CN107303500A - Metal/H-MCM-22 catalyst and its application in production cyclohexyl benzene - Google Patents
Metal/H-MCM-22 catalyst and its application in production cyclohexyl benzene Download PDFInfo
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- CN107303500A CN107303500A CN201610262527.0A CN201610262527A CN107303500A CN 107303500 A CN107303500 A CN 107303500A CN 201610262527 A CN201610262527 A CN 201610262527A CN 107303500 A CN107303500 A CN 107303500A
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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
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
- B01J29/76—Iron group metals or copper
- B01J29/7676—MWW-type, e.g. MCM-22, ERB-1, ITQ-1, PSH-3 or SSZ-25
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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
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
- B01J29/74—Noble metals
- B01J29/7476—MWW-type, e.g. MCM-22, ERB-1, ITQ-1, PSH-3 or SSZ-25
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/74—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition with simultaneous hydrogenation
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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
- B01J2229/183—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself in framework positions
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
- C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- C07C2529/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups C07C2529/08 - C07C2529/65
- C07C2529/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups C07C2529/08 - C07C2529/65 containing iron group metals, noble metals or copper
- C07C2529/74—Noble metals
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
- C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- C07C2529/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups C07C2529/08 - C07C2529/65
- C07C2529/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups C07C2529/08 - C07C2529/65 containing iron group metals, noble metals or copper
- C07C2529/76—Iron group metals or copper
Abstract
The present invention relates to a kind of metal/catalyst of H MCM 22, the ion of metal component and organic amine are subjected to complex reaction first, generate the complex compound of metal ion, then add silicon source, silicon source and template carry out plastic and crystallization generation metal/catalyst of H MCM 22, in the present invention, active metal directly participates in framework of molecular sieve building process, enter in molecular sieve pore passage, avoid and molecular sieve pore passage is easily blocked using mechanical mixture in the prior art, so as to cause the defect that catalyst activity is reduced, the catalyst activity position high uniformity distribution of the present invention, when therefore applied to benzene hydrogenation alkylated reaction, the conversion ratio of benzene and the selectivity of cyclohexyl benzene are higher, and the production process of catalyst is simple, it is reproducible, it is easy to industrialization amplification.
Description
Technical field
The present invention relates to a kind of there is catalyzing aromatic hydrocarbon to be hydrogenated with and be alkylated difunctional metal/H-MCM-22 catalyst.
Background technology
Phenol and cyclohexanone are all important basic chemical industry raw materials.At present, industrial main alkylation by benzene and propylene,
Oxidation, acidolysis production phenol, by-product acetone；Cyclohexanone (KA oil) is produced by cyclohexane oxidation.The two industrial mistakes
Journey once through yield is both less than 5%, and with a large amount of accessory substances.
2002, Arends et al. proposed cyclohexyl benzene oxidative synthesis phenol, the reaction path of coproduction cyclohexanone
(Tetrahedron,2002,58:9055).Such technique is compared with traditional cumene oxidation route, biggest advantage
It is that coproduction industrial requirement is big, costly cyclohexanone, so that the efficiency of process is greatly improved.The source of this raw materials technology benzene is rich
Rich, supply is stable, is a process route efficiently, environmentally friendly, economic.The key of process is benzene hydrogenation alkylation generation ring
The exploitation of hexyl benzene high performance catalyst.The technical principle of benzene hydrogenation alkylation production cyclohexyl benzene is benzene in hydrogenation catalyst
The lower partial hydrogenation of effect obtains cyclohexene, the cyclohexene generated occur alkylated reaction with benzene in the presence of acid catalyst and
Obtain cyclohexyl benzene.The method of early stage is on Metal Supported to X-type, Y types or zeolite beta, will to obtain metal/acidity point
Son sieve hydroalkylation bifunctional catalyst.United States Patent (USP) US 4177165 is disclosed is impregnated into X-type by nickel, rare earth and palladium
Or benzene hydrogenation alkylation catalyst is made on y-type zeolite；United States Patent (USP) US 5053571 is disclosed uses incipient wetness impregnation method respectively
The Ru-Ni/ beta catalysts prepared with ion-exchange.Fahy, J etc. report (Applied Catlysis A:Ger.
2001,211:259~268), nickel-platinum is loaded on the 13X molecular sieves crossed through RE-treated by multistep infusion process, benzene
Conversion ratio up to 20%, the selectivity of cyclohexyl benzene is up to 70%.Above-mentioned infusion process and ion-exchange prepare catalyst operation
Process is complicated, and prepared metal/molecular sieve catalyst, and the yield of cyclohexyl benzene is all than relatively low.Reason is analyzed, using leaching
During stain method, active component easily blocks the duct of molecular sieve, and then have impact on the activity of catalyst.
Exxon.Mobil chemical patents Corp has applied for that a series of benzene hydrogenations that prepared with dipping-mixing method are alkylated double work(in recent years
The patent of energy catalyst.Technology disclosed in US8217213 is first to load to hydrogenation active metals without airborne by infusion process
Load hydrogenation catalyst, such as Pd/Al are obtained on body2O3, then with alkylation catalyst EMM-12 molecular sieve mechanical blendings,
So as to obtain hydroalkylation bifunctional catalyst Pd/Al2O3/EMM-12；Technology disclosed in US20150011812 is metal
(such as palladium) dip loading on inorganic oxide carrier, then with the molecular sieves of MCM-22 families (such as MCM-22,
MCM-36, MCM-49, MCM-56, ITQ-1, ITQ-2 etc.) blending shaping.Exxon.Mobil chemical patents Corp is in Chinese Shen
It is also to use Pd/Al in patent CN101998942A (technique for preparing cyclohexyl benzene) please2O3With MCM-22 families
The method of molecular sieve physical contact prepares catalyst.Similar method for preparing catalyst is disclosed in Chinese patent CN10175490
By Pd/Al2O3It is blended and granulates with MCM-22 molecular sieves, when Al is 150 with Pd atomic ratios, in 150 DEG C, 1MPaH2
Reaction, benzene conversion ratio 42.5%, the selectivity of cyclohexyl benzene is up to 78%.
