CN102309968B - Aldehyde hydrogenation catalyst as well as preparation method and application thereof - Google Patents

Aldehyde hydrogenation catalyst as well as preparation method and application thereof Download PDF

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CN102309968B
CN102309968B CN 201010212107 CN201010212107A CN102309968B CN 102309968 B CN102309968 B CN 102309968B CN 201010212107 CN201010212107 CN 201010212107 CN 201010212107 A CN201010212107 A CN 201010212107A CN 102309968 B CN102309968 B CN 102309968B
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CN102309968A (en
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王秀玲
徐洋
戴伟
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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China Petroleum and Chemical Corp
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Abstract

The invention discloses an aldehyde hydrogenation catalyst and a preparation method thereof. The catalyst comprises the following components in percentage by weight: 8-35 percent of nickel or oxide thereof, 0.01-2.0 percent of at least one element or oxide thereof in IA or IIA family, 0.01-20.0 percent of at least one element or oxide thereof in IIA or IVA family and 0.01-5 percent of rare-earth element. An aluminum oxide carrier has the specific surface area of 40-180 m<2>/g and the total pore volume of 0.4-1.2ml/g; the pore volume with the pore diameter of smaller than 30 nano accounts for 5-50 percent of total pore volume; the pore volume with the pore diameter of 30-80 nano accounts for 20-50 percent of total pore volume; and the pore volume with the pore diameter of larger than 80 nano accounts for 20-75 percent of total pore volume. All components are soaked, washed, dried and roasted to obtain the catalyst. The invention is suitable for aldehyde hydrogenation and has favorable low-temperature activity and selectivity when the corresponding alcohol is prepared.

