CN109225342A - The preparation method and application of the ruthenium-based catalytic agent carrier of Hydrophilic modification for partial hydrogenation of benzene, carrier modification method and catalyst - Google Patents
The preparation method and application of the ruthenium-based catalytic agent carrier of Hydrophilic modification for partial hydrogenation of benzene, carrier modification method and catalyst Download PDFInfo
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
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- C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
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Abstract
The present invention discloses the preparation method and application of the ruthenium-based catalytic agent carrier of the Hydrophilic modification for partial hydrogenation of benzene, carrier modification method and catalyst.The Hydrophilic modification agent of catalyst carrier is poly-dopamine, polyethylene glycol, polyethylene oxide, polyvinyl alcohol, polyacrylic acid, polyacrylamide, polyethyleneimine, ethylene glycol, diethylene glycol (DEG), triethylene glycol or ethylenediamine, catalyst carrier is zirconium oxide, silica, zinc oxide, aluminium oxide, titanium oxide, MCM-41, SBA-15, ZSM-5, active carbon, carbon nanotube, one or both of carbon nano-fiber, the weight ratio of dressing agent and carrier is 0.01~0.5:1, catalyst carrier Hydrophilic modification uses induced oxidation autohemagglutination method or grafting copolymerization process, carrier loaded ruthenium-based catalyst after modification uses infusion process.Carrier loaded ruthenium-based catalyst after Hydrophilic modification in the present invention is used for benzene liquid phase part hydrogenation technique, has high-hydrophilic and high cyclohexene selectivity.
Description
Technical field
The present invention relates to chemical catalysts, and in particular to the ruthenium-based catalytic agent carrier of the Hydrophilic modification of partial hydrogenation of benzene,
The preparation method and application of carrier modification method and catalyst.
Background technique
Cyclohexene in partial hydrogenation of benzene product is a kind of important organic intermediate, due to its with active double bond and
It is widely used in the production of medicine, pesticide, agricultural chemicals, feed addictive, polyester and other fine chemical products, especially
It is that there is huge economic value and wide in the Fypros high value added product synthesis technology such as nylon 6, nylon66 fiber
Market prospects.Unique byproduct hexamethylene of partial hydrogenation of benzene, through oxidation, cyclohexanone oxamidinating, cyclohexanone oxime Beckmann rearrangement
Etc. processes caprolactam and adipic acid (raw materials of the Fypros such as nylon 6 and nylon66 fiber) can be obtained, which is current work
The main stream approach of caprolactam and adipic acid is produced in industry, that there are process flows is tediously long, energy and material consumption is big, yield is low, environment is dirty
The disadvantages of dye.
The new process tool that cyclohexene, cyclohexene oxide or hydration prepare caprolactam and cyclohexanol is prepared through partial hydrogenation of benzene
Have the advantages that process is short, atom utilization is high, environmental-friendly, safe and efficient.The method of traditional mode of production cyclohexene includes cyclohexanol
That all there is process flows is complicated for dehydration, cyclohexane halide dehydrohalogenation, cyclohexane dehydrogenation etc., energy consumption is high, yield is low, at high cost
The disadvantages of, it is unable to satisfy the demand for development of modern compound probability.1963, with ruthenium black catalyst first passage partial hydrogenation of benzene system
It obtains cyclohexene (J.Catal., 1963,2,79), is caused since then by the new process that partial hydrogenation of benzene prepares cyclohexene both domestic and external
Extensive concern and research.1989, partial hydrogenation of benzene was prepared cyclohexene applied to industrial production first by Japanese Asahi Kasei Corporation.
Currently, prepared from benzene and hydrogen includes liquid phase method, vapor phase method and complexometry for cyclohexene, wherein based on liquid phase method.Catalysis
Agent is broadly divided into non-loading type and two kinds of support type, using noble ruthenium as active component, also by the precipitation method, infusion process and chemistry
The preparation of the methods of former method.In the product of benzene hydrogenation, the thermodynamic stability of the hexamethylene (mark of hexamethylene more much higher than cyclohexene
It is -153.4 kJ/mol that standard, which generates heat, and cyclohexene is -63.9 kJ/mol), so benzene hydrogenation process is difficult to rest on intermediate production
The object cyclohexene stage.How effectively to promote the cyclohexene generated to be desorbed in time from catalyst surface and comes out and inhibit cyclohexene
Absorption becomes where the key technology of the technique.In order to improve the selectivity of cyclohexene in partial hydrogenation of benzene reaction, industrial production
In experimental study, by using one by water phase, oily phase (benzene, cyclohexene and hexamethylene), gas phase (hydrogen) and solid phase (catalysis
Agent) composition four phase reaction systems, design hydrophilic catalyst, allow catalyst surface to form stable aquitard, using anti-
Under the conditions of answering cyclohexene in water solubility be much smaller than benzene the characteristics of, the moisture film of catalyst surface can effectively promote product hexamethylene
The desorption of alkene simultaneously inhibits its absorption, and then improves the selectivity of cyclohexene.Therefore, the core of high cyclohexene selectivity is to design
Hydrophilic catalyst system.Current research work is based primarily upon the expansion of ruthenium-based catalyst system, surrounds hydrophilic catalyst
The selection of carrier, the influence of auxiliary agent, the influence of carrier cellular structure, the side such as influence of organic or inorganic additive in reaction system
Face has carried out a large amount of exploration.