Above-mentioned patent is all first to prepare hydrogenation catalyst and alkylation catalyst respectively, then carries out physical mixed, it is believed that so made
Standby bifunctional catalyst has higher cyclohexyl benzene and dicyclohexyl benzene selective, is also physically to be mixed with hydrogenation to urge
Agent and alkylation catalyst.This physical mixed causes active metal to be deposited in molecular sieve pore passage in fact, easily blocks up
Molecular sieve pore passage is filled in, causes catalyst activity to reduce, hydroalkylation selectively reduction and catalyst stability can be made to be deteriorated,
And be difficult well mixed on microcosmic when carrying out large-scale industry preparation, there is larger enlarge-effect.In addition, adding
In hydrogen alkylation process, the fuel factor of hydrogenation reaction is general very big, this by metal salt solution infusion process, will be hydrogenated with
Active component is concentrated on inorganic oxide, is unfavorable for the heat transfer on microcosmic, can cause hydroalkylation selectively reduction
It is deteriorated with catalyst stability.This can also cause catalyst when carrying out industry's enlarging production, and repeatability is poor.
The content of the invention
The purpose of the present invention is, cyclohexyl benzene yield low the problem of low for existing benzene hydrogenation alkylation bifunctional catalyst activity,
A kind of metal/H-MCM-22 catalyst is provided, when it is used for benzene hydrogenation alkylation, the activity of catalyst is high, and cyclohexyl benzene is received
Rate is high.
Technical scheme
The ion of metal component and organic amine be complexed instead by the present inventor first before synthesis H-MCM-22 molecular sieves
Should, the complex compound of metal ion is generated, silicon source, silicon source and template is then added and carries out plastic and crystallization generation metal
/ H-MCM-22 molecular sieves.
A kind of metal/H-MCM-22 catalyst, is made up of following preparation method：
(1) metal active constituent alcoholic solution and complexing agent are subjected to complex reaction, obtain metal active constituent ionic complex；
(2) silicon source, silicon source, alkali source, water and the template hexamethylene imine needed for synthesizing H-MCM-22 molecular sieves are mixed
After closing uniformly, step (1) is matched somebody with somebody into obtained metal active constituent ionic complex and is added thereto, is sufficiently stirred at room temperature
Aluminosilicate gels are obtained after even, aluminosilicate gels are transferred in autoclave pressure, crystallization；
(3) product after crystallization in step (2) is cooled to after room temperature, is washed with deionized to filtrate pH and is less than 9,
Then dried, be calcined, obtain solid；
(4) solid for obtaining step (3) is crushed, and is then washed, is removed with the cation-exchanger aqueous solution
The solid of alkali metal ion；
(5) solid of removing alkali metal ion in step (4) is molded successively, dried, be calcined, the catalysis being molded
Agent precursor；
(6) by the catalyst precarsor of shaping in step (5), H is used2-N2Gaseous mixture reduction activation, the metal activated
/ H-MCM-22 catalyst；
During metal active constituent described in step (1) is nickel, palladium, platinum, ruthenium, rhenium, iridium, copper, tin, lanthanum, cerium
The composition of a kind of, two kinds or three kinds, the combination of even more preferably wherein two kinds or three kinds metal components；The load capacity of metal
(SiO is based on for 0.3~10%2Weight)；Described alcohol is methanol or ethanol.
In step (1), the complexing agent is any one in piperazine, piperidines, homopiperazine or hexamethylene imine；Institute
The mol ratio for the complexing agent/metal stated is 3~6/1.
In step (1), described complex reaction temperature is 10~60 DEG C, and complexation time is 0.5~4h；
In step (2), the silicon source is any one in Ludox, Silica hydrogel or white carbon；Source of aluminium is aluminic acid
Any one in sodium, aluminum sulfate, boehmite or aluminium glue powder；The alkali source is sodium hydroxide or potassium hydroxide；Raw material
Mol ratio is：SiO2/Al2O3For 15~60, SiO2/OH-For 1.2~8；SiO2/ hexamethylene imine is 1~8, H2O/
SiO2For 15~50.1~4h of incorporation time, metal active group is stirred at room temperature in silicon source, silicon source, alkali source, water and template
The time that is stirred at room temperature divided after complex compound addition is 6~12h, makes the abundant aging of gel.
In step (2), 140~175 DEG C of the crystallization temperature, crystallization time is 48~120h.Because step (2)
Middle addition alkali, therefore autoclave pressure inwall needs alkali corrosion resistance, such as enamel still or the interior kettle for having an alkali prevention layer, such as liner poly- four
Fluorine kettle.
In step (3), described drying condition is 80~150 DEG C, 4~8h；Described roasting condition is 450~600 DEG C,
2~6h.This step main wash falls free sodium ion unnecessary in step (2) crystallization product, obtains alkaline molecular sieve.
Ammonium carbonate or oxalic acid aqueous solution that cation-exchanger described in step (4) is 0.5~1.5mol/L, exchange 2~5
It is secondary.This step mainly exchanges sodium ion unnecessary in framework of molecular sieve, obtains acidic molecular sieve.
In step (5), the forming method is tabletting or adds binding agent, and the binding agent used is aluminium glue powder, kaolin
Or zirconium oxide.
