CN112023941B - Catalyst for olefin isomerization and preparation method thereof - Google Patents

Catalyst for olefin isomerization and preparation method thereof Download PDF

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CN112023941B
CN112023941B CN202011063173.XA CN202011063173A CN112023941B CN 112023941 B CN112023941 B CN 112023941B CN 202011063173 A CN202011063173 A CN 202011063173A CN 112023941 B CN112023941 B CN 112023941B
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activated carbon
mass
catalyst
modified activated
aluminum
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CN112023941A (en
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王昭文
张磊
翟康
陈丹
闫江梅
李岳锋
高武
万克柔
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Kaili Catalyst New Materials Co Ltd
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    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/8946—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali or alkaline earth metals
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/18—Carbon
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    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
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    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
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    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/16—Reducing
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    • C01B32/30—Active carbon
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    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/22—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by isomerisation
    • C07C5/23—Rearrangement of carbon-to-carbon unsaturated bonds
    • C07C5/25—Migration of carbon-to-carbon double bonds
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    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

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Abstract

The invention discloses a catalyst for olefin isomerization, which comprises modified activated carbon and Pd and Cu loaded on the modified activated carbon, wherein in the catalyst, the mass of the Cu is 1-2% of that of the modified activated carbon, and the mass of the Pd is 1.5-3 times of that of the Cu; the modified activated carbon is aluminum, magnesium and transition metal modified activated carbon, the mass of aluminum in the aluminum, magnesium and transition metal modified activated carbon is 0.8-1.5% of the mass of the activated carbon, the mass ratio of the aluminum to the magnesium to the transition metal is 1. When the catalyst is used for catalyzing the double bond isomerization reaction of beta-pinene by using the pinene mixture as a raw material, the ring-opening products and the hydrogenated products are obviously reduced, the content of alpha-pinene is more than 99 percent, and the catalyst has good reaction performance.

Description

Catalyst for olefin isomerization and preparation method thereof
Technical Field
The invention belongs to the technical field of catalyst preparation, and particularly relates to a catalyst for olefin isomerization and a preparation method thereof.
Background
The double bond isomerization reaction is a chemical reaction of changing the position of a double bond under the condition of unchanging the molecular skeleton of an organic compound, and is one of important chemical reaction processes for synthesizing a plurality of chemical product intermediates relating to energy, spice, medicine, pesticide and the like. Pinene is used as an important raw material for the perfume industry and the synthesis of other fine chemicals, and is mainly prepared by taking a turpentine primary distillation product pinene mixture as a raw material through a double bond isomerization reaction.
At present, catalysts commonly used for double bond isomerization reaction comprise homogeneous catalysts containing palladium, rhodium or iridium, molecular sieve catalysts and Pd/Al 2 O 3 Or a Pd/C catalyst. The Pd/C catalyst is widely applied to double bond isomerization reaction due to rich species and low cost, but due to the limitation of the catalyst and reaction environment, the isomerization reaction carried out by taking the Pd/C as the catalyst often has the problems of poor selectivity and the like, and due to the occurrence of side reactions such as double bond hydrogenation in hydrogen atmosphere and ring opening of a ring structure in a molecule, a new challenge is provided for the research and development of the olefin isomerization catalyst.
Disclosure of Invention
The technical problem to be solved by the present invention is to provide a catalyst for olefin isomerization and a preparation method thereof, aiming at the defects of the prior art. The invention provides a catalyst for olefin isomerization, which takes ternary hydrotalcite-like structure modified active carbon generated by aluminum, magnesium and transition metal as a carrier to load Pd and Cu, and when the catalyst is used for catalyzing double bond isomerization reaction of beta-pinene by taking a pinene mixture as a raw material, ring-opening products and hydrogenation products are obviously reduced, the content of alpha-pinene is more than 99 percent, and the catalyst has good reaction performance.
In order to solve the technical problems, the invention adopts the technical scheme that: the catalyst for olefin isomerization is characterized by comprising modified activated carbon and Pd and Cu loaded on the modified activated carbon, wherein in the catalyst, the mass of the Cu is 1% -2% of that of the modified activated carbon, and the mass of the Pd is 1.5-3 times of that of the Cu;
the modified activated carbon is modified activated carbon of aluminum, magnesium and transition metal, wherein in the modified activated carbon of aluminum, magnesium and transition metal, the mass of aluminum is 0.8-1.5% of the mass of the activated carbon, the mass ratio of the aluminum to the magnesium to the transition metal is 1.
The catalyst for olefin isomerization is characterized in that the modified activated carbon is prepared by the following method, and the method comprises the following steps:
step one, mixing activated carbon and a urea aqueous solution to obtain slurry A; the granularity of the active carbon is 200 meshes-400 meshes, and the specific surface area is 800m 2 /g～1200m 2 /g；
And step two, mixing a mixed solution containing an aluminum source, a magnesium source and a transition metal soluble salt with the slurry A obtained in the step one, reacting for 8-12 h at the temperature of 120-140 ℃, cooling, filtering, washing, drying and roasting to obtain the modified activated carbon.