DE2221139 discloses a kind of RuCl3Catalyst, with water, metal carbonyl or some water-soluble metals without
Machine salt is additive, and under conditions of 177 DEG C, 7.0 MPa, benzene hydrogenation can prepare cyclohexene, this discovery is so that benzene hydrogenation is raw
It is possibly realized at the industrialization of cyclohexene.US5589600 disclose it is a kind of using the precipitation method and with hydrogen reducing prepare Ru-Ni
Bimetallic catalyst, the process for preparing cyclohexene from benzene added with hydrogen.US5973218 discloses a kind of preparation method of cyclohexene, institute
Catalyst is unsupported Ru metal, improves the selection of cyclohexene by adjusting the concentration of reaction dissolvent solution of zinc sulfate
Property.Japanese Asahi Kasei Corporation discloses a kind of method (US4734536) by prepared from benzene and hydrogen for cyclohexene, and used catalyst uses
The precipitation method preparation, using the metal Ru of partial size≤200 as active component, auxiliary agent is made with Zn salt, with Zr, Hf, Ti, Nb, Ta, Cr,
Oxide, hydroxide or the hydrate of Fe, Co, Al, Ga or Si make additive, this method successfully realizes industrialization,
Benzene conversion ratio 40%, cyclohexene selectivity 80%.But the method for preparing catalyst of non-loading type is complicated, the utilization of noble metal Ru
Rate is low, causes catalyst preparation at high cost.In addition the Ru catalyst of non-loading type is sensitive to sulfide, catalyst service life
There is difficult separation and recycling in short and unsupported nano-scale particle catalyst.US6060423 discloses a kind of use
The loaded catalyst of chemical reduction method preparation, with double oxide Ga2O3- ZnO is complex carrier, and carried noble metal Ru is catalyzed benzene
Hydrogen is added to prepare cyclohexene.US4678861 discloses a kind of loaded catalyst prepared using hydrogen reduction method, with rare-earth oxidation
Object La2O3Or La2O3- ZnO is carrier, and carried noble metal Ru catalytic benzene hydrogenation prepares cyclohexene.CN1337386 discloses one kind
Catalyst of preparing cyclohexene from benzene added with hydrogen and preparation method thereof, using chemical reduction method preparation catalyst by active component, auxiliary agent,
Additive and dispersing agent composition.Wherein, one of active component Ru, Th, Pa, auxiliary agent W, Fe, Co, Ni, Zn, Mo or Cd
One of, one of additive B, Na, K or Li, dispersing agent are zirconium oxide.CN1978056A discloses one kind with mercerising
The mixture of zeolite, ZSM-5 or β zeolite and zirconium oxide is carrier, load active component Ru and auxiliary agent Fe, with NaBH4For reduction
Agent prepares loaded catalyst using chemical reduction method, for prepared from benzene and hydrogen for cyclohexene.CN1978053A disclose it is a kind of with
Y2O3And ZrO2Mixture be carrier, load active component Ru and auxiliary agent, auxiliary agent be selected from Co, Fe, Ni or Cu, with NaBH4For also
Former agent prepares loaded catalyst using chemical reduction method, for prepared from benzene and hydrogen for cyclohexene.CN101269326A discloses one
Kind is using cordierite ceramic honeycomb or metal beehive as the integral catalyzer of carrier, using Ru, Pt, Pd or Rh as active component, with
Al2O3、SiO2、TiO2、ZrO2、La2O3、Fe2O3、ZnO、Cr2O3, one or more of GaO, CuO, BaO, CaO be auxiliary agent, benzene
The selectivity of cyclohexene is 56.4% when conversion ratio is 17.1%.This integral catalyzer preparation method is simple, and noble metal utilizes
Rate is high, and catalyst is at low cost, has certain application prospect.US5569803 and US5414171 individually discloses one kind to pass through
ZrO2And La2O3SiO after modification2For the Ru catalyst of carrier, prepared from benzene and hydrogen is used for for cyclohexene.CN101219391A is disclosed
One kind is using mesoporous molecular sieve SBA-15, HMS or MCM-41 as carrier, using Ru as active component, using Fe, Sn or Ba as auxiliary agent,
Using solvent pairs infusion process and use H2The method of/Ar reduction prepares a kind of loaded catalyst, for prepared from benzene and hydrogen for cyclohexene.
CN102600888B discloses a kind of benzene hydrogenating catalyst and its preparation method and application, and the carrier of the catalyst is to pass through
The MCM-41 of ZrO2, ZnO, CuO modification is heavy using dipping using La, Ce, Fe, Zn, Cu or B as auxiliary agent using Ru as active component
Shallow lake method or chemical reduction method preparation.
Summary of the invention
The purpose of the present invention is to provide the ruthenium-based catalytic agent carriers of the Hydrophilic modification of partial hydrogenation of benzene, carrier modification side
The preparation method and catalyst of method and catalyst prepare the application in cyclohexene in partial hydrogenation of benzene.Using induced oxidation autohemagglutination method
Or grafting copolymerization process carries out Hydrophilic modification to the ruthenium-based catalytic agent carrier of partial hydrogenation of benzene, using infusion process to the load after modification
Body carries out ruthenium load, obtains the ruthenium-based catalyst of the carrier loaded ruthenium of Hydrophilic modification, is applied to benzene liquid phase part and adds hydrogen
Cyclohexene is prepared, there is high-hydrophilic and high cyclohexene selectivity and yield.