Description

Aldehyde hydrogenation catalyst, preparation method and application thereof
Technical Field
The invention relates to the field of chemical industry, in particular to an aldehyde hydrogenation catalyst and a preparation method thereof.
Background
Butanol and octanol (2-hexanol) are important basic organic chemical raw materials. The former is mainly used for preparing butyric acid, butylamine, melamine formaldehyde resin, butyl acrylate, dibutyl phthalate, aliphatic dibasic acid ester and phosphate plasticizer, and is widely used in various plastic and rubber products, and ethers and amines prepared by the former are respectively used as emulsion paint, fabric processing adhesive, pesticide and rubber processing aid, leather treating agent and the like. The latter is mainly used for manufacturing a series of organic chemical products such as octyl acrylate, dioctyl sebacate, dioctyl phthalate and the like, and can also be used as raw materials of pesticide emulsifiers, surfactants, antifoaming agents, synthetic fiber oil agents and the like.
The aldehyde hydrogenation process is divided into a gas phase method and a liquid phase method. The gas-phase aldehyde hydrogenation process has the advantages of poor product quality (various impurities, high content and high sulfuric acid chroma), large reactor volume, high energy consumption and load which can not meet the design requirement, and the incomplete hydrogenation product 2-Ethylhexanal (EHA) of EPA (octenal) accounts for 0.2-0.5% (Wt) of the total amount of the reaction products. For the gas phase process, this amount is already in equilibrium. The liquid phase hydrogenation process adopts low temperature and high pressure, so that the defects of a gas phase method can be overcome.
Preparation of butane from corresponding aldehyde by CZ 280125B6 hydrogenation with nickel-chromium catalystAlcohol, isobutanol, 2-ethylhexanol. The related catalyst is prepared by mixing synthetic silica and diatomite, performing heat treatment at 800-1100 ℃, doping nickel and chromium salt, and activating at 300-500 ℃, wherein the catalyst comprises 20 percent of NiO and 20 percent of Cr2O33％、H2O3％、SiO274 percent, the catalyst is added with a toxic Cr compound, and is harmful to people and environment.
British patent GB 1443222 invention discloses C2-C20A process for preparing saturated fatty alcohol by hydrogenation catalysis of saturated fatty aldehyde. The catalyst consists of Ni and Mo, which respectively account for 5-15% and 5-20%; the carrier is silicic acid, and the specific surface area is 30-70m2The pore radius is 150-300A, the reaction condition is strict, and the reaction temperature is high.
Chinese patent CN 1275439 relates to an aldehyde liquid phase hydrogenation catalyst, a preparation method and application thereof. The carrier of the catalyst is selected from SiO2Or diatomite, nickel is the first active component, and other active components are selected from cobalt, molybdenum, chromium and potassium; the nickel content is 5-40% by weight percentage; 0.2-5.0% of cobalt and molybdenum, 0.5-6% of chromium and 0.5-2% of potassium, the pore diameter of the carrier is less than 1000A, and the pore diameter distribution is 5-15%. The active component is carried on SiO by impregnation or coprecipitation2Or on a diatomaceous earth support. Can be used in the liquid phase hydrogenation process for preparing saturated alcohol from saturated and unsaturated aldehyde, the reaction temperature is 120 ℃, and the pressure is 4 MPa.
A novel octanol liquid-phase hydrogenation catalyst is prepared by using an immersion method in Yangxin university, and the like, wherein the mass fraction of active components in the catalyst is about 20.0%, the mass fraction of magnesium is 1.9%, a carrier is hollow annular alumina, and the catalyst is used for octanol liquid-phase hydrorefining reaction with the overall dimension of 4mm multiplied by 2mm multiplied by 4 mm.
In the existing liquid phase aldehyde hydrogenation catalyst system, a nickel system is taken as a main catalyst, and the catalysts are poor in activity and low in selectivity. The reaction at a relatively high reaction temperature is required in order to improve the catalyst activity; in order to achieve a certain selectivity, an amine substance is added into the raw material aldehyde during the use process to improve the selectivitySelective, Ni-Cr/diatomaceous earth based catalysts were developed for C as Mitsubishi Kasei CORP (MITU)1～C5Aldehyde liquid phase hydrogenation is carried out at the reaction temperature of 140 ℃ and the operation pressure of 5 Mpa. The catalyst can also be used in C5The above aldehyde is hydrogenated, and C is added into the raw material to reduce the generation of by-products14～C20Tertiary amine, raw material conversion 94.4%.
The difficulty in preparing the aldehyde hydrogenation catalyst with high low-temperature activity, large treatment capacity and good selectivity is a technical problem to be solved at present.
Disclosure of Invention
In order to solve the technical problem that the aldehyde hydrogenation catalyst with high low-temperature activity, large treatment capacity and good selectivity is difficult to prepare in the prior art, the invention provides an aldehyde hydrogenation catalyst and a preparation method thereof. The catalyst is suitable for hydrogenation of at least one of normal butyl aldehyde, isobutyl aldehyde and octenal in any proportion to produce corresponding alcohol, and has good low-temperature activity and selectivity.
It is an object of the present invention to provide an aldehyde hydrogenation catalyst.
The aldehyde hydrogenation catalyst comprises an alumina carrier, and is characterized in that:
according to the weight of the alumina in the carrier being 100 percent, the weight percentages of other components and the alumina in the carrier are as follows:
a) 8-35% of nickel or its oxide;
b) 0.01 to 2.0% of at least one element of group IA or IIA or an oxide thereof;
c) 0.01 to 20.0% of at least one element of IIIA or IVA group or an oxide thereof;
d) 0.01-5% of rare earth elements;
the specific surface area of the alumina carrier is 40-180 m2The total pore volume is 0.4-1.2 ml/g, the pore volume with the pore diameter smaller than 30 nanometers accounts for 5-50% of the total pore volume, the pore volume with the pore diameter of 30-80 nanometers accounts for 20-50% of the total pore volume, and the pore volume with the pore diameter larger than 80 nanometers accounts for 20-75% of the total pore volume.