In step (6), described reduction activation, which refers to use, contains H2For 25~100v% H2-N2Gaseous mixture is at 200~500 DEG C
Handle 2~10h.
Application of the above-mentioned metal/H-MCM-22 catalyst in production cyclohexyl benzene：Benzene in metal/H-MCM-22 catalyst and
H2In the presence of, occur hydroalkylation, generate cyclohexyl benzene；Pass through the benzene of metal/H-MCM-22 beds
Liquid phase air speed is 0.5~1.5h-1, the mol ratio of hydrogen/benzene is 0.6~1.5：1, reaction temperature is 175~225 DEG C, instead
It is 1.0~3.0MPa to answer pressure.
Beneficial effect：The catalyst of two kinds of functions is made respectively with using in the prior art, then carries out the mode system of mechanical mixture
The bifunctional catalyst obtained is compared, the method for the invention without using mechanical mixture, but active metal is standby with system with molecular sieve for preparing
Raw material synchronization haptoreaction, is obtained with hydrogenation by chemically reacting and is alkylated difunctional catalyst, because the present invention is living
Property metal directly participate in framework of molecular sieve building process, enter in molecular sieve pore passage, it is to avoid in the prior art using machinery
Mixing easily blocks molecular sieve pore passage, so that cause the defect that catalyst activity is reduced, catalyst activity position of the invention
High uniformity is distributed, therefore during applied to benzene hydrogenation alkylated reaction, the conversion ratio of benzene and the selectivity of cyclohexyl benzene are higher.
The catalyst production process of the present invention is simple, reproducible, it is easy to industrialization amplification.
Brief description of the drawings
Fig. 1 is the XRD of 5%Ni/H-MCM-22 catalyst made from embodiment 1；
Fig. 2 schemes for the TEM of 5%Ni/H-MCM-22 catalyst made from embodiment 1；
Fig. 3 schemes for the TEM of 0.5%Ru/H-MCM-22 catalyst made from embodiment 2；
Fig. 4 schemes for the TEM of 0.3%Pd/H-MCM-22 catalyst made from embodiment 3；
Fig. 5 schemes for the TEM of 0.2%Cu4%Ni/H-MCM-22 catalyst made from embodiment 5；
Fig. 6 schemes for the TEM of 3%Sn3%Ce4%Ni/H-MCM-22 catalyst made from embodiment 8；
Fig. 7 schemes for the TEM of 0.15%Pd5%La4%Ni/H-MCM-22 catalyst made from embodiment 9；
Fig. 8 schemes for the TEM of 0.2%Cu3%La4%Ni/H-MCM-22 catalyst made from embodiment 10.
Embodiment
The embodiment to the present invention is described in detail below, it should be noted however that the protection of the present invention
Scope is not limited to these specific embodiments, but determined by claims.
Embodiment 1
(1) 7.4g nitric hydrates nickel (0.026mol) is dissolved in 15g methanol, adds piperidines 0.104mol,
20 DEG C of complex reaction 3h, obtain metal amine complexes alcoholic solution；(2) by 75g Ludox (SiO2Weight content be 40%),
After sodium metaaluminate, sodium hydroxide and deionized water are stirred and evenly mixed, template hexamethylene imine is added, 3h is stirred at room temperature
Afterwards, step (1) is obtained into metal amine complexes alcoholic solution to add, then is sufficiently stirred for 8h at room temperature, obtain aluminosilicate
Salt gel；Feeding quantity is controlled, makes the molar ratio of material in reactant mixture be：SiO2/Al2O3=15, SiO2/OH-=7, SiO2/
Hexamethylene imine=2, H2O/SiO2=40；In the autoclave pressure that foregoing gel is transferred to liner polytetrafluoro, 190 DEG C are controlled
Dynamic crystallization 36h；(3) product after crystallization is cooled to after room temperature, is washed with deionized to filtrate pH and is less than 9, connects
10h and 500 DEG C of roasting 4h of 100 DEG C of bakings in atmosphere；(4) resulting solid is crushed, uses 1.0M carbonic acid
Aqueous ammonium is washed 4 times, to remove the sodium ion in solid；(5) by the powder of removing sodium ion, aluminium glue powder binding agent is added
Shaping, then in atmosphere drying, 550 DEG C roasting 2h, obtain formation solid catalyst precarsor；(6) by solid forming
Catalyst precarsor, be fitted into fixed bed reactors, with containing H2For the H of 25% (volume)2-N2Gaseous mixture, at 500 DEG C
Lower reduction 10h activation, the 5%Ni/H-MCM-22 catalyst activated.
Product is shown in Fig. 1, the crystalline product of gained is the H-MCM-22 zeolites (θ of characteristic diffraction peak 2 through XRD powder diffraction analysis
For 6.6 °, 7.1 °, 8.0 °, 22.5 °, 26.0 °), it is to have faint Ni (1.1.1) near 44.5 ° in 2 θ
Characteristic diffraction peak.By ESEM tem observation to its flat crystal, Fig. 2 is seen, have no obvious carried metal particle.
Prepared 5%Ni/H-MCM-22 (being labeled as C1) is used for catalytic benzene hydrogenation alkylation process, table 1 is as a result listed in.
