 hours.
Described organic alcohol is selected from fatty alcohol and/or aromatic alcohol, and organic alcohol is methyl alcohol, ethanol, propyl alcohol, butanols, isobutanol, phenmethylol, if adopt the mixed alcohol of aromatic alcohol and fatty alcohol, wherein the volume ratio of fatty alcohol and aromatic alcohol is (1: 1) ~ (3:1).
Three of above-mentioned Preparation of catalysts method comprises the steps:
(1) the soluble metal saline solution is added in the deionized water of boiling, said soluble metallic salt is nitrate, sulfate, halide, carbonate, the acetate of Cu, Mn, Zn, Al, Ni, V, Fe, Co, Mo, W, Cr or Zr;
(2) soluble phosphate or phosphate aqueous solution are added drop-wise in the above-mentioned hot solution, in mixture, add cationic surfactant or organic polymer additive then, keeping the molar ratio of major components in the mixed liquor is M: P: H 2O: additive=1: (0.01 ~ 2): (1 ~ 10): (0.5 ~ 5); Soluble phosphate is ammonium phosphate or ammonium hydrogen phosphate;
(3) 100 ~ 150 oDry said mixture is 8 ~ 12 hours under the C, 400 ~ 700 oAfter the C roasting 4 ~ 8 hours, make catalyst.
Described cationic surfactant is selected from softex kw, sodium cetanesulfonate, hexadecylamine; Organic polymer is selected from polyethylene glycol, polyvinyl alcohol, acid polyethylene, polyacrylic acid, polyoxyethylene.
The reaction condition that above-mentioned catalyst is used for benzene and benzyl chloride reacted diphenyl-methane is: benzene and benzyl chloride mol ratio are 5 ~ 25: 1, and benzene is 100 ~ 200: 1 with the catalyst quality ratio, normal pressure, 30 ~ 120 oC, 5 ~ 240 minutes reaction time.
Advantage of the present invention and good effect:
(1) adopt the present invention to provide the catalyst can be under the reaction condition of gentleness, the realization benzene of high selectivity and high yield and benzyl chloride phenylating generation diphenyl-methane;
(2) conversion ratio of benzyl chloride of the present invention high (99 moles of %), the selectivity of diphenyl-methane high (100 moles of %), the diphenyl-methane yield is high on the unit mass catalyst; Catalyst amount is few, and is recyclable;
(3) the present invention is to equipment and environmental nonpollution, and reaction condition is gentle, the murder by poisoning ion that undopes in the product, and the benzene that uses in the reaction can reclaim use, has realized resource rational utilization basically.
The specific embodiment
Below will the present invention will be described with instantiation, but the present invention is not limited to this.
Embodiment 1-5
Embodiment 1-5 explains the catalyst that the employing precipitation method of the present invention prepare and is used for benzene and the catalytic performance of benzyl chloride reaction generation diphenyl-methane under various conditions.The Preparation of catalysts method is following: at first, dissolve soluble metallic salt and solubility phosphorus-containing compound respectively with proper amount of deionized water.Then, rapidly the phosphorous aqueous solution is joined in the aqueous solution of slaine while stirring, at this moment, the molar ratio of major components is M: P: H in the mixed liquor 2O=1: 0.01 ~ 2: 1 ~ 10.Then, be added drop-wise in the above-mentioned mixed liquor precipitating reagent complete until deposition; In the pH value static ageing under 6.5 ~ 7.5 the condition, through filtering, obtaining solids after spending deionised water.Solids in air in 100 ~ 150 oDry 6 ~ 12 hours of C, then, 400 ~ 700 oAfter the C roasting 4 ~ 8 hours, make catalyst.
In a certain amount of benzene and benzyl chloride mixture, add appropriate amount of catalysts, the reaction temperature that under the condition of continuous stirring, is heated to appointment is reacted, continuous stirring and backflow in the reaction.Reaction is normal pressure, and reaction temperature is 30 ~ 120 oC, 5 ~ 240 minutes reaction time.Reaction back product is lowered the temperature naturally.Reactant mixture carries out qualitative, quantitative analysis on gas chromatograph.
