CN107303500B - Metal/H-MCM-22 catalyst and application thereof in producing cyclohexylbenzene - Google Patents
Metal/H-MCM-22 catalyst and application thereof in producing cyclohexylbenzene Download PDFInfo
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- 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
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- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
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- 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
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- C—CHEMISTRY; METALLURGY
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- 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 invention relates to a metal/H-MCM-22 catalyst, firstly, ions of metal components and organic amine are subjected to complex reaction to generate a complex of metal ions, and then an aluminum source, a silicon source and a template agent are added to carry out gelling and crystallization to generate the metal/H-MCM-22 catalyst.
Description
Technical Field
The invention relates to a metal/H-MCM-22 catalyst with double functions of catalyzing aromatic hydrogenation and alkylation.
Background
Phenol and cyclohexanone are important basic chemical raw materials. At present, phenol is produced industrially mainly by alkylation, oxidation and acidolysis of benzene and propylene, and acetone is a byproduct; cyclohexanone (KA oil) is produced by oxidation of cyclohexane. Both industrial processes have single pass yields of less than 5% with a large number of by-products.
In 2002, Arends et al have proposed a reaction route for synthesizing phenol by oxidizing cyclohexylbenzene and co-producing cyclohexanone (Tetrahedron,2002,58:9055), the greatest advantage of such a process is the co-production of cyclohexanone, which is industrially in great demand and of high value, thereby greatly increasing the efficiency of the process, the source of the raw material benzene is abundant, the supply is stable, and it is an efficient, environment-friendly, economical process route, the key to the process is the development of a high-performance catalyst for benzene hydroalkylation to cyclohexylbenzene, the technical principle of benzene hydroalkylation to produce cyclohexylbenzene is that benzene is partially hydrogenated under the action of a hydrogenation catalyst to obtain cyclohexene, which is alkylated with benzene under the action of an acid catalyst to obtain cyclohexylbenzene, the early method is to load metals onto X-type, Y-type or β -type zeolites to obtain a metal/acidic molecular sieve hydroalkylation catalyst, US patent US 4177165 discloses that nickel, rare earth and palladium are impregnated onto X-type or Y-type zeolites to prepare benzene alkylation catalysts, US patent US 5053571 discloses that the catalysts are prepared by impregnation with metals such as Ni, Ni-ion impregnation, and Ru-ion-impregnation are easily treated by a multi-ion exchange method, and the above-ion-exchange method is easily carried by a multi-ion-exchange method, and the above-ion exchange method, which is easily carried out a multi-ion exchange process, the process is easily carried by a multi-ion exchange method, and the above-carried out by a multi-ion exchange method, the processes.
The exxonmobil chemical patent company has recently filed a series of patents for the preparation of benzene hydroalkylation bifunctional catalysts by the impregnation-mixing method. The technology disclosed in US8217213 is that hydrogenation active metal is loaded on an inorganic carrier by an impregnation methodTo supported hydrogenation catalysts, e.g. Pd/Al2O3Then mechanically blending with an alkylation catalyst EMM-12 molecular sieve to obtain the hydroalkylation dual-function catalyst Pd/Al2O3EMM-12; US20150011812 discloses a technique in which a metal (such as palladium) is impregnated and supported on an inorganic oxide carrier, and then blended with a molecular sieve of MCM-22 family (such as MCM-22, MCM-36, MCM-49, MCM-56, ITQ-1, ITQ-2, etc.) to form a shape. In the patent CN101998942A (process for preparing cyclohexylbenzene) applied in China by the company Exxon Mobil chemical patent, Pd/Al is also used2O3The catalyst is prepared by a method of physical contact with an MCM-22 family molecular sieve. A similar catalyst disclosed in Chinese patent CN10175490 is prepared by mixing Pd/Al2O3Mixing with MCM-22 molecular sieve, granulating, and granulating at 150 deg.C and 1MPaH when Al/Pd atomic ratio is 1502The conversion rate of benzene is 42.5 percent and the selectivity of the cyclohexylbenzene is up to 78 percent.
The above patents all prepared the hydrogenation catalyst and the alkylation catalyst separately and then physically mixed, and the bifunctional catalyst thus prepared is believed to have high selectivity to cyclohexylbenzene and dicyclohexylbenzene, and also physically mixed the hydrogenation catalyst and the alkylation catalyst. In fact, the physical mixing enables active metal to be deposited only in molecular sieve channels, the molecular sieve channels are easy to block, the activity of the catalyst is reduced, the hydroalkylation selectivity is reduced, the stability of the catalyst is poor, and the active metal is difficult to be uniformly mixed in a microcosmic aspect when large-scale industrial preparation is carried out, so that a large amplification effect exists. In addition, in the hydrogenation alkylation reaction process, the thermal effect of the hydrogenation reaction is generally large, and the hydrogenation active components are concentrated on the inorganic oxide by the metal salt solution impregnation method, so that the heat transfer on the microcosmic is not facilitated, and the reduction of the hydrogenation alkylation selectivity and the deterioration of the catalyst stability can be caused. This also leads to poor reproducibility of the catalyst when it is produced on an industrial scale.