Embodiment 2
(1) 0.31g hydrate ruthenium trichlorides (0.0015mol) are dissolved in 5g ethanol, add hexamethylene imine 0.0075
Mol, in 60 DEG C of complex reaction 0.5h, obtains metal amine complexes alcoholic solution；(2) by 75g Ludox (SiO2Weight
Amount content for 40%), after aluminum sulfate, sodium hydroxide and deionized water stir and evenly mix, add template hexamethylene imine,
It is stirred at room temperature after 3h, step (1) is obtained into metal amine complexes alcoholic solution adds, then is sufficiently stirred for 8h at room temperature,
Obtain aluminosilicate gels；Feeding quantity is controlled, makes the molar ratio of material in reactant mixture be：SiO2/Al2O3=25,
SiO2/OH-=5, SiO2/ hexamethylene imine=8, H2O/SiO2=30；Foregoing gel is transferred to the autoclave pressure of liner polytetrafluoro
In, control 180 DEG C of dynamic crystallization 48h；(3) product after crystallization is cooled to after room temperature, is washed with deionized to filter
Liquid pH is less than 9, and then 120 DEG C of 8h and 500 DEG C of bakings are calcined 4h in atmosphere；(4) resulting solid is crushed,
Washed with 0.5M ammonium carbonate solutions 5 times, to remove the sodium ion in solid；(5) by the powder of removing sodium ion, add
Aluminium glue powder binding agent be molded, then in atmosphere drying, 550 DEG C roasting 2h, obtain formation solid catalyst precarsor；(6)
It is fitted into the catalyst precarsor of solid forming in fixed bed reactors, with containing H2For the H of 85% (volume)2-N2Gaseous mixture,
Reductase 12 h is activated at 300 DEG C, the 0.5Ru%/H-MCM-22 catalyst activated.
Product through the crystalline product obtained by XRD powder diffraction analysis be H-MCM-22 zeolites (θ of characteristic diffraction peak 2 be 6.6 °,
7.1 °, 8.0 °, 22.5 °, 26.0 °), have no Ru characteristic diffraction peaks.Pass through ESEM tem observation to its sheet
Crystal, is shown in Fig. 3, has no obvious carried metal particle.
Prepared 0.5%Ru/H-MCM-22 (being labeled as C2) is used for catalytic benzene hydrogenation alkylation process, table is as a result listed in
1。
Embodiment 3
(1) 0.15g palladium bichlorides (0.00085mol) are dissolved in 5g methanol, add piperidines 0.0051mol,
10 DEG C of complex reaction 4h, obtain metal amine complexes alcoholic solution；(2) by 75g Ludox (SiO2Weight content be 40%),
After sodium aluminate, sodium hydroxide and deionized water is stirred and evenly mixed, template hexamethylene imine is added, is stirred at room temperature after 1h,
Step (1) is obtained into metal amine complexes alcoholic solution to add, then is sufficiently stirred for 6h at room temperature, alumino-silicate is obtained and coagulates
Glue；Feeding quantity is controlled, makes the molar ratio of material in reactant mixture be：SiO2/Al2O3=35, SiO2/OH-=8, SiO2/ six is sub-
Methylene imine=7, H2O/SiO2=50；In the autoclave pressure that foregoing gel is transferred to liner polytetrafluoro, 200 DEG C of dynamics are controlled
Crystallization 24h；(3) product after crystallization is cooled to after room temperature, is washed with deionized to filtrate pH and is less than 9, then exists
80 DEG C are dried 12h and 450 DEG C of roasting 6h in air；(4) resulting solid is crushed, with 1.5M ammonium carbonate water
Solution is washed 3 times, to remove the sodium ion in solid；(5) by the powder of removing sodium ion, the shaping of aluminium glue powder binding agent is added,
Subsequent drying in atmosphere, 550 DEG C of roasting 2h, obtain formation solid catalyst precarsor；(6) by the catalysis of solid forming
Agent precursor, is fitted into fixed bed reactors, with containing H2For the H of 95% (volume)2-N2Gaseous mixture, is reduced at 250 DEG C
8h is activated, the 0.3Pd%/H-MCM-22 catalyst activated.
Product through the crystalline product obtained by XRD powder diffraction analysis be H-MCM-22 zeolites (θ of characteristic diffraction peak 2 be 6.6 °,
7.1 °, 8.0 °, 22.5 °, 26.0 °), have no Pd characteristic diffraction peaks.Pass through ESEM tem observation to its sheet
Crystal (see Fig. 4), has no obvious carried metal particle.
Prepared 0.3%Pd/H-MCM-22 (being labeled as C3) is used for catalytic benzene hydrogenation alkylation process, table is as a result listed in
1。
Embodiment 4
(1) 0.1g palladium bichlorides (0.00056mol) and 5.96g nitric hydrates nickel (0.0205mol) are dissolved in 10g
In methanol, piperazine 0.126mol is added, in 30 DEG C of complex reaction 4h, metal amine complexes alcoholic solution is obtained；(2)
After 30g white carbons, aluminium glue powder, potassium hydroxide and deionized water are stirred and evenly mixed, template hexamethylene imine is added,
It is stirred at room temperature after 4h, step (1) is obtained into metal amine complexes alcoholic solution adds, then is sufficiently stirred for 12h at room temperature,
Obtain aluminosilicate gels；Feeding quantity is controlled, makes the molar ratio of material in reactant mixture be：SiO2/Al2O3=45,
SiO2/OH-=4, SiO2/ hexamethylene imine=6, H2O/SiO2=15；Foregoing gel is transferred to the autoclave pressure of liner polytetrafluoro
In, control 170 DEG C of dynamic crystallization 60h；(3) product after crystallization is cooled to after room temperature, is washed with deionized to filter
Liquid pH is less than 9, and then 150 DEG C of 4h and 600 DEG C of bakings are calcined 1h in atmosphere；(4) resulting solid is crushed,
Washed with 1.0M oxalic acid aqueous solutions 3 times, to remove the potassium ion in solid；(5) by the powder of de- potassium ion, oxygen is added
Change the shaping of zirconium powder binding agent, then drying, 550 DEG C of roasting 2h in atmosphere, obtain formation solid catalyst precarsor；(6)
It is fitted into the catalyst precarsor of solid forming in fixed bed reactors, with containing H2For the H of 75% (volume)2-N2Gaseous mixture,
4h activation, the 0.2%Pd4%Ni/H-MCM-22 catalyst activated are reduced at 250 DEG C.