The technical scheme is that
The ruthenium-based catalytic agent carrier of Hydrophilic modification for partial hydrogenation of benzene, which is characterized in that Hydrophilic modification agent is poly- more
Bar amine, polyethylene glycol, polyethylene oxide, polyvinyl alcohol, polyacrylic acid, polyvinyl acetate, polyacrylamide, polyethyleneimine
One of amine, ethylene glycol, diethylene glycol (DEG), triethylene glycol, ethylenediamine, the corresponding catalyst carrier that is modified is zirconium oxide, oxidation
Silicon, zinc oxide, aluminium oxide, titanium oxide, mesostructured material, SBA-15, zeolite molecular sieve zsm-5, active carbon, carbon nanometer
One or both of pipe, carbon nano-fiber.
Further, dressing agent and the mass ratio of catalyst carrier are 0.01~0.5: 1.
The method of modifying of above-mentioned carrier carries out catalyst carrier using induced oxidation autohemagglutination method or grafting copolymerization process hydrophilic
Sex modification.
When Hydrophilic modification agent is poly-dopamine, method of modifying is the following steps are included: at room temperature, by catalyst
It is filtered, filters after carrier supersound washing (successively washing 1~120 min in ultrasonic cleaner with ethyl alcohol and deionized water)
(dry 0.5~48 h at 30~120 DEG C) is dried in cake;After again will be dry by the solid-liquid mass volume ratio of 0.1~5 g/mL
Carrier impregnation in dopamine-sodium acetate buffer of 0.1~20 mg/mL, then be added sodium periodate (sodium periodate
Dosage be 0.01~5 times of dopamine quality), be stirred to react 0.5~24 h;Suspension after reaction is filtered, and is spent
Ion water washing 1~5 time;Filter cake after washing is dried in vacuo 0.5~48 h at 30~120 DEG C, obtains poly-dopamine modification
Catalyst carrier;
When Hydrophilic modification agent is polyethylene glycol, polyethylene oxide, ethylene glycol, diethylene glycol (DEG), triethylene glycol or ethylenediamine, modification side
Method is the following steps are included: under room temperature, be added ethyl acetate for polyethylene glycol, ethylene glycol, diethylene glycol (DEG), triethylene glycol or ethylenediamine
Or in toluene, 1~120 min is dissolved under ultrasound condition;Then catalyst carrier is added into solution, at 25~120 DEG C
Stir 0.5~48 h;Gained suspension is dried in vacuo 0.5~48 h at 30~150 DEG C, obtains polyethylene glycol, ethylene glycol, two
Glycol, triethylene glycol or ethylene diamine-modified catalyst carrier;
When Hydrophilic modification agent is polyvinyl alcohol, method of modifying is the following steps are included: under room temperature, polyvinyl alcohol is added
In deionized water, 0.5~24 h is dissolved at 30~120 DEG C, obtains poly-vinyl alcohol solution;Again by acetic acid, methanol, sulfuric acid group
At solution (volume ratio of three be 1~15: 1~10: 1) in glutaraldehyde (mole of glutaraldehyde and polyvinyl alcohol is added
Than for 0.05~1: 1), obtaining crosslinker solution;Then after mixing poly-vinyl alcohol solution and crosslinker solution, rapidly to mixed liquor
Middle addition catalyst carrier;Gained mixture is placed in vibrated bed again, 0.5~24 h is reacted at 30~100 DEG C;Reaction knot
Obtained suspension is dried 0.5~24 h by Shu Hou at 30~120 DEG C;Solid after drying is washed with deionized 0.5~
48 h;Wet solid object is dried in vacuo 0.5~48 h at 30~120 DEG C, obtains the catalyst carrier of polyvinyl alcohol modification;
When Hydrophilic modification agent is polyacrylic acid or polyvinyl acetate, method of modifying is the following steps are included: will be by acrylic acid
Monomer or vinyl acetate monomer, initiator (benzoyl peroxide or azodiisobutyronitrile), solvent (dioxane or toluene) group
At solution (molar ratio of monomer and initiator is 10~200: 1, and monomer and solvent volume ratio are 0.01~2: 1) using nitrogen
Qi exhaustion gas;Then the carrier after silanization is added into acquired solution, 0.5~24 h is reacted at 30~120 DEG C;Then it is added
1~10 times of reaction mixture volume hydroquinone-methanol solution (mass ratio of hydroquinone and methanol be 0.05~10:
100), to terminate polymerization reaction;After reaction terminating, gained reaction mixture is filtered, filter cake is washed with methanol, then in room
Dry 0.5~24 h at temperature~120 DEG C, obtains the catalyst carrier of polyacrylic acid or polyvinyl acetate modification;
When Hydrophilic modification agent is polyacrylamide, method of modifying is the following steps are included: will be by acrylamide, tetramethyl second two
(mass volume ratio of acrylamide is 0.1~2 g/mL, the quality of ammonium persulfate to the solution that amine, ammonium persulfate form in solution
Volume ratio is 0.1~5 mg/mL) it is deaerated with nitrogen;Then into acquired solution be added silanization after carrier, in room temperature~
0.5~24 h is reacted at 120 DEG C;Mixture after reaction is washed with deionized;By the wet solid after washing in room temperature~120
It is dried in vacuo 0.5~48 h at DEG C, obtains the catalyst carrier of Polyacrylamide-modified;
When Hydrophilic modification agent is polyethyleneimine, method of modifying is the following steps are included: by polyethyleneimine and 3- (2,3- rings
The third oxygen of oxygen) propyl trimethoxy silicane by 0.1~20: 1 mass ratio be added toluene in, keep 0.5 at room temperature~120 DEG C
~48 h, obtain toluene solution;In ethanol by catalyst carrier dispersion, gained dispersion liquid is added in toluene solution, in room temperature
0.5~48 h is stirred to react at~120 DEG C;By the suspension filtering after reaction, successively washed several times with water and ethyl alcohol;Washing
Sample with ethanol afterwards carries out 0.5~48 h of soxhlet's extraction, obtains the amine-modified catalyst carrier of polyethyleneimine.