The catalyst for olefin isomerization described above is characterized in that the ratio of the mass of the urea in the first step to the mass of the aluminum element in the aluminum source in the second step is (18 to 24): 1.
the catalyst for olefin isomerization is characterized in that, in the second step, the aluminum source is a nitrate of aluminum, the magnesium source is a nitrate of magnesium, and the soluble salt of the transition metal is a nitrate of the transition metal; the roasting temperature in the second step is 350-450 ℃, and the roasting time is 4-8 h.
In addition, the present invention provides a method for preparing the catalyst for olefin isomerization, which comprises the following steps:
step 101, mixing and stirring modified activated carbon and a sodium carbonate solution for 2-3 hours to obtain a mixed material A;
102, dripping a hydrazine hydrate solution into a mixed solution containing a palladium source, a copper source and polyoxyethylene lauryl ether, and stirring for 2-3 hours to obtain a mixed material B;
and 103, mixing the mixed material A obtained in the step 101 with the mixed material B obtained in the step 102, stirring and stabilizing for 4-8 h, filtering, and washing the retentate obtained by filtering to be neutral to obtain the catalyst for olefin isomerization.
The method is characterized in that in step 101, the volume of the sodium carbonate solution is 5 to 10 times of the mass of the modified activated carbon, the volume of the sodium carbonate solution is expressed by mL, the mass of the modified activated carbon is expressed by g, and the concentration of the sodium carbonate solution is 0.3 to 0.5mol/L.
The method is characterized in that the mass of the polyoxyethylene lauryl ether in the step 102 is 10 to 15 times of the mass of palladium element in the palladium source; in step 102, the palladium source is sodium chloropalladite, and the copper source is copper nitrate.
The method is characterized in that the time for dripping the hydrazine hydrate solution in the step 102 is 30-60 min, the volume of the hydrazine hydrate is 3-6 times of the mass of the palladium in the palladium source, and the content of the hydrazine hydrate in the hydrazine hydrate solution is 0.018-0.036 mL/mL.
Compared with the prior art, the invention has the following advantages:
1. the invention provides a catalyst for olefin isomerization, which takes ternary hydrotalcite-like structure modified active carbon generated by aluminum, magnesium and transition metal as a carrier to load Pd and Cu, and when the catalyst is used for catalyzing double bond isomerization reaction of beta-pinene by taking a pinene mixture as a raw material, ring-opening products and hydrogenation products are obviously reduced, the content of alpha-pinene is more than 99 percent, and the catalyst has good reaction performance.
2. The preparation method of the modified activated carbon in the catalyst for olefin isomerization comprises the steps of mixing the activated carbon with a urea aqueous solution, then reacting the mixture with a mixed solution containing an aluminum source, a magnesium source and a transition metal soluble salt in a stainless steel reaction kettle with a polytetrafluoroethylene lining, fully playing the role of modifying the activated carbon by a ternary hydrotalcite-like structure formed by aluminum, magnesium and the transition metal, and improving the surface acidity and alkalinity of the activated carbon.
3. The preparation method of the catalyst for olefin isomerization comprises the steps of mixing a mixed solution containing a palladium source, a copper source and polyoxyethylene lauryl ether after a hydrazine hydrate solution is dripped with modified activated carbon for reaction, introducing Pd and Cu onto the modified activated carbon, inhibiting double bond hydrogenation reaction through the synergistic effect of bimetal Pd and Cu, and improving the selectivity of the catalyst in the double bond isomerization reaction.
The technical solution of the present invention is further described in detail with reference to the following examples.
Detailed Description
In the following examples of the present invention, polyoxyethylene lauryl ether is preferably Brij-35, which is purchased from Allantin, and the remaining reagents and materials are commercially available, and the experimental methods in the following examples, which are not specified to specific conditions, are performed according to conventional methods and conditions.
Example 1
The embodiment provides a catalyst for olefin isomerization, which comprises modified activated carbon and Pd and Cu loaded on the modified activated carbon, wherein in the catalyst, the mass of Pd is 3% of that of the modified activated carbon, and the mass of Cu is 2% of that of the modified activated carbon;
the modified activated carbon is modified activated carbon of aluminum, magnesium and transition metal, wherein in the modified activated carbon of aluminum, magnesium and transition metal, the mass of aluminum is 0.8% of the mass of the activated carbon, the mass ratio of the aluminum to the magnesium to the transition metal is 1.