Product through the crystalline product obtained by XRD powder diffraction analysis be H-MCM-22 zeolites (θ of characteristic diffraction peak 2 be 6.6 °,
7.1 °, 8.0 °, 22.5 °, 26.0 °), it is to have faint Ni (1.1.1) feature diffraction near 44.5 ° in 2 θ
Peak.By ESEM tem observation to its flat crystal, obvious carried metal particle is had no.
Prepared 0.2%Pd4%Ni/H-MCM-22 (being labeled as C4) is used for catalytic benzene hydrogenation alkylation process, as a result arranged
In table 1.
Embodiment 5
(1) 0.23g nitric hydrates copper (0.001mol) and 5.1g are hydrated into nickel acetate (0.0205mol) to be dissolved in
In 10g ethanol, homopiperazine 0.086mol is added, in 40 DEG C of complex reaction 1h, metal amine complexes alcoholic solution is obtained；
(2) after stirring and evenly mixing 30g Silica hydrogels, sodium aluminate, sodium hydroxide and deionized water, template hexa-methylene is added sub-
Amine, is stirred at room temperature after 3h, and step (1) is obtained into metal amine complexes alcoholic solution adds, then is sufficiently stirred at room temperature
10h, obtains aluminosilicate gels；Feeding quantity is controlled, makes the molar ratio of material in reactant mixture be：SiO2/Al2O3=20,
SiO2/OH-=1.2, SiO2/ hexamethylene imine=4, H2O/SiO2=20；Foregoing gel is transferred to the pressure of liner polytetrafluoro
In kettle, 160 DEG C of dynamic crystallization 72h are controlled；(3) product after crystallization is cooled to after room temperature, be washed with deionized to
Filtrate pH is less than 9, and then 130 DEG C of 6h and 550 DEG C of bakings are calcined 2h in atmosphere；(4) by resulting solid powder
It is broken, washed with 0.5M oxalic acid aqueous solutions 4 times, to remove the sodium ion in solid；(5) by the powder of removing sodium ion, plus
Enter kaolin powder binding agent shaping, then in atmosphere drying, 550 DEG C roasting 2h, obtain formation solid catalyst precarsor；
(6) by the catalyst precarsor of solid forming, it is fitted into fixed bed reactors, with containing H2For the H of 50% (volume)2-N2
Gaseous mixture, reduces 6h activation, the 0.2%Cu4%Ni/H-MCM-22 catalyst activated at 400 DEG C.
Product through the crystalline product obtained by XRD powder diffraction analysis be H-MCM-22 zeolites (θ of characteristic diffraction peak 2 be 6.6 °,
7.1 °, 8.0 °, 22.5 °, 26.0 °), it is to have faint Ni (1.1.1) feature diffraction near 44.5 ° in 2 θ
Peak.By ESEM tem observation to its flat crystal, Fig. 5 is seen.
Prepared 0.2%Cu4%Ni/H-MCM-22 (being labeled as C5) is used for catalytic benzene hydrogenation alkylation process, as a result
It is listed in table 1.
Embodiment 6
(1) by 0.116g hydrated iridium trichlorides (0.00031mol) and 5.96g nitric hydrates nickel (0.0205mol)
It is dissolved in 10g methanol, adds piperazine 0.0624mol, in 50 DEG C of complex reaction 2h, obtain metal amine complexes alcohol
Solution；(2) by 75g Ludox (SiO2Weight content be 40%), boehmite, sodium hydroxide and deionized water stir
Mix after mixing, add template hexamethylene imine, be stirred at room temperature after 4h, step (1) is obtained into metal amine complexes
Alcoholic solution is added, then is sufficiently stirred for 10h at room temperature, obtains aluminosilicate gels；Feeding quantity is controlled, reaction is mixed
Molar ratio of material is in thing：SiO2/Al2O3=60, SiO2/OH-=3, SiO2/ hexamethylene imine=1, H2O/SiO2=25；Will
Foregoing gel is transferred in the autoclave pressure of liner polytetrafluoro, controls 150 DEG C of dynamic crystallization 120h；(3) product after crystallization
It is cooled to after room temperature, is washed with deionized to filtrate pH and is less than 9, then 120 DEG C of 6h and 550 DEG C of baking in atmosphere
It is calcined 2h；(4) resulting solid is crushed, washed with 1.5M oxalic acid aqueous solutions 2 times, to remove the sodium in solid
Ion；(5) by the powder of removing sodium ion, the shaping of aluminium glue powder binding agent is added, then drying, 550 DEG C of roastings in atmosphere
2h, obtains formation solid catalyst precarsor；(6) by the catalyst precarsor of solid forming, it is fitted into fixed bed reactors,
With containing H2For the H of 50% (volume)2-N2Gaseous mixture, 4h activation is reduced at 450 DEG C, is activated
0.2%Ir4%Ni/H-MCM-22 catalyst.
Product through the crystalline product obtained by XRD powder diffraction analysis be H-MCM-22 zeolites (θ of characteristic diffraction peak 2 be 6.6 °,
7.1 °, 8.0 °, 22.5 °, 26.0 °), it is to have faint Ni (1.1.1) feature diffraction near 44.5 ° in 2 θ
Peak.Pass through ESEM tem observation to its flat crystal.
Prepared 0.2%Ir4%Ni/H-MCM-22 (being labeled as C6) is used for catalytic benzene hydrogenation alkylation process, as a result
It is listed in table 1.