Disclosure of Invention
The invention aims to solve the problems of low activity and low yield of cyclohexylbenzene of the conventional benzene hydroalkylation bifunctional catalyst, and provides a metal/H-MCM-22 catalyst which is high in activity and high in yield of cyclohexylbenzene when used for benzene hydroalkylation.
Technical scheme
Before synthesizing the H-MCM-22 molecular sieve, ions of metal components and organic amine are subjected to a complex reaction to generate a complex of metal ions, and then an aluminum source, a silicon source and a template agent are added to perform gelling and crystallization to generate the metal/H-MCM-22 molecular sieve.
A metal/H-MCM-22 catalyst is prepared by the following preparation method:
(1) carrying out a complexing reaction on the metal active component alcohol solution and a complexing agent to obtain a metal active component ionic complex;
(2) uniformly mixing a silicon source, an aluminum source, an alkali source, water and a template agent hexamethyleneimine required by synthesizing the H-MCM-22 molecular sieve, adding the metal active component ion complex prepared in the step (1), fully and uniformly stirring at room temperature to obtain aluminosilicate gel, transferring the aluminosilicate gel into a pressure kettle, and crystallizing;
(3) cooling the product crystallized in the step (2) to room temperature, washing the product with deionized water until the pH of the filtrate is less than 9, and then drying and roasting the filtrate to obtain a solid;
(4) crushing the solid obtained in the step (3), and then washing the solid with a cation exchanger aqueous solution to obtain a solid without alkali metal ions;
(5) sequentially forming, drying and roasting the solid from which the alkali metal ions are removed in the step (4) to obtain a formed catalyst precursor;
(6) subjecting the catalyst precursor shaped in step (5) to reaction with H2-N2Reducing and activating the mixed gas to obtain an activated metal/H-MCM-22 catalyst;
the metal active component in the step (1) is one, two or three of nickel, palladium, platinum, ruthenium, rhenium, iridium, copper, tin, lanthanum and cerium, and the combination of two or three metal components is more preferable; the metal loading is 0.3-10% (based on SiO)2Weight); the alcohol is methanol or ethanol.
In the step (1), the complexing agent is any one of piperazine, piperidine, homopiperazine or hexamethyleneimine; the mol ratio of the complexing agent to the metal is 3-6/1.
In the step (1), the temperature of the complexation reaction is 10-60 ℃, and the complexation time is 0.5-4 h;
in the step (2), the silicon source is any one of silica sol, silica gel or white carbon black; the aluminum source is any one of sodium aluminate, aluminum sulfate, pseudo-boehmite or alumina powder; the alkali source is sodium hydroxide or potassium hydroxide; the molar ratio of the raw materials is as follows: SiO 22/Al2O315 to 60 of SiO2/OH-1.2 to 8; SiO 22The amount of hexamethyleneimine is 1-8, H2O/SiO215 to 50. And stirring and mixing the silicon source, the aluminum source, the alkali source, the water and the template agent for 1-4 hours at room temperature, and stirring and mixing the metal active component complex for 6-12 hours at room temperature after adding, so that the gel is fully aged.
In the step (2), the crystallization temperature is 140-175 ℃, and the crystallization time is 48-120 h. Because alkali is added in the step (2), the inner wall of the pressure kettle needs to be resistant to alkali corrosion, such as an enamel kettle or a kettle with an alkali-proof layer inside, such as a polytetrafluoroethylene kettle.
In the step (3), the drying condition is 80-150 ℃ and 4-8 h; the roasting condition is 450-600 ℃ and 2-6 h. In the step (2), redundant free sodium ions in the crystallized product are mainly washed away to obtain the alkaline molecular sieve.
And (4) exchanging the cation exchanger in the step (4) for 2-5 times by using 0.5-1.5 mol/L ammonium carbonate or oxalic acid aqueous solution. The method mainly exchanges redundant sodium ions in the molecular sieve framework to obtain the acidic molecular sieve.
In the step (5), the forming method is tabletting or adding a binder, and the adopted binder is alumina powder, kaolin or zirconia.
In the step (6), the reduction activation refers to the use of a catalyst containing H225 to 100% by volume of H2-N2Treating the mixed gas at 200-500 ℃ for 2-10 h.
The application of the metal/H-MCM-22 catalyst in producing the cyclohexylbenzene comprises the following steps: benzene in metal/H-MCM-22 catalyst and H2In the presence of (3), carrying out a hydroalkylation reaction to generate cyclohexylbenzene; the benzene liquid phase airspeed of the benzene passing through the metal/H-MCM-22 catalyst bed layer is 0.5-1.5H-1The molar ratio of hydrogen to benzene is 0.6-1.5: 1, the reaction temperature is 175-225 ℃, and the reaction pressure is 1.0-3.0 MPa.
Has the advantages that: compared with the prior art, the dual-function catalyst is prepared by respectively preparing two kinds of functional catalysts and then mechanically mixing the two kinds of functional catalysts, a mechanical mixing method is not adopted, active metal and molecular sieve preparation raw materials are subjected to synchronous contact reaction, and the catalyst with double functions of hydrogenation and alkylation is obtained through chemical reaction. The catalyst of the invention has simple production process and good repeatability, and is easy for industrial amplification.