The preparation method of the ruthenium-based catalyst of Hydrophilic modification, comprising the following steps:
(1) ruthenium trichloride is dissolved in deionized water and is made into aqueous solution;
(2) carrier of above-mentioned Hydrophilic modification, dipping 0.5~48 is added into step (1) obtained aqueous solution at 4~90 DEG C
h;
(3) suspension after the completion of dipping is filtered, obtains black precipitate;
(4) black precipitate is dried to 0.5~48 h at 30~200 DEG C, obtains the precursor of catalyst;
(5) catalyst precursor is subjected to reduction activation, concrete operations with liquid phase hydrogen reduction method are as follows: presoma is placed in and is had
In the autoclave of polytetrafluoroethyllining lining, sealing autoclave after deionized water is added;With in inert nitrogen gas displacement kettle
Air;It is passed through 0.1~10 MPa hydrogen, sets reduction temperature as 80~200 DEG C, stirring rate is 200~1200 r/min, also
The former time is 0.5~48 h;It after reduction, is cooled to room temperature, obtains the mixed liquor containing catalyst, catalyst is hydrophily
The ruthenium-based catalyst of modification.
Above-mentioned catalyst is prepared in the reaction of cyclohexene for partial hydrogenation of benzene.
Further, application method specifically: directly by liquid phase hydrogen reducing and be cooled to room temperature containing hydrophily
In the autoclave of the mixed liquor of the ruthenium-based catalyst of modification, benzene feedstock is added, and deionized water is added, controls benzene water volume
Than being 0.5~50: 100 for 1: 0.5~200, catalyst and benzene mass ratio, Hydrogen Vapor Pressure is 0.1~10 MPa, and temperature is
130~200 DEG C, stirring rate is 200~1200 r/min, with raw material in quantitative analysis by gas chromatography reaction solution and product
Content.
The beneficial effects of the present invention are:
The present invention is with poly-dopamine, polyethylene glycol, polyethylene oxide, polyvinyl alcohol, polyacrylic acid, polyvinyl acetate, poly- third
Acrylamide, polyethyleneimine, ethylene glycol, diethylene glycol (DEG), triethylene glycol or ethylenediamine are Hydrophilic modification agent, are aoxidized to catalyst carrier
Zirconium, silica, zinc oxide, aluminium oxide, titanium oxide, mesostructured material, SBA-15, zeolite molecular sieve zsm-5, activity
One or both of charcoal, carbon nanotube, carbon nano-fiber progress Hydrophilic modification, the carrier-supported precious metal Ru after modification,
Gained catalyst has excellent partial hydrogenation of benzene catalytic performance, and height is shown in the reaction that partial hydrogenation of benzene prepares cyclohexene
Hydrophily and high cyclohexene selectivity.
Specific embodiment
Following embodiment is intended to illustrate invention rather than limitation of the invention.
Embodiment 1
The preparation of the MCM-41 supported ruthenium catalyst of poly-dopamine modification and its application in partial hydrogenation of benzene reaction
1, the preparation of the MCM-41 carrier of poly-dopamine modification:
(1) at room temperature, successively use 100 mL ethyl alcohol and 100 mL deionized waters in ultrasonic cleaner 2 g MCM-41
Wash 15 min;
(2) after washing, suspension is filtered, gained filter cake is placed at 70 DEG C dry 4 h, obtains pretreated MCM-41
White powder;
(3) pretreated MCM-41 powder is immersed in dopamine-sodium acetate buffer of 5 mL, 2 mg/mL, is added
0.2 mg sodium periodate, is stirred to react 1 h;
(4) suspension after reaction is filtered, is washed 3 times with 200 mL deionized waters, the filter cake of obtained brown color exists
It is dried in vacuo 12 h at 40 DEG C, obtains the MCM-41 carrier of the poly-dopamine modification of brown color, is labeled as PDA@MCM-41.