This example provides a method for preparing a catalyst for olefin isomerization, which includes the following steps:
step one, dissolving 4.32g of urea in 200mL of water to obtain a urea aqueous solution, adding 30g of activated carbon into the urea aqueous solution, and stirring to uniformly mix to obtain slurry A; the particle size of the active carbon is 200 meshes, and the specific surface area is 814m 2 /g；
Step two, dissolving 3.34g of aluminum nitrate nonahydrate, 4.56g of magnesium nitrate hexahydrate and 2.59g of nickel nitrate hexahydrate in 100mL of water to obtain a mixed solution containing an aluminum source, a magnesium source and transition metal soluble salt, mixing the mixed solution containing the aluminum source, the magnesium source and the transition metal soluble salt with the slurry A obtained in the step one, placing the mixed solution in a stainless steel reaction kettle with a polytetrafluoroethylene lining, reacting for 12 hours at the temperature of 120 ℃, naturally cooling to room temperature, carrying out suction filtration, washing a solid material obtained by suction filtration with deionized water, drying, and roasting the dried material for 8 hours at the temperature of 350 ℃ to obtain modified activated carbon;
step three, mixing and stirring 20g of the modified activated carbon obtained in the step two and 160mL of sodium carbonate solution with the concentration of 0.3mol/L for 3 hours to obtain a mixed material A;
step four, dissolving 1.67g of sodium chloropalladite in 100mL of water to obtain a sodium chloropalladite solution, dissolving 1.52g of copper nitrate trihydrate in 100mL of water to obtain a copper nitrate solution, dissolving 9g of polyoxyethylene lauryl ether in 500mL of water to obtain a polyoxyethylene lauryl ether solution, mixing the sodium chloropalladite solution, the copper nitrate solution and the polyoxyethylene lauryl ether solution, fixing the volume to 1000mL, stirring for 30min to obtain a mixed solution containing a palladium source, a copper source and polyoxyethylene lauryl ether, dropwise adding 100mL of a hydrazine hydrate solution with the hydrazine hydrate content of 0.036mL/mL into the mixed solution containing the palladium source, the copper source and the polyoxyethylene lauryl ether under the stirring condition, and continuously stirring and stabilizing for 2h to obtain a mixed material B; the time for dripping the hydrazine hydrate solution is 45min;
and step five, mixing the mixed material A obtained in the step three and the mixed material B obtained in the step four, stirring and stabilizing for 4 hours, filtering, washing the retentate obtained by filtering to be neutral, and obtaining the catalyst for olefin isomerization.
Example 2
The embodiment provides a catalyst for olefin isomerization, which comprises modified activated carbon and Pd and Cu loaded on the modified activated carbon, wherein in the catalyst, the mass of Pd is 3% of that of the modified activated carbon, and the mass of Cu is 1% of that of the modified activated carbon;
the modified activated carbon is modified activated carbon of aluminum, magnesium and transition metal, wherein in the modified activated carbon of aluminum, magnesium and transition metal, the mass of aluminum is 1.5% of the mass of the activated carbon, the mass ratio of the aluminum to the magnesium to the transition metal is 1.
This example provides a method for preparing a catalyst for olefin isomerization, comprising the steps of:
step one, dissolving 10.8g of urea in 200mL of water to obtain a urea aqueous solution, adding 30g of activated carbon into the urea aqueous solution, and stirring to uniformly mix to obtain slurry A; the particle size of the active carbon is 300 meshes, and the specific surface area is 1168m 2 /g；
Step two, dissolving 6.26g of aluminum nitrate nonahydrate, 8.55g of magnesium nitrate hexahydrate and 4.85g of nickel nitrate hexahydrate in 100mL of water to obtain a mixed solution containing an aluminum source, a magnesium source and transition metal soluble salt, mixing the mixed solution containing the aluminum source, the magnesium source and the transition metal soluble salt with the slurry A obtained in the step one, placing the mixed solution in a stainless steel reaction kettle with a polytetrafluoroethylene lining, reacting for 8 hours at the temperature of 140 ℃, naturally cooling to room temperature, carrying out suction filtration, washing a solid material obtained by suction filtration with deionized water, drying, and roasting the dried material for 4 hours at the temperature of 450 ℃ to obtain modified activated carbon;
step three, mixing and stirring 20g of the modified activated carbon obtained in the step two and 100mL of sodium carbonate solution with the concentration of 0.5mol/L for 2 hours to obtain a mixed material A;
dissolving 1.67g of sodium chloropalladite in 100mL of water to obtain a sodium chloropalladite solution, dissolving 0.76g of copper nitrate trihydrate in 100mL of water to obtain a copper nitrate solution, dissolving 6g of polyoxyethylene lauryl ether in 500mL of water to obtain a polyoxyethylene lauryl ether solution, mixing the sodium chloropalladite solution, the copper nitrate solution and the polyoxyethylene lauryl ether solution, fixing the volume to 1000mL, stirring for 30min to obtain a mixed solution containing a palladium source, a copper source and polyoxyethylene lauryl ether, dropwise adding 100mL of a hydrazine hydrate solution with the hydrazine hydrate content of 0.018mL/mL into the mixed solution containing the palladium source, the copper source and the polyoxyethylene lauryl ether under the stirring condition, and continuously stirring for 2h to obtain a mixed material B; the hydrazine hydrate solution is dripped for 30min;
and step five, mixing the mixed material A obtained in the step three and the mixed material B obtained in the step four, stirring and stabilizing for 8 hours, filtering, washing the retentate obtained by filtering to be neutral, and obtaining the catalyst for olefin isomerization.