Preparation of catalysts condition, reaction condition and catalytic performance are as shown in table 1.
Figure 519196DEST_PATH_IMAGE002
Instance 6-9
Embodiment 6-9 explains the catalyst that employing mixing method of the present invention prepares and is used for benzene and the catalytic performance of benzyl chloride reaction generation diphenyl-methane under various conditions.The Preparation of catalysts method is following: at first, the soluble metallic salt or its oxide that measure are mixed with an amount of organic alcohol; Mixture is being heated to 50 ~ 80 under the stirring condition fast oC, and kept 4 ~ 8 hours.Then, in mixture, add an amount of soluble phosphate or phosphorous oxide or phosphoric acid under these conditions, continued heated and stirred 4 ~ 8 hours; At this moment, the molar ratio of major components is Me: P in the mixed liquor: alcohol=1: 0.01 ~ 2: 0.1 ~ 2.Then, 50 ~ 150 oSlow evaporate to dryness said mixture obtains solids under the condition of C; Then, 400 ~ 700 oAfter the C roasting 4 ~ 8 hours, make catalyst.
In a certain amount of benzene and benzyl chloride mixture, add appropriate amount of catalysts, the reaction temperature that under the condition of continuous stirring, is heated to appointment is reacted, continuous stirring and backflow in the reaction.Reaction is normal pressure, and reaction temperature is 30 ~ 120 oC, 5 ~ 240 minutes reaction time.Reaction back product is lowered the temperature naturally.Reactant mixture carries out qualitative, quantitative analysis on gas chromatograph.
Preparation of catalysts condition, reaction condition and catalytic performance are as shown in table 2.
Figure 235392DEST_PATH_IMAGE003
Instance 10-14
Embodiment 10-14 explains the catalyst that employing sol-gel process of the present invention prepares and is used for benzene and the catalytic performance of benzyl chloride reaction generation diphenyl-methane under various conditions.The Preparation of catalysts method is following: at first, dissolve soluble metallic salt and solubility phosphorus-containing compound respectively with proper amount of deionized water.Under quick stirring condition, metal salt solution slowly is added drop-wise in the deionized water of boiling and goes; After dropwising, the phosphorous aqueous solution is added drop-wise in the mixture of above-mentioned heat; Then, in mixture, add an amount of additive; At this moment, the molar ratio of major components is M: P: H in the mixed liquor 2O: additive=1: 0.01 ~ 2: 1 ~ 10: 0 ~ 5.Then, 100 ~ 150 oDry said mixture is 8 ~ 12 hours under the C, 400 ~ 700 oAfter the C roasting 4 ~ 8 hours, make catalyst.
In a certain amount of benzene and benzyl chloride mixture, add appropriate amount of catalysts, the reaction temperature that under the condition of continuous stirring, is heated to appointment is reacted, continuous stirring and backflow in the reaction.Reaction is normal pressure, and reaction temperature is 30 ~ 120 oC, 5 ~ 240 minutes reaction time.Reaction back product is lowered the temperature naturally.Reactant mixture carries out qualitative, quantitative analysis on gas chromatograph.
Preparation of catalysts condition, reaction condition and catalytic performance are as shown in table 3.
Figure 665236DEST_PATH_IMAGE004
Comparative Examples 1
Catalyst, Fe that the explanation of this Comparative Examples adopts instance 9 said preparation methods to obtain 2O 3Catalytic performance when fine catalyst is used for benzene and benzyl chloride reacted diphenyl-methane.Reaction condition and process are following: in a certain amount of benzene and benzyl chloride mixture, add appropriate amount of catalysts, the reaction temperature that under the condition of continuous stirring, is heated to appointment is reacted, continuous stirring and backflow in the reaction.Reaction is normal pressure, and reaction temperature is 50 oC, 180 minutes reaction time.Reaction back product is lowered the temperature naturally.Reactant mixture carries out qualitative, quantitative analysis on gas chromatograph.
Figure 844544DEST_PATH_IMAGE005