2, the preparation of the MCM-41 supported ruthenium catalyst of poly-dopamine modification
(1) 0.2696 g RuCl of precise3·xH2O is dissolved in 5 mL deionized waters and is configured to ruthenium trichloride aqueous solution;
(2) it takes 1 g PDA@MCM-41 that step (1) resulting aqueous solution is added, impregnates 2 h;
(3) suspension after the completion of dipping is filtered, gained filter cake dry 12 h at 100 DEG C obtain the presoma of catalyst;
(4) 0.2 g catalyst precursor, 30 mL deionized waters are added to stainless steel of 100 mL with polytetrafluoroethyllining lining
In autoclave, sealing autoclave;Pressurized with hydrogen is passed through to 3.0 MPa with air 3 times in nitrogen displacement kettle, then into kettle;
Autoclave is placed in oil bath pan, is warming up to 150 DEG C, 2 h are stirred to react at 1000 rpm;After reduction reaction, wait
Reacting liquid temperature is down to room temperature, obtains the MCM-41 supported ruthenium catalyst sample of poly-dopamine modification, is labeled as Ru/PDA@MCM-
41。
3, application of the Ru/PDA@MCM-41 catalyst in partial hydrogenation of benzene reaction: the reaction kettle in above-mentioned steps (4)
In, 10 mL benzene feedstocks are added, supplement appropriate amount of deionized water, control benzene water volume ratio is 1: 3;Controlling Hydrogen Vapor Pressure is 4
MPa, temperature are 150 DEG C, and stirring rate is 1000 r/min, carry out the reaction that partial hydrogenation of benzene prepares cyclohexene;Reaction terminates
Afterwards, it is cooled to room temperature to reacting liquid temperature in kettle, the oily phase in reaction solution is taken out, in quantitative analysis by gas chromatography reaction solution
The content of raw material and product, analysis the results are shown in Table 1.
Table 1 Ru/PDA@MCM-41 and Ru/MCM-41aThe performance that catalysis partial hydrogenation of benzene prepares cyclohexene compares
Catalyst | Reaction time (min) | Benzene conversion ratio (%) | Cyclohexene selectivity (%) | Cyclohexane selectivity (%) |
Ru/PDA@MCM-41 | 20 | 44.9 | 80.9 | 19.1 |
Ru/MCM-41 | 5 | 45.5 | 48.6 | 51.4 |
a Ru/MCM-41 catalyst, which refers to, to be prepared using the MCM-41 without Hydrophilic modification as carrier, based on identical infusion process
Ruthenium-based catalyst (similarly hereinafter).
Embodiment 2
The preparation of polyethyleneglycol modified MCM-41 supported ruthenium catalyst and its application in partial hydrogenation of benzene reaction
1, the preparation of polyethyleneglycol modified MCM-41 carrier:
(1) at room temperature, successively use 100 mL ethyl alcohol and 100 mL deionized waters in ultrasonic cleaner 2 g MCM-41
Wash 15 min;
(2) after washing, suspension is filtered, gained filter cake is placed at 70 DEG C dry 4 h, obtains pretreated MCM-41
White powder;
(3) 0.1 g polyethylene glycol is added in 20 mL ethyl acetate, 30 min of room-temperature dissolution under ultrasound condition;
(4) by pretreated MCM-41 powder be added step (3) in polyethylene glycol-ethyl acetate solution in, 50 DEG C,
4 h are stirred to react under conditions of 500 rpm;
(5) after reaction, reaction suspension is dried in vacuo at 30 DEG C 48 h, obtains polyethyleneglycol modified MCM-41 and carries
Body is labeled as PEG@MCM-41.
2, the preparation of polyethyleneglycol modified MCM-41 supported ruthenium catalyst
(1) 0.2696 g RuCl of precise3·xH2O is dissolved in 5 mL deionized waters and is configured to ruthenium trichloride aqueous solution;
(2) it takes 1 g PEG@MCM-41 that step (1) resulting aqueous solution is added, impregnates 2 h;
(3) suspension after the completion of dipping is filtered, gained filter cake dry 12 h at 100 DEG C obtain the presoma of catalyst;
(4) 0.2 g catalyst precursor, 30 mL deionized waters are added to stainless steel of 100 mL with polytetrafluoroethyllining lining
In autoclave, sealing autoclave;Pressurized with hydrogen is passed through to 3.0 MPa with air 3 times in nitrogen displacement kettle, then into kettle;
Autoclave is placed in oil bath pan, is warming up to 150 DEG C, 2 h are stirred to react at 1000 rpm;After reduction reaction, wait
Reacting liquid temperature is down to room temperature, obtains polyethyleneglycol modified MCM-41 supported ruthenium catalyst sample, is labeled as Ru/PEG@MCM-
41。
3, application of the Ru/PEG@MCM-41 catalyst in partial hydrogenation of benzene reaction: the reaction kettle in above-mentioned steps (4)
In, 10 mL benzene feedstocks are added, supplement appropriate amount of deionized water, control benzene water volume ratio is 1: 3;Controlling Hydrogen Vapor Pressure is 4
MPa, temperature are 150 DEG C, and stirring rate is 1000 r/min, carry out the reaction that partial hydrogenation of benzene prepares cyclohexene;Reaction terminates
Afterwards, it is cooled to room temperature to reacting liquid temperature in kettle, the oily phase in reaction solution is taken out, in quantitative analysis by gas chromatography reaction solution
The content of raw material and product, analysis the results are shown in Table 2.