Example 3
The embodiment provides a catalyst for olefin isomerization, which comprises modified activated carbon and Pd and Cu loaded on the modified activated carbon, wherein in the catalyst, the mass of Pd is 3% of that of the modified activated carbon, and the mass of Cu is 1.4% of that of the modified activated carbon;
the modified activated carbon is modified activated carbon of aluminum, magnesium and transition metal, wherein in the modified activated carbon of aluminum, magnesium and transition metal, the mass of aluminum is 1.0% of the mass of the activated carbon, the mass ratio of the aluminum to the magnesium to the transition metal is 1.
This example provides a method for preparing a catalyst for olefin isomerization, which includes the following steps:
step one, dissolving 6.32g of urea in 200mL of water to obtain a urea aqueous solution, adding 30g of activated carbon into the urea aqueous solution, and stirring to uniformly mix to obtain slurry A; the granularity of the active carbon is 400 meshes, and the specific surface area is 983m 2 /g；
Step two, dissolving 4.17g of aluminum nitrate nonahydrate, 5.70g of magnesium nitrate hexahydrate and 3.23g of cobalt nitrate hexahydrate in 100mL of water to obtain a mixed solution containing an aluminum source, a magnesium source and transition metal soluble salt, mixing the mixed solution containing the aluminum source, the magnesium source and the transition metal soluble salt with the slurry A obtained in the step one, placing the mixture in a stainless steel reaction kettle with a polytetrafluoroethylene lining, reacting at the temperature of 130 ℃ for 10 hours, naturally cooling to room temperature, carrying out suction filtration, washing solid materials obtained by suction filtration with deionized water, drying, roasting the dried materials at the temperature of 400 ℃ for 5 hours to obtain modified activated carbon;
step three, mixing and stirring 20g of the modified activated carbon obtained in the step two and 200mL of sodium carbonate solution with the concentration of 0.4mol/L for 3 hours to obtain a mixed material A;
dissolving 1.67g of sodium chloropalladite in 100mL of water to obtain a sodium chloropalladite solution, dissolving 1.07g of copper nitrate trihydrate in 100mL of water to obtain a copper nitrate solution, dissolving 7.2g of polyoxyethylene lauryl ether in 500mL of water to obtain a polyoxyethylene lauryl ether solution, mixing the sodium chloropalladite solution, the copper nitrate solution and the polyoxyethylene lauryl ether solution, fixing the volume to 1000mL, stirring for 30min to obtain a mixed solution containing a palladium source, a copper source and the polyoxyethylene lauryl ether, dropwise adding 100mL of a hydrazine hydrate solution with the hydrazine hydrate content of 0.030mL/mL into the mixed solution containing the palladium source, the copper source and the polyoxyethylene lauryl ether under the stirring condition, and continuously stirring for 2 hours to obtain a mixed material B; the time for dripping the hydrazine hydrate solution is 60min;
and step five, mixing the mixed material A obtained in the step three and the mixed material B obtained in the step four, stirring and stabilizing for 6 hours, filtering, washing the retentate obtained by filtering to be neutral, and obtaining the catalyst for olefin isomerization.
Example 4
The embodiment provides a catalyst for olefin isomerization, which comprises modified activated carbon and Pd and Cu loaded on the modified activated carbon, wherein in the catalyst, the mass of Pd is 3% of that of the modified activated carbon, and the mass of Cu is 2% of that of the modified activated carbon;
the modified activated carbon is modified activated carbon of aluminum, magnesium and transition metal, wherein in the modified activated carbon of aluminum, magnesium and transition metal, the mass of aluminum is 1.0% of the mass of the activated carbon, the mass ratio of the aluminum to the magnesium to the transition metal is 1.