Claims (9)

1. the method for benzene and benzyl chloride prepared in reaction diphenyl-methane, it is characterized in that reaction condition is: benzene and benzyl chloride mol ratio are 5 ~ 25: 1, benzene is 100 ~ 200: 1 with the catalyst quality ratio, normal pressure, 30 ~ 120 oC, 5 ~ 240 minutes reaction time,
Said catalyst is metal phosphate catalyst system and catalyzing M xP yO, metal M is selected from Cu, Mn, Zn, Al, Ni, V, Fe, Co, Mo, W, Cr, Zr, and P is a P elements, and O is an oxygen element, and wherein the mol ratio of x and y is (1: 0.01) ~ (1: 2).
2. according to the method for said benzene of claim 1 and benzyl chloride prepared in reaction diphenyl-methane, it is characterized in that: M and P mol ratio are (1: 0.05) ~ (1: 1).
3. according to the method for said benzene of claim 1 and benzyl chloride prepared in reaction diphenyl-methane, it is characterized in that Preparation of catalysts comprises the steps:
(1) soluble phosphate or phosphoric acid and soluble metallic salt aqueous solution is even, keeping the mol ratio of metal M and P is (1: 0.01) ~ (1: 2), M and H 2The O mol ratio is 1: (1 ~ 10), said soluble metallic salt are nitrate, sulfate, halide, the acetate of Cu, Mn, Zn, Al, Ni, V, Fe, Co, Mo, W, Cr or Zr; Soluble phosphate is ammonium phosphate or ammonium hydrogen phosphate;
(2) in above-mentioned mixed liquor, add alkaline precipitating agent fully until deposition;
(3) be ageing 24 hours under 6.5 ~ 7.5 the condition in the pH value, through filtering, obtaining solids after the washing;
(4) solids in air in 100 ~ 150 oDry 6 ~ 12 hours of C, 400 ~ 700 oThe C roasting made catalyst in 4 ~ 8 hours.
4. according to the method for said benzene of claim 3 and benzyl chloride prepared in reaction diphenyl-methane; It is characterized in that: alkaline precipitating agent is inorganic base or organic base; Inorganic base is ammoniacal liquor, sodium hydrate aqueous solution or potassium hydroxide aqueous solution, and organic base is ethamine, propylamine or ethylenediamine.
5. according to the method for said benzene of claim 4 and benzyl chloride prepared in reaction diphenyl-methane, it is characterized in that: alkaline precipitating agent is an ammoniacal liquor.
6. according to the method for said benzene of claim 1 and benzyl chloride prepared in reaction diphenyl-methane, it is characterized in that Preparation of catalysts comprises the steps:
(1) soluble metallic salt or metal oxide are mixed with organic alcohol, 50 ~ 80 oC kept 4 ~ 8 hours, and said soluble metallic salt is nitrate, sulfate, halide, the acetate of Cu, Mn, Zn, Al, Ni, V, Fe, Co, Mo, W, Cr or Zr;
(2) in mixture, add soluble phosphate or phosphoric acid; Heated and stirred 4 ~ 8 hours; Keeping the mol ratio of metal M and P is (1: 0.01) ~ (1: 2), and M and organic pure mol ratio are 1: (0.1 ~ 2), soluble phosphate are ammonium phosphate or ammonium hydrogen phosphate;
(3) 50 ~ 150 oThe slow evaporate to dryness said mixture of C obtains solids, in 400 ~ 700 oThe C roasting made catalyst in 4 ~ 8 hours.
7. according to the method for said benzene of claim 6 and benzyl chloride prepared in reaction diphenyl-methane, it is characterized in that: organic alcohol is methyl alcohol, ethanol, propyl alcohol, butanols, isobutanol, phenmethylol.
8. according to the method for said benzene of claim 1 and benzyl chloride prepared in reaction diphenyl-methane, it is characterized in that Preparation of catalysts comprises the steps:
(1) the soluble metal saline solution is added in the deionized water of boiling, said soluble metallic salt is nitrate, sulfate, halide, the acetate of Cu, Mn, Zn, Al, Ni, V, Fe, Co, Mo, W, Cr or Zr;
(2) soluble phosphate or phosphate aqueous solution are added drop-wise in the above-mentioned hot solution, in mixture, add cationic surfactant or organic polymer additive then, keeping the molar ratio of major components in the mixed liquor is M: P: H 2O: additive=1: (0.01 ~ 2): (1 ~ 10): (0.5 ~ 5); Soluble phosphate is ammonium phosphate or ammonium hydrogen phosphate;
(3) 100 ~ 150 oDry said mixture is 8 ~ 12 hours under the C, 400 ~ 700 oAfter the C roasting 4 ~ 8 hours, make catalyst.
9. the method for said according to Claim 8 benzene and benzyl chloride prepared in reaction diphenyl-methane, it is characterized in that: described cationic surfactant is selected from softex kw, sodium cetanesulfonate, hexadecylamine; Organic polymer is selected from polyethylene glycol, polyvinyl alcohol, acid polyethylene, polyacrylic acid, polyoxyethylene.
CN2010105471008A 2010-11-17 2010-11-17 Catalyst for synthesizing diphenylmethane and preparation method thereof Expired - Fee Related CN102029171B (en)

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CN103508838B (en) * 2012-06-29 2015-01-14 中国科学院大连化学物理研究所 Preparation method of diphenylmethane compounds
CN107199043B (en) * 2016-03-18 2020-03-24 中国石油化工股份有限公司 Solid acid catalyst, preparation method and application thereof, and method for preparing furfural compound
CN110479325A (en) * 2019-09-04 2019-11-22 上海大学 A kind of catalyst and preparation method thereof for synthesizing guaiacol

Citations (3)

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Publication number Priority date Publication date Assignee Title
US5627297A (en) * 1995-04-10 1997-05-06 Rhone-Poulenc Chimie Process for cleaving the by-products of the direct synthesis of alkylchlorosilanes
CN101445228A (en) * 2008-12-25 2009-06-03 广西大学 Spherical nano-aluminum phosphate powder and preparation method
CN101519195A (en) * 2009-03-24 2009-09-02 河南师范大学 Preparation method of high-density non-ball shape ferric phosphate powder body

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5627297A (en) * 1995-04-10 1997-05-06 Rhone-Poulenc Chimie Process for cleaving the by-products of the direct synthesis of alkylchlorosilanes
CN101445228A (en) * 2008-12-25 2009-06-03 广西大学 Spherical nano-aluminum phosphate powder and preparation method
CN101519195A (en) * 2009-03-24 2009-09-02 河南师范大学 Preparation method of high-density non-ball shape ferric phosphate powder body

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