Drawings
FIG. 1 is an XRD pattern of a 5% Ni/H-MCM-22 catalyst prepared in example 1;
FIG. 2 is a TEM image of a 5% Ni/H-MCM-22 catalyst prepared in example 1;
FIG. 3 is a TEM image of 0.5% Ru/H-MCM-22 catalyst prepared in example 2;
FIG. 4 is a TEM image of 0.3% Pd/H-MCM-22 catalyst obtained in example 3;
FIG. 5 is a TEM image of 0.2% Cu 4% Ni/H-MCM-22 catalyst prepared in example 5;
FIG. 6 is a TEM image of the 3% Sn 3% Ce 4% Ni/H-MCM-22 catalyst prepared in example 8;
FIG. 7 is a TEM image of 0.15% Pd 5% La 4% Ni/H-MCM-22 catalyst prepared in example 9;
FIG. 8 is a TEM image of 0.2% Cu 3% La 4% Ni/H-MCM-22 catalyst prepared in example 10.
Detailed Description
The following detailed description of the embodiments of the present invention is provided, but it should be noted that the scope of the present invention is not limited by the embodiments, but is defined by the appended claims.
Example 1
(1) Dissolving 7.4g of hydrated nickel nitrate (0.026mol) in 15g of methanol, adding 0.104mol of piperidine, and carrying out a complex reaction at 20 ℃ for 3h to obtain a metal amine complex alcoholic solution; (2) 75g of silica Sol (SiO)240 percent of sodium metaaluminate, sodium hydroxide and deionized water are stirred and mixed evenly, then template agent hexamethyleneimine is added, stirring is carried out for 3 hours at room temperature, then the metal amine complex alcohol solution obtained in the step (1) is added, and stirring is carried out fully for 8 hours at room temperature, thus obtaining aluminosilicate gel; the feeding amount is controlled to ensure that the molar ratio of materials in the reaction mixture is as follows: SiO 22/Al2O3＝15、SiO2/OH-＝7、SiO2Hexamethyleneimine (2), H2O/SiO 240; transferring the gel into a pressure kettle with polytetrafluoroethylene lining, and controlling the temperature of 190 ℃ to dynamically crystallize for 36 hours; (3) cooling the crystallized product to room temperature, washing the crystallized product with deionized water until the pH of the filtrate is less than 9, and then baking the filtrate in the air at 100 ℃ for 10 hours and at 500 ℃ for 4 hours; (4) the resulting solid was pulverized and washed 4 times with 1.0M aqueous ammonium carbonate to remove sodium ions from the solid; (5) adding an alumina powder binder into the powder subjected to sodium ion removal for molding, and then drying in air and roasting at 550 ℃ for 2h to obtain a molded solid catalyst precursor; (6) charging solid shaped catalyst precursor into fixed bed reactor, using catalyst containing H225% by volume of H2-N2Reducing the mixed gas at 500 ℃ for 10H for activation to obtain the activated 5% Ni/H-MCM-22 catalyst.
The product was analyzed by XRD powder diffraction, and the obtained crystalline product was H-MCM-22 zeolite (characteristic diffraction peak 2 θ was 6.6 °, 7.1 °, 8.0 °, 22.5 °, 26.0 °), and had a weak Ni (1.1.1) characteristic diffraction peak near 44.5 ° 2 θ. The flaky crystals were observed by a scanning electron microscope (TEM), and as shown in FIG. 2, no significant supported metal particles were observed.
The 5% Ni/H-MCM-22 (labeled C1) prepared was used to catalyze the benzene hydroalkylation process and the results are listed in Table 1.
Example 2
(1) Dissolving 0.31g of ruthenium trichloride hydrate (0.0015mol) in 5g of ethanol, adding 0.0075mol of hexamethyleneimine, and carrying out complex reaction at 60 ℃ for 0.5h to obtain a metal amine complex alcoholic solution; (2) 75g of silica Sol (SiO)240 percent of aluminum sulfate, sodium hydroxide and deionized water are stirred and mixed uniformly, then template agent hexamethyleneimine is added, stirring is carried out for 3 hours at room temperature, then the metal amine complex alcohol solution obtained in the step (1) is added, and stirring is carried out fully for 8 hours at room temperature, thus obtaining aluminosilicate gel; the feeding amount is controlled to ensure that the molar ratio of materials in the reaction mixture is as follows: SiO 22/Al2O3＝25、SiO2/OH-＝5、SiO2Hexamethyleneimine (8), H2O/SiO230; transferring the gel into a pressure kettle with polytetrafluoroethylene lining, and controlling the temperature to be 180 ℃ for dynamic crystallization for 48 hours; (3) cooling the crystallized product to room temperature, washing the crystallized product with deionized water until the pH of the filtrate is less than 9, and then baking the filtrate in the air at 120 ℃ for 8 hours and at 500 ℃ for 4 hours; (4) the resulting solid was pulverized and washed 5 times with 0.5M aqueous ammonium carbonate to remove sodium ions from the solid; (5) adding an alumina powder binder into the powder subjected to sodium ion removal for molding, and then drying in air and roasting at 550 ℃ for 2h to obtain a molded solid catalyst precursor; (6) charging solid shaped catalyst precursor into fixed bed reactor, using catalyst containing H285% by volume of H2-N2Reducing the mixed gas at 300 ℃ for 2H for activation to obtain the activated 0.5 Ru%/H-MCM-22 catalyst.