This example provides a method for preparing a catalyst for olefin isomerization, which includes the following steps:
step one, dissolving 7.0g of urea in 200mL of water to obtain a urea aqueous solution, adding 30g of activated carbon into the urea aqueous solution, and stirring to uniformly mix to obtain slurry A; the granularity of the active carbon is 400 meshes, and the specific surface area is 983m 2 /g；
Step two, dissolving 4.17g of aluminum nitrate nonahydrate, 5.70g of magnesium nitrate hexahydrate and 3.23g of nickel nitrate hexahydrate in 100mL of water to obtain a mixed solution containing an aluminum source, a magnesium source and transition metal soluble salt, mixing the mixed solution containing the aluminum source, the magnesium source and the transition metal soluble salt with the slurry A obtained in the step one, placing the mixed solution in a stainless steel reaction kettle with a polytetrafluoroethylene lining, reacting for 10 hours at the temperature of 130 ℃, naturally cooling to room temperature, carrying out suction filtration, washing a solid material obtained by suction filtration with deionized water, drying, and roasting the dried material for 5 hours at the temperature of 400 ℃ to obtain modified activated carbon;
step three, mixing and stirring 20g of the modified activated carbon obtained in the step two with 200mL of 0.4mol/L sodium carbonate solution for 3 hours to obtain a mixed material A;
dissolving 1.67g of sodium chloropalladite in 100mL of water to obtain a sodium chloropalladite solution, dissolving 1.52g of copper nitrate trihydrate in 100mL of water to obtain a copper nitrate solution, dissolving 9g of polyoxyethylene lauryl ether in 500mL of water to obtain a polyoxyethylene lauryl ether solution, mixing the sodium chloropalladite solution, the copper nitrate solution and the polyoxyethylene lauryl ether solution, fixing the volume to 1000mL, stirring for 30min to obtain a mixed solution containing a palladium source, a copper source and polyoxyethylene lauryl ether, dropwise adding 100mL of a hydrazine hydrate solution with the hydrazine hydrate content of 0.030mL/mL into the mixed solution containing the palladium source, the copper source and the polyoxyethylene lauryl ether under the stirring condition, and continuously stirring for 2.5 hours to obtain a mixed material B; the time for dripping the hydrazine hydrate solution is 45min;
and step five, mixing the mixed material A obtained in the step three and the mixed material B obtained in the step four, stirring and stabilizing for 6 hours, filtering, washing the retentate obtained by filtering to be neutral, and obtaining the catalyst for olefin isomerization.
Example 5
The embodiment provides a catalyst for olefin isomerization, which comprises modified activated carbon and Pd and Cu loaded on the modified activated carbon, wherein in the catalyst, the mass of Pd is 3% of that of the modified activated carbon, and the mass of Cu is 1% of that of the modified activated carbon;
the modified activated carbon is modified activated carbon of aluminum, magnesium and transition metal, wherein in the modified activated carbon of aluminum, magnesium and transition metal, the mass of aluminum is 0.8% of the mass of the activated carbon, the mass ratio of the aluminum to the magnesium to the transition metal is 1.
This example provides a method for preparing a catalyst for olefin isomerization, which includes the following steps:
step one, dissolving 5.5g of urea in 200mL of water to obtain a urea aqueous solutionAdding 30g of activated carbon into the urea aqueous solution, and stirring to uniformly mix to obtain slurry A; the particle size of the active carbon is 200 meshes, and the specific surface area is 814m 2 /g；
Step two, dissolving 3.34g of aluminum nitrate nonahydrate, 4.56g of magnesium nitrate hexahydrate and 2.59g of cobalt nitrate hexahydrate in 100mL of water to obtain a mixed solution containing an aluminum source, a magnesium source and transition metal soluble salt, mixing the mixed solution containing the aluminum source, the magnesium source and the transition metal soluble salt with the slurry A obtained in the step one, placing the mixture in a stainless steel reaction kettle with a polytetrafluoroethylene lining, reacting at the temperature of 120 ℃ for 12 hours, naturally cooling to room temperature, carrying out suction filtration, washing solid materials obtained by suction filtration with deionized water, drying, roasting the dried materials at the temperature of 350 ℃ for 8 hours to obtain modified activated carbon;
step three, mixing and stirring 20g of the modified activated carbon obtained in the step two and 100mL of sodium carbonate solution with the concentration of 0.3mol/L for 2.5 hours to obtain a mixed material A;
dissolving 1.67g of sodium chloropalladite in 100mL of water to obtain a sodium chloropalladite solution, dissolving 0.76g of copper nitrate trihydrate in 100mL of water to obtain a copper nitrate solution, dissolving 6g of polyoxyethylene lauryl ether in 500mL of water to obtain a polyoxyethylene lauryl ether solution, mixing the sodium chloropalladite solution, the copper nitrate solution and the polyoxyethylene lauryl ether solution, fixing the volume to 1000mL, stirring for 30min to obtain a mixed solution containing a palladium source, a copper source and polyoxyethylene lauryl ether, dropwise adding 100mL of a hydrazine hydrate solution with the hydrazine hydrate content of 0.018mL/mL into the mixed solution containing the palladium source, the copper source and the polyoxyethylene lauryl ether under the stirring condition, and continuously stirring for 3 hours to obtain a mixed material B; the hydrazine hydrate solution is dripped for 30min;
and step five, mixing the mixed material A obtained in the step three and the mixed material B obtained in the step four, stirring and stabilizing for 4 hours, filtering, washing the intercepted substances obtained by filtering to be neutral, and obtaining the catalyst for olefin isomerization.