Embodiment 7
(1) 0.362g ammonium perrhenates (0.00135mol) and 5.96g nitric hydrates nickel (0.0205mol) are dissolved in
In 10g methanol, piperazine 0.065mol is added, in 30 DEG C of complex reaction 2h, metal amine complexes alcoholic solution is obtained；
(2) after stirring and evenly mixing 30g Silica hydrogels, sodium metaaluminate, sodium hydroxide and deionized water, template hexa-methylene is added
Imines, is stirred at room temperature after 4h, and step (1) is obtained into metal amine complexes alcoholic solution adds, then fully stirs at room temperature
12h is mixed, aluminosilicate gels are obtained；Feeding quantity is controlled, makes the molar ratio of material in reactant mixture be：SiO2/Al2O3=50,
SiO2/OH-=2, SiO2/ hexamethylene imine=2, H2O/SiO2=35；Foregoing gel is transferred to the autoclave pressure of liner polytetrafluoro
In, control 150 DEG C of dynamic crystallization 108h；(3) product after crystallization is cooled to after room temperature, is washed with deionized to filter
Liquid pH is less than 9, and then 120 DEG C of 6h and 550 DEG C of bakings are calcined 2h in atmosphere；(4) resulting solid is crushed,
Washed with 0.5M oxalic acid aqueous solutions 3 times, to remove the sodium ion in solid；(5) by the powder of removing sodium ion, aluminium is added
Rubber powder binding agent be molded, then in atmosphere drying, 550 DEG C roasting 2h, obtain formation solid catalyst precarsor；(6)
It is fitted into the catalyst precarsor of solid forming in fixed bed reactors, with containing H2For the H of 50% (volume)2-N2Gaseous mixture,
4h activation, the 0.2%Re4%Ni/H-MCM-22 catalyst activated are reduced at 450 DEG C.
Product through the crystalline product obtained by XRD powder diffraction analysis be H-MCM-22 zeolites (θ of characteristic diffraction peak 2 be 6.6 °,
7.1 °, 8.0 °, 22.5 °, 26.0 °), it is to have faint Ni (1.1.1) feature diffraction near 44.5 ° in 2 θ
Peak.Pass through ESEM tem observation to its flat crystal.
Prepared 0.2%Re4%Ni/H-MCM-22 (being labeled as C7) is used for catalytic benzene hydrogenation alkylation process, as a result arranged
In table 1.
Embodiment 8
(1) by 1.717g hydrated stannous chlorides (0.0076mol), 2.81g nitric hydrates cerium (0.0065mol) and
5.96g nitric hydrates nickel (0.0205mol) is dissolved in 10g methanol, piperidines 0.122mol is added, in 30 DEG C of networks
Reaction 4h is closed, metal amine complexes alcoholic solution is obtained；(2) by 75g Ludox (SiO2Weight content is 40%), partially
After sodium aluminate, sodium hydroxide and deionized water is stirred and evenly mixed, template hexamethylene imine is added, is stirred at room temperature after 4h,
Step (1) is obtained into metal amine complexes alcoholic solution to add, then is sufficiently stirred for 12h at room temperature, alumino-silicate is obtained and coagulates
Glue；Feeding quantity is controlled, makes the molar ratio of material in reactant mixture be：SiO2/Al2O3=25, SiO2/OH-=6, SiO2/ six is sub-
Methylene imine=8, H2O/SiO2=35；In the autoclave pressure that foregoing gel is transferred to liner polytetrafluoro, 155 DEG C of dynamics are controlled
Crystallization 96h；(3) product after crystallization is cooled to after room temperature, is washed with deionized to filtrate pH and is less than 9, then exists
120 DEG C are dried 6h and 550 DEG C of roasting 2h in air；(4) resulting solid is crushed, it is water-soluble with 0.5M oxalic acid
Liquid is washed 3 times, to remove the sodium ion in solid；(5) by the powder of removing sodium ion, the shaping of aluminium glue powder binding agent is added,
Subsequent drying in atmosphere, 550 DEG C of roasting 2h, obtain formation solid catalyst precarsor；(6) by the catalysis of solid forming
Agent precursor, is fitted into fixed bed reactors, with containing H2For the H of 50% (volume)2-N2Gaseous mixture, is reduced at 450 DEG C
4h is activated, the 3%Sn3%Ce4%Ni/H-MCM-22 catalyst activated.
Product through the crystalline product obtained by XRD powder diffraction analysis be H-MCM-22 zeolites (θ of characteristic diffraction peak 2 be 6.6 °,
7.1 °, 8.0 °, 22.5 °, 26.0 °), it is to have faint Ni (1.1.1) feature diffraction near 44.5 ° in 2 θ
Peak.By ESEM tem observation to its flat crystal, Fig. 6 is seen.
Prepared 3%Sn3%Ce4%Ni/H-MCM-22 (being labeled as C8) is used for catalytic benzene hydrogenation alkylation process, as a result
It is listed in table 1.