The crystal product obtained by XRD powder diffraction analysis of the product is H-MCM-22 zeolite (the characteristic diffraction peak 2 theta is 6.6 degrees, 7.1 degrees, 8.0 degrees, 22.5 degrees and 26.0 degrees), and the Ru characteristic diffraction peak is not seen. The flaky crystals were observed by a scanning electron microscope (TEM), and as shown in FIG. 3, no significant supported metal particles were observed.
The 0.5% Ru/H-MCM-22 (labeled C2) prepared was used to catalyze the benzene hydroalkylation process and the results are listed in Table 1.
Example 3
(1) 0.15g of palladium chloride (0.00085mol) are dissolved inAdding 0.0051mol of piperidine into 5g of methanol, and carrying out complexation reaction for 4h at 10 ℃ to obtain a metal amine complex alcoholic solution; (2) 75g of silica Sol (SiO)240 percent of sodium aluminate, sodium hydroxide and deionized water are stirred and mixed uniformly, then template agent hexamethyleneimine is added, stirred for 1 hour at room temperature, then the metal amine complex alcohol solution obtained in the step (1) is added, and stirred for 6 hours at room temperature, thus obtaining aluminosilicate gel; the feeding amount is controlled to ensure that the molar ratio of materials in the reaction mixture is as follows: SiO 22/Al2O3＝35、SiO2/OH-＝8、SiO2Hexamethyleneimine (H) 72O/SiO250; transferring the gel into a pressure kettle with polytetrafluoroethylene lining, and controlling the temperature to be 200 ℃ for dynamic crystallization for 24 hours; (3) cooling the crystallized product to room temperature, washing the crystallized product with deionized water until the pH of the filtrate is less than 9, and then baking the filtrate in the air at 80 ℃ for 12 hours and at 450 ℃ for 6 hours; (4) the resulting solid was pulverized and washed 3 times with 1.5M aqueous ammonium carbonate to remove sodium ions from the solid; (5) adding an alumina powder binder into the powder subjected to sodium ion removal for molding, and then drying in air and roasting at 550 ℃ for 2h to obtain a molded solid catalyst precursor; (6) charging solid shaped catalyst precursor into fixed bed reactor, using catalyst containing H295% by volume of H2-N2Reducing the mixed gas at 250 ℃ for 8H for activation to obtain the activated 0.3 Pd%/H-MCM-22 catalyst.
The crystal product obtained by XRD powder diffraction analysis of the product is H-MCM-22 zeolite (the characteristic diffraction peak 2 theta is 6.6 degrees, 7.1 degrees, 8.0 degrees, 22.5 degrees and 26.0 degrees), and no Pd characteristic diffraction peak is seen. The flaky crystals were observed by scanning electron microscopy (TEM) (see fig. 4), and no significant supported metal particles were observed.
The 0.3% Pd/H-MCM-22 (labeled C3) prepared was used to catalyze the benzene hydroalkylation process and the results are listed in Table 1.
Example 4
(1) Dissolving 0.1g of palladium chloride (0.00056mol) and 5.96g of hydrated nickel nitrate (0.0205mol) in 10g of methanol, adding 0.126mol of piperazine, and carrying out complex reaction at 30 ℃ for 4 hours to obtain a metal amine complex alcoholic solution; (2) 30g of white carbon black, alumina powder, potassium hydroxide and deionized water are stirred and mixed uniformlyAdding template agent hexamethyleneimine, stirring at room temperature for 4h, adding the metal amine complex alcohol solution obtained in the step (1), and fully stirring at room temperature for 12h to obtain aluminosilicate gel; the feeding amount is controlled to ensure that the molar ratio of materials in the reaction mixture is as follows: SiO 22/Al2O3＝45、SiO2/OH-＝4、SiO2Hexamethyleneimine 6, H2O/SiO215; transferring the gel into a pressure kettle with polytetrafluoroethylene lining, and controlling the temperature to be 170 ℃ for dynamic crystallization for 60 hours; (3) cooling the crystallized product to room temperature, washing the crystallized product with deionized water until the pH of the filtrate is less than 9, and then baking the filtrate in the air at 150 ℃ for 4h and 600 ℃ for 1 h; (4) pulverizing the obtained solid, and washing with 1.0M oxalic acid water solution for 3 times to remove potassium ions in the solid; (5) adding zirconium oxide powder binder into the powder with potassium ions removed for molding, and then drying in air and roasting at 550 ℃ for 2h to obtain a molded solid catalyst precursor; (6) charging solid shaped catalyst precursor into fixed bed reactor, using catalyst containing H275% by volume of H2-N2Reducing the mixed gas at 250 ℃ for 4H for activation to obtain the activated 0.2% Pd 4% Ni/H-MCM-22 catalyst.
The product was analyzed by XRD powder diffraction to obtain a crystalline product of H-MCM-22 zeolite (characteristic diffraction peak 2 theta of 6.6 DEG, 7.1 DEG, 8.0 DEG, 22.5 DEG, 26.0 DEG), and a weak Ni (1.1.1) characteristic diffraction peak near 44.5 DEG 2 theta. The flaky crystal is observed by a scanning electron microscope (TEM), and no obvious loaded metal particles are observed.