Example 6
The embodiment provides a catalyst for olefin isomerization, which comprises modified activated carbon and Pd and Cu loaded on the modified activated carbon, wherein in the catalyst, the mass of Pd is 3% of that of the modified activated carbon, and the mass of Cu is 1.5% of that of the modified activated carbon;
the modified activated carbon is modified activated carbon of aluminum, magnesium and transition metal, wherein in the modified activated carbon of aluminum, magnesium and transition metal, the mass of aluminum is 1.5% of the mass of the activated carbon, the mass ratio of the aluminum to the magnesium to the transition metal is 1.
This example provides a method for preparing a catalyst for olefin isomerization, which includes the following steps:
step one, dissolving 9.0g of urea in 200mL of water to obtain a urea aqueous solution, adding 30g of activated carbon into the urea aqueous solution, and stirring to uniformly mix to obtain slurry A; the particle size of the active carbon is 300 meshes, and the specific surface area is 1168m 2 /g；
Step two, dissolving 6.26g of aluminum nitrate nonahydrate, 8.55g of magnesium nitrate hexahydrate and 4.85g of cobalt nitrate hexahydrate in 100mL of water to obtain a mixed solution containing an aluminum source, a magnesium source and transition metal soluble salt, mixing the mixed solution containing the aluminum source, the magnesium source and the transition metal soluble salt with the slurry A obtained in the step one, placing the mixed solution in a stainless steel reaction kettle with a polytetrafluoroethylene lining, reacting for 8 hours at the temperature of 140 ℃, naturally cooling to room temperature, carrying out suction filtration, washing a solid material obtained by suction filtration with deionized water, drying, and roasting the dried material for 4 hours at the temperature of 450 ℃ to obtain modified activated carbon;
step three, mixing and stirring 20g of the modified activated carbon obtained in the step two and 160mL of sodium carbonate solution with the concentration of 0.5mol/L for 2.5h to obtain a mixed material A;
dissolving 1.67g of sodium chloropalladite in 100mL of water to obtain a sodium chloropalladite solution, dissolving 1.14g of copper nitrate trihydrate in 100mL of water to obtain a copper nitrate solution, dissolving 7.2g of polyoxyethylene lauryl ether in 500mL of water to obtain a polyoxyethylene lauryl ether solution, mixing the sodium chloropalladite solution, the copper nitrate solution and the polyoxyethylene lauryl ether solution, fixing the volume to 1000mL, stirring for 30min to obtain a mixed solution containing a palladium source, a copper source and the polyoxyethylene lauryl ether, dropwise adding 100mL of a hydrazine hydrate solution with the hydrazine hydrate content of 0.036mL/mL into the mixed solution containing the palladium source, the copper source and the polyoxyethylene lauryl ether under the stirring condition, and continuously stirring for 3 hours to obtain a mixed material B; the time for dripping the hydrazine hydrate solution is 60min;
and step five, mixing the mixed material A obtained in the step three and the mixed material B obtained in the step four, stirring and stabilizing for 8 hours, filtering, washing the retentate obtained by filtering to be neutral, and obtaining the catalyst for olefin isomerization.
Comparative example 1
This comparison investigated the effect of unmodified activated carbon on the performance of catalysts for olefin isomerization. The present comparative example provides a catalyst for olefin isomerization, which comprises activated carbon and Pd and Cu supported on the activated carbon, wherein in the catalyst, the mass of Pd is 3% of the mass of activated carbon, and the mass of Cu is 1% of the mass of activated carbon.
This comparative example provides a method of making the above catalyst, the method comprising:
step one, mixing 20g of activated carbon and 160mL of sodium carbonate solution with the concentration of 0.3mol/L for 3 hours to obtain a mixed material A; the particle size of the active carbon is 200 meshes, and the specific surface area is 814m 2 /g；
Dissolving 1.67g of sodium chloropalladite in 100mL of water to obtain a sodium chloropalladite solution, dissolving 0.76g of copper nitrate trihydrate in 100mL of water to obtain a copper nitrate solution, dissolving 6g of polyoxyethylene lauryl ether in 500mL of water to obtain a polyoxyethylene lauryl ether solution, mixing the sodium chloropalladite solution, the copper nitrate solution and the polyoxyethylene lauryl ether solution, fixing the volume to 1000mL, stirring for 30min to obtain a mixed solution containing a palladium source, a copper source and polyoxyethylene lauryl ether, dropwise adding 100mL of a hydrazine hydrate solution with the hydrazine hydrate content of 0.018mL/mL into the mixed solution containing the palladium source, the copper source and the polyoxyethylene lauryl ether under the stirring condition, and continuously stirring for 2h to obtain a mixed material B; the time for dripping the hydrazine hydrate solution is 45min;
and step three, mixing the mixed material A obtained in the step one and the mixed material B obtained in the step two, stirring and stabilizing for 8 hours, filtering, washing the retentate obtained by filtering to be neutral, and obtaining the catalyst for olefin isomerization.