The performance that table 2 Ru/PEG@MCM-41 and Ru/MCM-41 catalysis partial hydrogenation of benzene prepare cyclohexene compares
Catalyst | Reaction time (min) | Benzene conversion ratio (%) | Cyclohexene selectivity (%) | Cyclohexane selectivity (%) |
Ru/PEG@MCM-41 | 25 | 48.3 | 80.1 | 19.9 |
Ru/MCM-41 | 5 | 45.5 | 48.6 | 51.4 |
Embodiment 3
The preparation of polyethyleneglycol modified SBA-15 supported ruthenium catalyst and its application in partial hydrogenation of benzene reaction
1, the preparation of polyethyleneglycol modified SBA-15 carrier:
(1) at room temperature, successively use 100 mL ethyl alcohol and 100 mL deionized waters in ultrasonic cleaner 2 g SBA-15
Wash 15 min;
(2) after washing, suspension is filtered, gained filter cake is placed at 70 DEG C dry 4 h, obtains pretreated SBA-15
White powder;
(3) 0.2 g polyethylene glycol is added in 30 mL ethyl acetate, 1 h of room-temperature dissolution under ultrasound condition;
(4) by pretreated SBA-15 powder be added step (3) in polyethylene glycol-ethyl acetate solution in, 50 DEG C,
10 h are stirred to react under conditions of 500 rpm;
(5) after reaction, reaction suspension is dried in vacuo at 30 DEG C 48 h, obtains polyethyleneglycol modified SBA-15 and carries
Body is labeled as PEG@SBA-15.
2, the preparation of polyethyleneglycol modified SBA-15 supported ruthenium catalyst
(1) 0.5258 g RuCl of precise3·xH2O is dissolved in 10 mL deionized waters and is configured to ruthenium trichloride aqueous solution;
(2) it takes 1 g PEG@SBA-15 that step (1) resulting aqueous solution is added, impregnates 2 h;
(3) suspension after the completion of dipping is filtered, gained filter cake dry 12 h at 100 DEG C obtain the presoma of catalyst;
(4) 0.2 g catalyst precursor, 30 mL deionized waters are added to stainless steel of 100 mL with polytetrafluoroethyllining lining
In autoclave, sealing autoclave;Pressurized with hydrogen is passed through to 3.0 MPa with air 3 times in nitrogen displacement kettle, then into kettle;
Autoclave is placed in oil bath pan, is warming up to 150 DEG C, 2 h are stirred to react at 1000 rpm;After reduction reaction, wait
Reacting liquid temperature is down to room temperature, obtains polyethyleneglycol modified SBA-15 supported ruthenium catalyst sample, is labeled as Ru/PEG@SBA-
15。
3, application of the Ru/PEG@SBA-15 catalyst in partial hydrogenation of benzene reaction: the reaction kettle in above-mentioned steps (4)
In, 10 mL benzene feedstocks are added, supplement appropriate amount of deionized water, control benzene water volume ratio is 1: 3;Controlling Hydrogen Vapor Pressure is 4
MPa, temperature are 150 DEG C, and stirring rate is 1000 r/min, carry out the reaction that partial hydrogenation of benzene prepares cyclohexene;Reaction terminates
Afterwards, it is cooled to room temperature to reacting liquid temperature in kettle, the oily phase in reaction solution is taken out, in quantitative analysis by gas chromatography reaction solution
The content of raw material and product, analysis the results are shown in Table 3.
Table 3 Ru/PEG@SBA-15 and Ru/SBA-15bThe performance that catalysis partial hydrogenation of benzene prepares cyclohexene compares
Catalyst | Reaction time (min) | Benzene conversion ratio (%) | Cyclohexene selectivity (%) | Cyclohexane selectivity (%) |
Ru/PEG@SBA-15 | 30 | 45.1 | 85.8 | 14.2 |
Ru/SBA-15 | 5 | 42.3 | 53.5 | 46.4 |
b Ru/SBA-15 catalyst, which refers to, to be prepared using the SBA-15 without Hydrophilic modification as carrier, based on identical infusion process
Ruthenium-based catalyst.
Embodiment 4
The preparation of the carbon nanotube loaded ruthenium catalyst of poly-dopamine modification and its application in partial hydrogenation of benzene reaction
1, the preparation of the carbon nanotube carrier of poly-dopamine modification:
(1) at room temperature, successively use 100 mL ethyl alcohol and 100 mL deionized waters in ultrasonic cleaner 2 g carbon nanotubes
30 min of middle washing;
(2) after washing, suspension is filtered, gained filter cake is placed at 60 DEG C dry 6 h, obtains pretreated carbon nanometer
Pipe black powder;
(3) pretreated carbon nanotube powder is immersed in dopamine-sodium acetate buffer of 5 mL, 2 mg/mL, is added
Enter 0.2 mg sodium periodate, is stirred to react 1 h;
(4) suspension after reaction is filtered, is washed 3 times with 200 mL deionized waters, the filter cake of obtained dark brown exists
It is dried in vacuo 24 h at 40 DEG C, obtains the carbon nanotube carrier of poly-dopamine modification, is labeled as PDA@CNTs.