The prepared 0.2% Pd 4% Ni/H-MCM-22 (labeled C4) was used to catalyze the benzene hydroalkylation process and the results are listed in Table 1.
Example 5
(1) Dissolving 0.23g of hydrated copper nitrate (0.001mol) and 5.1g of hydrated nickel acetate (0.0205mol) in 10g of ethanol, adding 0.086mol of homopiperazine, and carrying out a complexation reaction at 40 ℃ for 1h to obtain a metal amine complex alcoholic solution; (2) stirring and uniformly mixing 30g of silica gel, sodium aluminate, sodium hydroxide and deionized water, adding template agent hexamethyleneimine, stirring at room temperature for 3 hours, adding the metal amine complex alcohol solution obtained in the step (1), and fully stirring at room temperature for 10 hours to obtain aluminosilicateGelling; the feeding amount is controlled to ensure that the molar ratio of materials in the reaction mixture is as follows: SiO 22/Al2O3＝20、SiO2/OH-＝1.2、SiO2Hexamethyleneimine (4), H2O/SiO220; transferring the gel into a pressure kettle with polytetrafluoroethylene lining, and controlling the temperature of 160 ℃ for dynamic crystallization for 72 hours; (3) cooling the crystallized product to room temperature, washing the crystallized product with deionized water until the pH of the filtrate is less than 9, and then baking the crystallized product in the air at 130 ℃ for 6 hours and at 550 ℃ for 2 hours; (4) pulverizing the obtained solid, and washing with 0.5M oxalic acid water solution for 4 times to remove sodium ions in the solid; (5) adding kaolin powder adhesive into the powder without sodium ions for molding, and then drying in the air and roasting at 550 ℃ for 2h to obtain a molded solid catalyst precursor; (6) charging solid shaped catalyst precursor into fixed bed reactor, using catalyst containing H250% by volume of H2-N2Reducing the mixed gas at 400 ℃ for 6H for activation to obtain the activated 0.2% Cu 4% Ni/H-MCM-22 catalyst.
The product was analyzed by XRD powder diffraction to obtain a crystalline product of H-MCM-22 zeolite (characteristic diffraction peak 2 theta of 6.6 DEG, 7.1 DEG, 8.0 DEG, 22.5 DEG, 26.0 DEG), and a weak Ni (1.1.1) characteristic diffraction peak near 44.5 DEG 2 theta. The plate-like crystals were observed by scanning electron microscope TEM, see FIG. 5.
The prepared 0.2% Cu 4% Ni/H-MCM-22 (labeled C5) was used to catalyze the benzene hydroalkylation process and the results are listed in Table 1.
Example 6
(1) Dissolving 0.116g of iridium trichloride hydrate (0.00031mol) and 5.96g of nickel nitrate hydrate (0.0205mol) in 10g of methanol, adding 0.0624mol of piperazine, and carrying out a complex reaction at 50 ℃ for 2 hours to obtain a metal amine complex alcoholic solution; (2) 75g of silica Sol (SiO)240 percent of pseudo-boehmite, sodium hydroxide and deionized water are stirred and mixed evenly, template agent hexamethyleneimine is added, stirring is carried out for 4 hours at room temperature, the metal amine complex alcohol solution obtained in the step (1) is added, and then stirring is carried out fully for 10 hours at room temperature, so as to obtain aluminosilicate gel; the feeding amount is controlled to ensure that the molar ratio of materials in the reaction mixture is as follows: SiO 22/Al2O3＝60、SiO2/OH-＝3、SiO2Hexamethyleneimine 1, H2O/SiO225; transferring the gel into a pressure kettle with polytetrafluoroethylene lining, and controlling the temperature to be 150 ℃ for dynamic crystallization for 120 h; (3) cooling the crystallized product to room temperature, washing the crystallized product with deionized water until the pH of the filtrate is less than 9, and then baking the crystallized product in the air at 120 ℃ for 6 hours and at 550 ℃ for 2 hours; (4) pulverizing the obtained solid, and washing with 1.5M oxalic acid water solution for 2 times to remove sodium ions in the solid; (5) adding an alumina powder binder into the powder subjected to sodium ion removal for molding, and then drying in air and roasting at 550 ℃ for 2h to obtain a molded solid catalyst precursor; (6) charging solid shaped catalyst precursor into fixed bed reactor, using catalyst containing H250% by volume of H2-N2Reducing the mixed gas for 4H at 450 ℃ for activation to obtain the activated 0.2% Ir 4% Ni/H-MCM-22 catalyst.
The product was analyzed by XRD powder diffraction to obtain a crystalline product of H-MCM-22 zeolite (characteristic diffraction peak 2 theta of 6.6 DEG, 7.1 DEG, 8.0 DEG, 22.5 DEG, 26.0 DEG), and a weak Ni (1.1.1) characteristic diffraction peak near 44.5 DEG 2 theta. The plate-like crystals were observed by scanning electron microscopy (TEM).
The 0.2% Ir 4% Ni/H-MCM-22 (labeled C6) prepared was used to catalyze the benzene hydroalkylation process and the results are listed in Table 1.