Comparative example 2
This comparative example examines the effect of not adding Cu on the performance of the catalyst for olefin isomerization. The present comparative example provides a catalyst for olefin isomerization, the catalyst comprising modified activated carbon and Pd supported on the modified activated carbon, wherein the mass of Pd in the catalyst is 3% of the mass of the modified activated carbon.
This comparative example provides a method of making the above catalyst, the method comprising:
step one, dissolving 4.32g of urea in 200mL of water to obtain a urea aqueous solution, adding 30g of activated carbon into the urea aqueous solution, and stirring to uniformly mix to obtain slurry A; the granularity of the active carbon is 200 meshes, and the specific surface area is 814m 2 /g；
Step two, dissolving 3.34g of aluminum nitrate nonahydrate, 4.56g of magnesium nitrate hexahydrate and 2.59g of nickel nitrate hexahydrate in 100mL of water to obtain a mixed solution containing an aluminum source, a magnesium source and transition metal soluble salt, mixing the mixed solution containing the aluminum source, the magnesium source and the transition metal soluble salt with the slurry A obtained in the step one, placing the mixed solution in a stainless steel reaction kettle with a polytetrafluoroethylene lining, reacting for 12 hours at the temperature of 120 ℃, naturally cooling to room temperature, carrying out suction filtration, washing a solid material obtained by suction filtration with deionized water, drying, and roasting the dried material for 8 hours at the temperature of 350 ℃ to obtain modified activated carbon;
step three, mixing and stirring 20g of the modified activated carbon obtained in the step two and 160mL of sodium carbonate solution with the concentration of 0.3mol/L for 3 hours to obtain a mixed material A;
dissolving 1.67g of sodium chloropalladite in 100mL of water to obtain a sodium chloropalladite solution, dissolving 9g of polyoxyethylene lauryl ether in 100mL of water to obtain a polyoxyethylene lauryl ether solution, mixing the sodium chloropalladite solution and the polyoxyethylene lauryl ether solution, fixing the volume to 1000mL, stirring for 30min to obtain a mixed solution containing a palladium source and polyoxyethylene lauryl ether, dropwise adding 100mL of a hydrazine hydrate solution with the hydrazine hydrate content of 0.036mL/mL into the mixed solution containing the palladium source and the polyoxyethylene lauryl ether under the stirring condition, and continuously stirring for 2h to obtain a mixed material B; dropwise adding hydrazine hydrate solution for 45min;
and step five, mixing the mixed material A obtained in the step three and the mixed material B obtained in the step four, stirring and stabilizing for 4 hours, filtering, washing the retentate obtained by filtering to be neutral, and obtaining the catalyst for olefin isomerization.
And (3) performance testing:
the catalysts of examples 1 to 6 and comparative examples 1 to 2 are used for double bond isomerization of beta-pinene, and the specific method comprises the following steps: adding 150mL of raw material (the volume percentage of beta-pinene in the raw material is 70 percent and the volume percentage of alpha-pinene in the raw material is 30 percent) into a 250mL stainless steel high-pressure reaction kettle, adding 1.5g of the catalyst, sealing the high-pressure kettle, replacing air in the reaction kettle with nitrogen for three times, replacing the air with hydrogen for three times, raising the temperature to 80 ℃, stirring and reacting for 5 hours under the condition that the hydrogen pressure is 0.05MPa, stopping the reaction, taking out reaction liquid after the temperature is reduced to the room temperature, filtering to remove the catalyst, analyzing filtrate by gas chromatography, and obtaining an analysis result shown in Table 1.
TABLE 1 chromatographic analysis of pinene isomerization product
Figure BDA0002713011220000131
According to table 1, compared with comparative examples 1 and 2, the double bond isomerization of beta-pinene is carried out by using the modified activated carbon of the invention and Pd and Cu loaded on the modified activated carbon, the content of the obtained alpha-pinene exceeds 99%, both the ring-opening product and the hydrogenation product are obviously lower than the comparative examples, and the catalyst of the invention has good double bond isomerization performance of catalyzing beta-pinene.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and all simple modifications, changes and equivalent structural changes made to the above embodiment according to the technical spirit of the present invention still fall within the protection scope of the technical solution of the present invention.