Embodiment 9
(1) by 0.075g palladium bichlorides (0.00043mol), 4.68g nitric hydrates lanthanum (0.0108mol) and 5.96g
Nitric hydrate nickel (0.0205mol) is dissolved in 15g methanol, adds piperidines 0.1mol, in 30 DEG C of complex reaction 4h,
Obtain metal amine complexes alcoholic solution；(2) by 75g Ludox (SiO2Weight content be 40%), sodium metaaluminate, hydrogen-oxygen
After change sodium and deionized water are stirred and evenly mixed, template hexamethylene imine is added, is stirred at room temperature after 3h, by step (1)
The addition of metal amine complexes alcoholic solution is obtained, then is sufficiently stirred for 8h at room temperature, aluminosilicate gels are obtained；Control charging
Amount, makes the molar ratio of material in reactant mixture be：SiO2/Al2O3=25, SiO2/OH-=6, SiO2/ hexamethylene imine=4,
H2O/SiO2=20；In the autoclave pressure that foregoing gel is transferred to liner polytetrafluoro, 160 DEG C of dynamic crystallization 84h are controlled；(3)
Product after crystallization is cooled to after room temperature, is washed with deionized to filtrate pH and is less than 9, then 120 DEG C of bakings in atmosphere
6h and 550 DEG C of roasting 2h；(4) resulting solid is crushed, washed with 0.5M oxalic acid aqueous solutions 3 times, with except
The sodium ion gone in solid；(5) by the powder of removing sodium ion, the shaping of aluminium glue powder binding agent is added, then dry in atmosphere,
550 DEG C of roasting 2h, obtain formation solid catalyst precarsor；(6) by the catalyst precarsor of solid forming, fixed bed is loaded
In reactor, with containing H2For the H of 50% (volume)2-N2Gaseous mixture, 4h activation is reduced at 450 DEG C, is activated
0.15%Pd5%La4%Ni/H-MCM-22 catalyst.
Product through the crystalline product obtained by XRD powder diffraction analysis be H-MCM-22 zeolites (θ of characteristic diffraction peak 2 be 6.6 °,
7.1 °, 8.0 °, 22.5 °, 26.0 °), it is to have faint Ni (1.1.1) feature diffraction near 44.5 ° in 2 θ
Peak.By ESEM tem observation to its flat crystal, Fig. 7 is seen.
Prepared 0.15%Pd5%La4%Ni/H-MCM-22 (being labeled as C9) is used for catalytic benzene hydrogenation alkylation process,
As a result it is listed in table 1.
Embodiment 10
(1) by 0.229g nitric hydrates copper (0.00095mol), 2.815g nitric hydrates lanthanum (0.0065mol)
It is dissolved in 5.96g nitric hydrates nickel (0.0205mol) in 10g methanol, piperidines 0.084mol is added, at 30 DEG C
Complex reaction 4h, obtains metal amine complexes alcoholic solution；(2) by 75g Ludox (SiO2Weight content be 40%),
After sodium metaaluminate, sodium hydroxide and deionized water are stirred and evenly mixed, template hexamethylene imine is added, 3h is stirred at room temperature
Afterwards, step (1) is obtained into metal amine complexes alcoholic solution to add, then is sufficiently stirred for 8h at room temperature, obtain aluminosilicate
Salt gel；Feeding quantity is controlled, makes the molar ratio of material in reactant mixture be：SiO2/Al2O3=25, SiO2/OH-=6, SiO2/
Hexamethylene imine=4, H2O/SiO2=20；In the autoclave pressure that foregoing gel is transferred to liner polytetrafluoro, 160 DEG C are controlled
Dynamic crystallization 84h；(3) product after crystallization is cooled to after room temperature, is washed with deionized to filtrate pH and is less than 9, connects
6h and 550 DEG C of roasting 2h of 120 DEG C of bakings in atmosphere；(4) resulting solid is crushed, uses 0.5M oxalic acid
The aqueous solution is washed 3 times, to remove the sodium ion in solid；(5) by the powder of removing sodium ion, add aluminium glue powder binding agent into
Type, then in atmosphere drying, 550 DEG C roasting 2h, obtain formation solid catalyst precarsor；(6) by solid forming
Catalyst precarsor, is fitted into fixed bed reactors, with containing H2For the H of 50% (volume)2-N2Gaseous mixture, at 450 DEG C
Reduce 4h activation, the 0.2%Cu3%La4%Ni/H-MCM-22 catalyst activated.
Product through the crystalline product obtained by XRD powder diffraction analysis be H-MCM-22 zeolites (θ of characteristic diffraction peak 2 be 6.6 °,
7.1 °, 8.0 °, 22.5 °, 26.0 °), it is to have faint Ni (1.1.1) feature diffraction near 44.5 ° in 2 θ
Peak.By ESEM tem observation to its flat crystal, Fig. 8 is seen.
Prepared 0.2%Cu3%La4%Ni/H-MCM-22 (being labeled as C10) is used for catalytic benzene hydrogenation alkylation process,
As a result it is listed in table 1.
Comparative example 1
According to the disclosed techniques for preparing cyclohexyl benzene of Chinese patent CN101998942A (technique for preparing cyclohexyl benzene),
The load that 3h prepares Pd on Pd catalyst, aluminum oxide is calcined by using palladium nitrate solution oxide impregnation aluminium and at 350 DEG C
Measure as 0.3%.Then by Pd/Al2O3With MCM-49 with 1：3 mass ratioes are mixed, and the catalyst of comparative example is made.Reaction
Condition includes 140~175 DEG C of temperature, 135~175psig (931kPag~1207kPag) pressure, 0.30~0.65
Hydrogen/benzene mole ratio, and 0.26~1.05h-1Benzene weight (hourly) space velocity (WHSV).
Catalyst made from comparative example 1 is used for catalytic benzene hydrogenation alkylation process, experiment measures the conversion ratio 28.6% of benzene,
The selectivity 68.3% of cyclohexyl benzene.
Catalyst benzene hydrogenation made from the embodiment of table 1 is alkylated result
Note：Reactor is Ф 22x3 stainless steel tube, loads 20~40 mesh catalyst 10.0mL.
BZ is benzene, and CHB is cyclohexyl benzene, and DCB is dicyclohexyl benzene, and CH is hexamethylene.
PH2For gauge pressure, S is selectivity.