Example 7
(1) 0.362g of ammonium perrhenate (0.00135mol) and 5.96g of hydrated nickel nitrate (0.0205mol) are dissolved in 10g of methanol, 0.065mol of piperazine is added, and complexation reaction is carried out for 2h at 30 ℃ to obtain a metal amine complex alcoholic solution; (2) uniformly stirring 30g of silica gel, sodium metaaluminate, sodium hydroxide and deionized water, adding a template agent hexamethyleneimine, stirring at room temperature for 4 hours, adding the metal amine complex alcohol solution obtained in the step (1), and fully stirring at room temperature for 12 hours to obtain aluminosilicate gel; the feeding amount is controlled to ensure that the molar ratio of materials in the reaction mixture is as follows: SiO 22/Al2O3＝50、SiO2/OH-＝2、SiO2Hexamethyleneimine (2), H2O/SiO235; transferring the gel into a pressure kettle with polytetrafluoroethylene lining, and controlling the temperature to be 150 ℃ for dynamic crystallization for 108 hours; (3) product after crystallizationCooling the product to room temperature, washing the product with deionized water until the pH of the filtrate is less than 9, and then baking the product in the air at 120 ℃ for 6h and at 550 ℃ for 2 h; (4) pulverizing the obtained solid, and washing with 0.5M oxalic acid water solution for 3 times to remove sodium ions in the solid; (5) adding an alumina powder binder into the powder subjected to sodium ion removal for molding, and then drying in air and roasting at 550 ℃ for 2h to obtain a molded solid catalyst precursor; (6) charging solid shaped catalyst precursor into fixed bed reactor, using catalyst containing H250% by volume of H2-N2Reducing the mixed gas at 450 ℃ for 4H for activation to obtain the activated 0.2 percent Re4 percent Ni/H-MCM-22 catalyst.
The product was analyzed by XRD powder diffraction to obtain a crystalline product of H-MCM-22 zeolite (characteristic diffraction peak 2 theta of 6.6 DEG, 7.1 DEG, 8.0 DEG, 22.5 DEG, 26.0 DEG), and a weak Ni (1.1.1) characteristic diffraction peak near 44.5 DEG 2 theta. The plate-like crystals were observed by scanning electron microscopy (TEM).
The prepared 0.2% Re 4% Ni/H-MCM-22 (labeled C7) was used to catalyze the benzene hydroalkylation process and the results are listed in Table 1.
Example 8
(1) 1.717g of stannous chloride hydrate (0.0076mol), 2.81g of cerium nitrate hydrate (0.0065mol) and 5.96g of nickel nitrate hydrate (0.0205mol) are dissolved in 10g of methanol, 0.122mol of piperidine is added, and complexation reaction is carried out for 4h at 30 ℃ to obtain a metal amine complex alcoholic solution; (2) 75g of silica Sol (SiO)240 percent of sodium metaaluminate, sodium hydroxide and deionized water are stirred and mixed evenly, then template agent hexamethyleneimine is added, stirred for 4 hours at room temperature, the metal amine complex alcohol solution obtained in the step (1) is added, and then stirred for 12 hours at room temperature, thus obtaining aluminosilicate gel; the feeding amount is controlled to ensure that the molar ratio of materials in the reaction mixture is as follows: SiO 22/Al2O3＝25、SiO2/OH-＝6、SiO2Hexamethyleneimine (8), H2O/SiO235; transferring the gel into a pressure kettle with polytetrafluoroethylene lining, and controlling dynamic crystallization at 155 ℃ for 96 hours; (3) cooling the crystallized product to room temperature, washing the crystallized product with deionized water until the pH of the filtrate is less than 9, and then baking the crystallized product in the air at 120 ℃ for 6 hours and at 550 ℃ for 2 hours; (4) subjecting the obtained product toPulverizing the solid, washing with 0.5M oxalic acid water solution for 3 times to remove sodium ions in the solid; (5) adding an alumina powder binder into the powder subjected to sodium ion removal for molding, and then drying in air and roasting at 550 ℃ for 2h to obtain a molded solid catalyst precursor; (6) charging solid shaped catalyst precursor into fixed bed reactor, using catalyst containing H250% by volume of H2-N2Reducing the mixed gas for 4H and activating at 450 ℃ to obtain the activated 3% Sn 3% Ce 4% Ni/H-MCM-22 catalyst.
The product was analyzed by XRD powder diffraction to obtain a crystalline product of H-MCM-22 zeolite (characteristic diffraction peak 2 theta of 6.6 DEG, 7.1 DEG, 8.0 DEG, 22.5 DEG, 26.0 DEG), and a weak Ni (1.1.1) characteristic diffraction peak near 44.5 DEG 2 theta. The plate-like crystals were observed by scanning electron microscopy (TEM), see FIG. 6.
The 3% Sn 3% Ce 4% Ni/H-MCM-22 (labeled C8) prepared was used to catalyze the benzene hydroalkylation process and the results are listed in Table 1.