Claims (6)

1. The catalyst for olefin isomerization is characterized by comprising modified activated carbon and Pd and Cu loaded on the modified activated carbon, wherein in the catalyst, the mass of the Cu is 1% -2% of that of the modified activated carbon, and the mass of the Pd is 1.5-3 times of that of the Cu;
the modified activated carbon is modified activated carbon of aluminum, magnesium and transition metal, wherein in the modified activated carbon of aluminum, magnesium and transition metal, the mass of aluminum is 0.8-1.5% of the mass of the activated carbon, the mass ratio of the aluminum to the magnesium to the transition metal is 1; the modified activated carbon is prepared by the following method, and the method comprises the following steps:
step one, mixing activated carbon and a urea aqueous solution to obtain slurry A; the granularity of the active carbon is 200 meshes-400 meshes, and the specific surface area is 800m 2 /g～1200m 2 /g；
Step two, mixing a mixed solution containing an aluminum source, a magnesium source and a transition metal soluble salt with the slurry A obtained in the step one, reacting at the temperature of 120-140 ℃ for 8-12h, cooling, performing suction filtration, washing, drying and roasting to obtain the ternary hydrotalcite-like structure modified activated carbon;
the catalyst for olefin isomerization is a catalyst for olefin isomerization prepared by the following method, and the method comprises the following steps:
step 101, mixing and stirring modified activated carbon and a sodium carbonate solution for 2h to 3h to obtain a mixed material A;
102, dripping a hydrazine hydrate solution into a mixed solution containing a palladium source, a copper source and polyoxyethylene lauryl ether, and stirring for 2h to 3h to obtain a mixed material B;
and 103, mixing the mixed material A obtained in the step 101 and the mixed material B obtained in the step 102, stirring and stabilizing for 4 to 8 hours, filtering, and washing a retentate obtained by filtering to be neutral to obtain the catalyst for olefin isomerization.
2. The catalyst for olefin isomerization according to claim 1, wherein the ratio of the mass of the urea in the first step to the mass of the aluminum element in the aluminum source in the second step is (18 to 24): 1.
3. the olefin isomerization catalyst as claimed in claim 1, wherein in the second step, the aluminum source is a nitrate of aluminum, the magnesium source is a nitrate of magnesium, and the soluble salt of the transition metal is a nitrate of the transition metal; the roasting temperature in the second step is 350-450 ℃, and the roasting time is 4-8 h.
4. The olefin isomerization catalyst according to claim 1, wherein the volume of the sodium carbonate solution in step 101 is 5 to 10 times the mass of the modified activated carbon, the volume of the sodium carbonate solution is in mL, the mass of the modified activated carbon is in g, and the concentration of the sodium carbonate solution is 0.3 to 0.5mol/L.
5. The olefin isomerization catalyst according to claim 1, wherein the mass of the polyoxyethylene lauryl ether in the step 102 is 10 to 15 times of the mass of palladium element in the palladium source; in the step 102, the palladium source is sodium chloropalladite, and the copper source is copper nitrate.
6. The catalyst of claim 1, wherein the time for dripping the hydrazine hydrate solution in the step 102 is 30min to 60min, the volume of the hydrazine hydrate is 3-6 times of the mass of palladium in the palladium source, the volume unit of the hydrazine hydrate is mL, the mass unit of palladium in the palladium source is g, and the content of hydrazine hydrate in the hydrazine hydrate solution is 0.018mL/mL to 0.036mL/mL.
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4518488A (en) * 1983-02-28 1985-05-21 Standard Oil Company (Indiana) Metal-containing active carbon and methods for making and using same
CN103007962A (en) * 2012-12-14 2013-04-03 北京格林凯默科技有限公司 Metal oxide assisted palladium carbon catalyst and preparation method thereof
CN110227487A (en) * 2019-06-24 2019-09-13 西安凯立新材料股份有限公司 A kind of preparation method and application of carbonyl hydrogen catalyst
CN111233626A (en) * 2020-01-21 2020-06-05 浙江师范大学 Method for preparing benzhydryl alcohol by hydrogenation of benzophenone

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7446223B2 (en) * 2004-06-04 2008-11-04 Mitsubishi Rayon Co., Ltd. Palladium-containing catalyst and method for producing same

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4518488A (en) * 1983-02-28 1985-05-21 Standard Oil Company (Indiana) Metal-containing active carbon and methods for making and using same
CN103007962A (en) * 2012-12-14 2013-04-03 北京格林凯默科技有限公司 Metal oxide assisted palladium carbon catalyst and preparation method thereof
CN110227487A (en) * 2019-06-24 2019-09-13 西安凯立新材料股份有限公司 A kind of preparation method and application of carbonyl hydrogen catalyst
CN111233626A (en) * 2020-01-21 2020-06-05 浙江师范大学 Method for preparing benzhydryl alcohol by hydrogenation of benzophenone

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
对甲基苯乙酮催化加氢用钯炭催化剂研究;翟康等;《工业催化》;20191231(第12期);第34-38页 *

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