2, the preparation of the carbon nanotube loaded ruthenium catalyst of poly-dopamine modification
(1) 0.2696 g RuCl of precise3·xH2O is dissolved in 5 mL deionized waters and is configured to ruthenium trichloride aqueous solution;
(2) it takes 1 g PDA@CNTs that step (1) resulting aqueous solution is added, impregnates 2 h;
(3) suspension after the completion of dipping is filtered, gained filter cake is dried in vacuo 12 h at 100 DEG C, before obtaining catalyst
Drive body;
(4) 0.2 g catalyst precursor, 30 mL deionized waters are added to stainless steel of 100 mL with polytetrafluoroethyllining lining
In autoclave, sealing autoclave;Pressurized with hydrogen is passed through to 3.0 MPa with air 3 times in nitrogen displacement kettle, then into kettle;
Autoclave is placed in oil bath pan, is warming up to 150 DEG C, 2 h are stirred to react at 1000 rpm;After reduction reaction, wait
Reacting liquid temperature is down to room temperature, obtains the carbon nanotube loaded ruthenium catalyst sample of poly-dopamine modification, is labeled as Ru/PDA@
CNTs。
3, application of the Ru/PDA@CNTs catalyst in partial hydrogenation of benzene reaction: the reaction kettle in above-mentioned steps (4)
In, 10 mL benzene feedstocks are added, supplement appropriate amount of deionized water, control benzene water volume ratio is 1: 3;Controlling Hydrogen Vapor Pressure is 4
MPa, temperature are 150 DEG C, and stirring rate is 1000 r/min, carry out the reaction that partial hydrogenation of benzene prepares cyclohexene;Reaction terminates
Afterwards, it is cooled to room temperature to reacting liquid temperature in kettle, the oily phase in reaction solution is taken out, in quantitative analysis by gas chromatography reaction solution
The content of raw material and product, analysis the results are shown in Table 4.
Table 4 Ru/PDA@CNTs and Ru/CNTscThe performance that catalysis partial hydrogenation of benzene prepares cyclohexene compares
Catalyst | Reaction time (min) | Benzene conversion ratio (%) | Cyclohexene selectivity (%) | Cyclohexane selectivity (%) |
Ru/PDA@CNTs | 20 | 49.9 | 55.9 | 44.1 |
Ru/CNTs | 3 | 47.2 | 10.1 | 89.9 |
cRu/CNTs catalyst refers to using the CNTs without Hydrophilic modification as carrier, based on identical ruthenium prepared by infusion process
Base catalyst.
Claims (10)
1. the ruthenium-based catalytic agent carrier of the Hydrophilic modification for partial hydrogenation of benzene, which is characterized in that Hydrophilic modification agent is poly-
Dopamine, polyethylene glycol, polyethylene oxide, polyvinyl alcohol, polyacrylic acid, polyvinyl acetate, polyacrylamide, polyethyleneimine
One of amine, ethylene glycol, diethylene glycol (DEG), triethylene glycol, ethylenediamine, the corresponding catalyst carrier that is modified is zirconium oxide, oxidation
Silicon, zinc oxide, aluminium oxide, titanium oxide, mesostructured material, SBA-15, zeolite molecular sieve zsm-5, active carbon, carbon nanometer
One or both of pipe, carbon nano-fiber.
2. the ruthenium-based catalytic agent carrier of the Hydrophilic modification according to claim 1 for partial hydrogenation of benzene, feature exist
In the mass ratio of dressing agent and catalyst carrier is 0.01~0.5: 1.
3. the method for modifying of carrier described in claim 1, which is characterized in that use induced oxidation autohemagglutination method or grafting copolymerization process
Hydrophilic modification is carried out to catalyst carrier.
4. the method for modifying of carrier according to claim 1, which is characterized in that when Hydrophilic modification agent is poly-dopamine
When, the following steps are included: at room temperature, will be filtered after catalyst carrier supersound washing, filter cake carries out method of modifying
It is dry;Again by 0.1~5 g/mL solid-liquid mass volume ratio by the carrier impregnation after drying in the DOPA of 0.1~20 mg/mL
In amine-sodium acetate buffer, sodium periodate is then added, is stirred to react 0.5~24 h;Suspension after reaction carried out
Filter, is washed with deionized 1~5 time;Filter cake after washing is dried in vacuo 0.5~48 h at 30~120 DEG C, obtains poly- DOPA
Amine-modified catalyst carrier;
When Hydrophilic modification agent is polyethylene glycol, polyethylene oxide, ethylene glycol, diethylene glycol (DEG), triethylene glycol or ethylenediamine, modification side
Method is the following steps are included: under room temperature, be added ethyl acetate for polyethylene glycol, ethylene glycol, diethylene glycol (DEG), triethylene glycol or ethylenediamine
Or in toluene, 1~120 min is dissolved under ultrasound condition;Then catalyst carrier is added into solution, at 25~120 DEG C
Stir 0.5~48 h;Gained suspension is dried in vacuo 0.5~48 h at 30~150 DEG C, obtains polyethylene glycol, ethylene glycol, two
Glycol, triethylene glycol or ethylene diamine-modified catalyst carrier;
When Hydrophilic modification agent is polyvinyl alcohol, method of modifying is the following steps are included: under room temperature, polyvinyl alcohol is added
In deionized water, 0.5~24 h is dissolved at 30~120 DEG C, obtains poly-vinyl alcohol solution;Again by acetic acid, methanol, sulfuric acid group
At solution in glutaraldehyde is added, obtain crosslinker solution;Then after mixing poly-vinyl alcohol solution and crosslinker solution, rapidly to mixed