Example 9
(1) Dissolving 0.075g of palladium chloride (0.00043mol), 4.68g of lanthanum nitrate hydrate (0.0108mol) and 5.96g of nickel nitrate hydrate (0.0205mol) in 15g of methanol, adding 0.1mol of piperidine, and carrying out a complexation reaction at 30 ℃ for 4 hours to obtain an alcoholic solution of a metal amine complex; (2) 75g of silica Sol (SiO)240 percent of sodium metaaluminate, sodium hydroxide and deionized water are stirred and mixed evenly, then template agent hexamethyleneimine is added, stirring is carried out for 3 hours at room temperature, then the metal amine complex alcohol solution obtained in the step (1) is added, and stirring is carried out fully for 8 hours at room temperature, thus obtaining aluminosilicate gel; the feeding amount is controlled to ensure that the molar ratio of materials in the reaction mixture is as follows: SiO 22/Al2O3＝25、SiO2/OH-＝6、SiO2Hexamethyleneimine (4), H2O/SiO220; transferring the gel into a pressure kettle with polytetrafluoroethylene lining, and controlling the temperature of 160 ℃ for dynamic crystallization for 84 hours; (3) cooling the crystallized product to room temperature, washing the crystallized product with deionized water until the pH of the filtrate is less than 9, and then baking the crystallized product in the air at 120 ℃ for 6 hours and at 550 ℃ for 2 hours; (4) pulverizing the obtained solid, and washing with 0.5M oxalic acid water solution for 3 times to remove sodium ions in the solid; (5) the sodium ion-removed powder is mixed with sodium chloride,adding an alumina powder adhesive for molding, then drying in the air, and roasting at 550 ℃ for 2h to obtain a molded solid catalyst precursor; (6) charging solid shaped catalyst precursor into fixed bed reactor, using catalyst containing H250% by volume of H2-N2Reducing the mixed gas at 450 ℃ for 4H for activation to obtain the activated 0.15% Pd 5% La 4% Ni/H-MCM-22 catalyst.
The product was analyzed by XRD powder diffraction to obtain a crystalline product of H-MCM-22 zeolite (characteristic diffraction peak 2 theta of 6.6 DEG, 7.1 DEG, 8.0 DEG, 22.5 DEG, 26.0 DEG), and a weak Ni (1.1.1) characteristic diffraction peak near 44.5 DEG 2 theta. The plate-like crystals were observed by a scanning electron microscope (TEM), and are shown in FIG. 7.
The prepared 0.15% Pd 5% La 4% Ni/H-MCM-22 (labeled C9) was used to catalyze the benzene hydroalkylation process and the results are listed in Table 1.
Example 10
(1) Dissolving 0.229g of hydrated copper nitrate (0.00095mol), 2.815g of hydrated lanthanum nitrate (0.0065mol) and 5.96g of hydrated nickel nitrate (0.0205mol) in 10g of methanol, adding 0.084mol of piperidine, and carrying out complex reaction at 30 ℃ for 4 hours to obtain a metal amine complex alcoholic solution; (2) 75g of silica Sol (SiO)240 percent of sodium metaaluminate, sodium hydroxide and deionized water are stirred and mixed evenly, then template agent hexamethyleneimine is added, stirring is carried out for 3 hours at room temperature, then the metal amine complex alcohol solution obtained in the step (1) is added, and stirring is carried out fully for 8 hours at room temperature, thus obtaining aluminosilicate gel; the feeding amount is controlled to ensure that the molar ratio of materials in the reaction mixture is as follows: SiO 22/Al2O3＝25、SiO2/OH-＝6、SiO2Hexamethyleneimine (4), H2O/SiO220; transferring the gel into a pressure kettle with polytetrafluoroethylene lining, and controlling the temperature of 160 ℃ for dynamic crystallization for 84 hours; (3) cooling the crystallized product to room temperature, washing the crystallized product with deionized water until the pH of the filtrate is less than 9, and then baking the crystallized product in the air at 120 ℃ for 6 hours and at 550 ℃ for 2 hours; (4) pulverizing the obtained solid, and washing with 0.5M oxalic acid water solution for 3 times to remove sodium ions in the solid; (5) adding the powder without sodium ions into an alumina powder adhesive for molding, then drying in the air, and roasting at 550 ℃ for 2h to obtain a molded solid catalystA precursor; (6) charging solid shaped catalyst precursor into fixed bed reactor, using catalyst containing H250% by volume of H2-N2Reducing the mixed gas at 450 ℃ for 4H for activation to obtain the activated 0.2% Cu 3% La 4% Ni/H-MCM-22 catalyst.
The product was analyzed by XRD powder diffraction to obtain a crystalline product of H-MCM-22 zeolite (characteristic diffraction peak 2 theta of 6.6 DEG, 7.1 DEG, 8.0 DEG, 22.5 DEG, 26.0 DEG), and a weak Ni (1.1.1) characteristic diffraction peak near 44.5 DEG 2 theta. The plate-like crystals were observed by a scanning electron microscope (TEM), and are shown in FIG. 8.
The prepared 0.2% Cu 3% La 4% Ni/H-MCM-22 (labeled C10) was used to catalyze the benzene hydroalkylation process and the results are listed in Table 1.
Comparative example 1
According to the process for preparing cyclohexylbenzene disclosed in chinese patent CN101998942A (process for preparing cyclohexylbenzene), a Pd catalyst was prepared by impregnating alumina with a palladium nitrate solution and calcining at 350 ℃ for 3 hours, and the loading amount of Pd on the alumina was 0.3%. Then Pd/Al2O3With MCM-49 at a molar ratio of 1: 3 to prepare the catalyst of the comparative example. The reaction conditions include a temperature of 140 to 175 deg.C, a pressure of 135 to 175psig (931 to 1207kPag), a hydrogen/benzene molar ratio of 0.30 to 0.65, and a time of 0.26 to 1.05h-1The weight hourly space velocity of benzene.