Metal/H-MCM-22 catalyst preparation the cyclohexyl prepared it can be seen from the test result of upper table using the present invention
Benzene, the conversion ratio of benzene and the selectivity of cyclohexyl benzene are higher.
Claims (10)
1. a kind of metal/H-MCM-22 catalyst, it is characterised in that be made up of following preparation method：
(1) metal active constituent alcoholic solution and complexing agent are subjected to complex reaction, obtain metal active constituent ionic complex；
(2) silicon source, silicon source, alkali source, water and the template hexamethylene imine needed for synthesizing H-MCM-22 molecular sieves are mixed
After closing uniformly, step (1) is matched somebody with somebody into obtained metal active constituent ionic complex and is added thereto, is sufficiently stirred at room temperature
Aluminosilicate gels are obtained after even, aluminosilicate gels are transferred in autoclave pressure, crystallization；
(3) product after crystallization in step (2) is cooled to after room temperature, is washed with deionized to filtrate pH and is less than 9,
Then dried, be calcined, obtain solid；
(4) solid for obtaining step (3) is crushed, and is then washed, is removed with the cation-exchanger aqueous solution
The solid of alkali metal ion；
(5) solid of removing alkali metal ion in step (4) is molded successively, dried, be calcined, the catalysis being molded
Agent precursor；
(6) by the catalyst precarsor of shaping in step (5), H is used2-N2Gaseous mixture reduction activation, the metal activated
/ H-MCM-22 catalyst；
During metal active constituent described in step (1) is nickel, palladium, platinum, ruthenium, rhenium, iridium, copper, tin, lanthanum, cerium
The composition of a kind of, two kinds or three kinds, the combination of even more preferably wherein two kinds or three kinds metal components；Described alcohol is first
Alcohol or ethanol；The complexing agent is any one in piperazine, piperidines, homopiperazine or hexamethylene imine.
2. metal as claimed in claim 1/H-MCM-22 catalyst, it is characterised in that in step (1), the network
The mol ratio of mixture and metal active constituent is 3~6：1.
3. metal as claimed in claim 1/H-MCM-22 catalyst, it is characterised in that in step (1), the network
The temperature for closing reaction is 10~60 DEG C, and complexation time is 0.5~4h.
4. metal as claimed in claim 1/H-MCM-22 catalyst, it is characterised in that in step (2), the silicon
Source is any one in Ludox, Silica hydrogel or white carbon；Source of aluminium be sodium aluminate, aluminum sulfate, boehmite or
Any one in aluminium glue powder；The alkali source is sodium hydroxide or potassium hydroxide；Material molar ratio is：SiO2/Al2O3For 15~
60、SiO2/OH-For 1.2~8；SiO2/ hexamethylene imine is 1~8, H2O/SiO2For 15~50.
5. metal as claimed in claim 1/H-MCM-22 catalyst, it is characterised in that in step (2), the crystalline substance
Change 140~175 DEG C of temperature, crystallization time is 48~120h.
6. metal as claimed in claim 1/H-MCM-22 catalyst, it is characterised in that in step (3), described to dry
Dry temperature is 80~150 DEG C, and the time is 4~8h.
7. metal as claimed in claim 1/H-MCM-22 catalyst, it is characterised in that in step (3), the roasting
The temperature of burning is 450~600 DEG C, and the time is 2~6h.
8. metal as claimed in claim 1/H-MCM-22 catalyst, it is characterised in that described in step (4)
Cation-exchanger is 0.5~1.5mol/L ammonium carbonate or oxalic acid aqueous solution, is exchanged 2~5 times.
9. metal/H-MCM-22 catalyst as described in any one of claim 1 to 8, it is characterised in that step (6)
In, described reduction activation, which refers to use, contains H2For 25~100v% H2-N2Gaseous mixture handles 2~10h at 200~500 DEG C.
10. application of any one of claim 1 to the 9 metal/H-MCM-22 catalyst in production cyclohexyl benzene, its
It is characterised by, benzene is in metal/H-MCM-22 catalyst and H2In the presence of, occur hydroalkylation, generate hexamethylene
Base benzene；Benzene liquid phase air speed by metal/MCM-49 beds is 0.5~1.5h-1, the mol ratio of hydrogen/benzene is
0.6~1.5：1, reaction temperature is 175~225 DEG C, and reaction pressure is 1.0~3.0MPa.
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| CN109772431A (en) * | 2019-01-30 | 2019-05-21 | 绍兴文理学院 | The preparation method and application of Y modified MC M-22 load Pd nanocrystalline catalyst |
| CN110483227A (en) * | 2019-09-03 | 2019-11-22 | 中触媒新材料股份有限公司 | A kind of method that catalytic distillation device prepares cyclohexyl benzene |
| CN112169832A (en) * | 2020-12-02 | 2021-01-05 | 富海(东营)新材料科技有限公司 | Catalyst for synthesizing 1, 3-cyclohexyldimethylamine by m-xylylenediamine hydrogenation and preparation method thereof |
| CN114130421A (en) * | 2020-09-04 | 2022-03-04 | 中国石油化工股份有限公司 | Hydroalkylation catalyst and its preparing process and application |
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| CN109772431A (en) * | 2019-01-30 | 2019-05-21 | 绍兴文理学院 | The preparation method and application of Y modified MC M-22 load Pd nanocrystalline catalyst |
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| CN114130421B (en) * | 2020-09-04 | 2024-01-09 | 中国石油化工股份有限公司 | Hydroalkylation catalyst and preparation method and application thereof |
| CN112169832A (en) * | 2020-12-02 | 2021-01-05 | 富海(东营)新材料科技有限公司 | Catalyst for synthesizing 1, 3-cyclohexyldimethylamine by m-xylylenediamine hydrogenation and preparation method thereof |
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