It closes in liquid and catalyst carrier is added;Gained mixture is placed in vibrated bed again, 0.5~24 h is reacted at 30~100 DEG C;Instead
After answering, obtained suspension is dried into 0.5~24 h at 30~120 DEG C;Solid after drying is washed with deionized
0.5~48 h;Wet solid object is dried in vacuo 0.5~48 h at 30~120 DEG C, the catalyst for obtaining polyvinyl alcohol modification carries
Body;
When Hydrophilic modification agent is polyacrylic acid or polyvinyl acetate, method of modifying is the following steps are included: will be by acrylic acid
The solution that monomer or vinyl acetate monomer, initiator, solvent form is deaerated with nitrogen;Then silanization is added into acquired solution
Carrier afterwards reacts 0.5~24 h at 30~120 DEG C;Then 1~10 times of reaction mixture volume of hydroquinone-is added
Methanol solution, to terminate polymerization reaction;After reaction terminating, gained reaction mixture is filtered, filter cake is washed with methanol, then
Dry 0.5~24 h at room temperature~120 DEG C, obtains the catalyst carrier of polyacrylic acid or polyvinyl acetate modification;
When Hydrophilic modification agent is polyacrylamide, method of modifying is the following steps are included: will be by acrylamide, tetramethyl second two
The solution that amine, ammonium persulfate form is deaerated with nitrogen;Then into acquired solution be added silanization after carrier, in room temperature~
0.5~24 h is reacted at 120 DEG C;Mixture after reaction is washed with deionized;By the wet solid after washing in room temperature~120
It is dried in vacuo 0.5~48 h at DEG C, obtains the catalyst carrier of Polyacrylamide-modified;
When Hydrophilic modification agent is polyethyleneimine, method of modifying is the following steps are included: by polyethyleneimine and 3- (2,3- rings
The third oxygen of oxygen) propyl trimethoxy silicane by 0.1~20: 1 mass ratio be added toluene in, keep 0.5 at room temperature~120 DEG C
~48 h, obtain toluene solution;In ethanol by catalyst carrier dispersion, gained dispersion liquid is added in toluene solution, in room temperature
0.5~48 h is stirred to react at~120 DEG C;By the suspension filtering after reaction, successively washed several times with water and ethyl alcohol;Washing
Sample with ethanol afterwards carries out 0.5~48 h of soxhlet's extraction, obtains the amine-modified catalyst carrier of polyethyleneimine.
5. the method for modifying of carrier according to claim 4, which is characterized in that the dosage of sodium periodate is dopamine quality
0.01~5 times;The molar ratio of glutaraldehyde and polyvinyl alcohol is 0.05~1: 1.
6. the method for modifying of carrier according to claim 4, which is characterized in that initiator is benzoyl peroxide or azo
Bis-isobutyronitrile, solvent are dioxane or toluene;The molar ratio of monomer and initiator is 10~200: 1, monomer and solvent
Volume ratio is 0.01~2: 1;The mass ratio of hydroquinone and methanol is 0.05~10: 100.
7. the method for modifying of carrier according to claim 4, which is characterized in that acrylamide, tetramethylethylenediamine, over cure
In the solution of sour ammonium composition, the mass volume ratio of acrylamide is 0.1~2 g/mL, and the mass volume ratio of ammonium persulfate is 0.1
~5 mg/mL.
8. a kind of preparation method of the ruthenium-based catalyst of Hydrophilic modification, which comprises the following steps:
(1) ruthenium trichloride is dissolved in deionized water and is made into aqueous solution;
(2) carrier of above-mentioned Hydrophilic modification, dipping 0.5~48 is added into step (1) obtained aqueous solution at 4~90 DEG C
h;
(3) suspension after the completion of dipping is filtered, obtains black precipitate;
(4) black precipitate is dried to 0.5~48 h at 30~200 DEG C, obtains the precursor of catalyst;
(5) catalyst precursor is subjected to reduction activation, concrete operations with liquid phase hydrogen reduction method are as follows: presoma is placed in and is had
In the autoclave of polytetrafluoroethyllining lining, sealing autoclave after deionized water is added;With in inert nitrogen gas displacement kettle
Air;It is passed through 0.1~10 MPa hydrogen, sets reduction temperature as 80~200 DEG C, stirring rate is 200~1200 r/min, also
The former time is 0.5~48 h;It after reduction, is cooled to room temperature, obtains the mixed liquor containing catalyst, catalyst, that is, hydrophily is repaired
The ruthenium-based catalyst of decorations.
9. a kind of application of ruthenium-based catalyst of Hydrophilic modification in the reaction that partial hydrogenation of benzene prepares cyclohexene.
10. application according to claim 9, which is characterized in that specifically comprise the following steps: directly passing through liquid phase hydrogen
It restores and in the autoclave of the mixed liquor of the ruthenium-based catalyst containing Hydrophilic modification that is cooled to room temperature, benzene feedstock is added,
And deionized water is added, control benzene water volume ratio is 1: 0.5~200, catalyst and benzene mass ratio is 0.5~50: 100,
Hydrogen Vapor Pressure is 0.1~10 MPa, and temperature is 130~200 DEG C, and stirring rate is 200~1200 r/min, uses gas chromatography
The content of raw material and product in quantitative analysis reaction solution.
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