The catalyst prepared in comparative example 1 was used to catalyze the benzene hydroalkylation process, and the experimental results showed that the conversion of benzene was 28.6% and the selectivity of cyclohexylbenzene was 68.3%.
TABLE 1 results of the catalytic benzene hydroalkylation of the catalysts prepared in the examples
Note: the reactor is a stainless steel tube with phi 22x3, and 10.0mL of 20-40 mesh catalyst is filled in the reactor.
BZ is benzene, CHB is cyclohexylbenzene, DCB is dicyclohexylbenzene, and CH is cyclohexane.
PH2S is the gauge pressure and S is the selectivity.
As can be seen from the test results in the table above, when the metal/H-MCM-22 catalyst prepared by the method is used for preparing the cyclohexylbenzene, the conversion rate of the benzene and the selectivity of the cyclohexylbenzene are both high.
Claims (9)
1. A preparation method of a metal/H-MCM-22 catalyst is characterized by comprising the following steps:
(1) carrying out a complexing reaction on the metal active component alcohol solution and a complexing agent to obtain a metal active component ionic complex;
(2) uniformly mixing a silicon source, an aluminum source, an alkali source, water and a template agent hexamethyleneimine required by synthesizing the H-MCM-22 molecular sieve, adding the metal active component ion complex prepared in the step (1), fully and uniformly stirring at room temperature to obtain aluminosilicate gel, transferring the aluminosilicate gel into a pressure kettle, and crystallizing;
(3) cooling the product crystallized in the step (2) to room temperature, washing the product with deionized water until the pH of the filtrate is less than 9, and then drying and roasting the filtrate to obtain a solid;
(4) crushing the solid obtained in the step (3), and then washing the solid with a cation exchanger aqueous solution to obtain a solid without alkali metal ions;
(5) sequentially forming, drying and roasting the solid from which the alkali metal ions are removed in the step (4) to obtain a formed catalyst precursor;
(6) subjecting the catalyst precursor shaped in step (5) to reaction with H2-N2Reducing and activating the mixed gas to obtain an activated metal/H-MCM-22 catalyst;
the metal active component in the step (1) is one, two or three of nickel, palladium, platinum, ruthenium, rhenium, iridium, copper, tin, lanthanum and cerium; the alcohol is methanol or ethanol; the complexing agent is any one of piperazine, piperidine, homopiperazine or hexamethyleneimine;
the silicon source is any one of silica sol, silica gel or white carbon black; the aluminum source is any one of sodium aluminate, aluminum sulfate, pseudo-boehmite or alumina powder; the alkali source is sodium hydroxide or potassium hydroxide; original sourceThe material molar ratio is as follows: SiO 22/Al2O315 to 60 of SiO2/OH-1.2 to 8; SiO 22The amount of hexamethyleneimine is 1-8, H2O/ SiO215 to 50.
2. The method for preparing a metal/H-MCM-22 catalyst of claim 1, wherein the metal active component in step (1) is a combination of two or three metal components selected from nickel, palladium, platinum, ruthenium, rhenium, iridium, copper, tin, lanthanum, and cerium.
3. The method for preparing a metal/H-MCM-22 catalyst of claim 1, wherein in step (1), the mole ratio of the complexing agent to the metal active component is 3-6: 1.
4. the method for preparing a metal/H-MCM-22 catalyst of claim 1, wherein in step (1), the temperature of the complexation reaction is 10-60 ℃, and the complexation time is 0.5-4H.
5. The method for preparing the metal/H-MCM-22 catalyst of claim 1, wherein in step (2), the crystallization temperature is 140-175 ℃ and the crystallization time is 48-120H.
6. The method for preparing the metal/H-MCM-22 catalyst of claim 1, wherein in the step (3), the drying temperature is 80-150 ℃ and the drying time is 4-8H.
7. The method for preparing the metal/H-MCM-22 catalyst of claim 1, wherein in step (3), the roasting temperature is 450-600 ℃ and the roasting time is 2-6H.
8. The method for preparing a metal/H-MCM-22 catalyst of claim 1, wherein in step (4), the cation exchanger is 0.5-1.5 mol/L ammonium carbonate or oxalic acid water solution, and the exchange is carried out for 2-5 times.
9. The process for preparing a metal/H-MCM-22 catalyst of any of claims 1 to 8, wherein in step (6), said reductive activation is by H-containing225 to 100% by volume of H2-N2Treating the mixed gas at 200-500 ℃ for 2-10 h.
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| CN103551192A (en) * | 2013-11-22 | 2014-02-05 | 东北石油大学 | Preparation method of rare-earth modified MCM-48 loaded double-function catalyst |
| CN105170178A (en) * | 2015-08-21 | 2015-12-23 | 宁波海越新材料有限公司 | Catalyst for propane dehydrogenation to prepare propylene and preparation method thereof |
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| CN103551192A (en) * | 2013-11-22 | 2014-02-05 | 东北石油大学 | Preparation method of rare-earth modified MCM-48 loaded double-function catalyst |
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