In particular implementations, conditions that may be preferred are:
a) 12-30% of nickel or its oxide;
b) 0.2 to 0.8% of at least one element of group IA or IIA or an oxide thereof;
c) 0.2 to 10.0% of at least one element of group IIIA or IVA or an oxide thereof;
d) 0.1-3.0% of rare earth elements; .
The IA group in b) is potassium, and the IIA group is at least one of calcium, magnesium or barium;
in the c), IIIA group is boron, IVA group is silicon;
the rare earth element in d) is lanthanum and/or cerium.
The specific surface area of the alumina carrier is 40-165 m2Per gram; the total pore volume is 0.5-1.1 ml/g; the pore volume with the pore diameter less than 30 nanometers accounts for 20-40% of the total pore volume; the pore volume of the pores with the diameter of 30-80 nanometers accounts for 20-45% of the total pore volume; the pore volume with the pore diameter larger than 80 nanometers accounts for 25 to 60 percent of the total pore volume
The aldehyde hydrogenation catalyst of the present invention may be prepared by the following method:
preparation of alumina carrier:
a) mixing alumina powder, a modification auxiliary agent, a peptizing agent, an extrusion aid and water, and then extruding into strips for forming; wherein,
the alumina powder is a mixture of pseudo-boehmite and alumina calcined at 900-1200 ℃, and the weight ratio of the two alumina powders is (1-200) to 1, preferably (9-100) to 1;
the modifying assistant is selected from rare earth and salts of metals selected from IIA in the periodic table of elements, and acid containing IIIA elements in the periodic table of elements and/or compounds of IVA group element silicon.
b) Drying the extruded strips obtained in the step a) for 1-24 hours at 50-120 ℃;
c) roasting at 800-1150 ℃ for 1-10 hours to obtain an alumina carrier;
preparation of (di) aldehyde hydrogenation catalyst:
and (2) impregnating the alumina carrier obtained in the step (I) with a nickel-containing salt solution, and washing, drying and roasting the impregnated carrier to obtain the aldehyde hydrogenation catalyst.
The second purpose of the invention is to provide a preparation method of the aldehyde hydrogenation catalyst.
The preparation steps comprise:
preparation of alumina carrier:
a) mixing alumina powder, a modification auxiliary agent, a peptizing agent, an extrusion aid and water, and then extruding into strips for forming; wherein,
the alumina powder is a mixture of pseudo-boehmite and alumina calcined at 900-1200 ℃, and the weight ratio of the two kinds of alumina powder is (1-200) to 1;
the modification auxiliary agent is selected from rare earth and salts of metals selected from IIA in the periodic table of elements, and acid containing IIIA elements in the periodic table of elements and/or compounds of IVA group element silicon;
b) drying the extruded strips obtained in the step a) for 1-24 hours at 50-120 ℃;
c) roasting at 800-1150 ℃ for 1-10 hours to obtain an alumina carrier;
preparation of (di) aldehyde hydrogenation catalyst:
and (2) impregnating the alumina carrier obtained in the step (I) with a nickel-containing salt solution, and washing, drying and roasting the impregnated carrier to obtain the aldehyde hydrogenation catalyst.
In the detailed description
In the preparation of the (one) alumina carrier,
the weight ratio of the two kinds of alumina powder is (9-100) to 1.
The modifying assistant is selected from rare earth and salts of metals selected from IIA in the periodic table of elements, and the rare earth element is preferably lanthanum or cerium. The metal in IIA is preferably at least one of calcium, magnesium or barium, preferably its chlorides, nitrates, acetates, sulfates, phosphates, silicates, oxides and organic compounds. For example: cerium oxide, lanthanum nitrate, cerium nitrate, magnesium chloride and calcium citrate;
the acid containing IIIA of the periodic Table is preferably boric acid;
the group IVA element is preferably a compound of silicon, such as: silicate, silica gel, silica sol, silicate ester, and more preferably sodium silicate, ethyl silicate, and silicon carbide.
The dosage and kind of the peptizing agent and the extrusion assistant are not particularly limited, and are conventional dosage in the field, in the invention, the dosage can be 0.1-10%, preferably 0.5-5% of the weight of the alumina in the carrier, and the peptizing agent can be one or more of commercially available nitric acid, formic acid, acetic acid, citric acid, phosphoric acid and oxalic acid; the extrusion aid can be one or more of cellulose, starch and sesbania powder which are sold in the market.
The carrier after impregnation is washed, dried and roasted in the air at the temperature of 300-600 ℃ to obtain the oxidative catalyst.
The catalyst can be used only by introducing hydrogen into a reactor for reduction.
The invention also aims to provide the application of the aldehyde hydrogenation catalyst in the aldehyde hydrogenation reaction.
The catalyst of the invention adopts an alumina carrier with bimodal or multimodal pore distribution, and the larger pore diameter can be several. The smaller pores in the carrier provide enough dynamic active centers for reaction, and the larger pores provide enough pore channels for mass transfer, so that the catalyst has a larger diffusion coefficient, the common external diffusion effect of a common catalyst is effectively eliminated, and the catalyst has good low-temperature activity and selectivity when corresponding alcohol is prepared.
Detailed Description
The present invention will be further described with reference to the following examples.
The pseudoboehmite used in the examples and comparative examples was produced by Tay gloss chemical Co., Ltd, and the remaining raw materials were commercially available.
Example 1
200 g of pseudo-boehmite, 75 g of alumina roasted at 980 ℃ and 5 g of sesbania powder are weighed, mixed, added with 10 g of solution (mass concentration is 2%) containing methylcellulose, 2.0 g of nitric acid, 1.3 g of boric acid, 16 g of magnesium nitrate and 240 ml of aqueous solution of 3.3 lanthanum nitrate, and extruded intoAnd (3) drying the millimeter tooth balls at 50 ℃ for 24 hours, and then roasting the millimeter tooth balls at 1000 ℃ for 4 hours to obtain the modified alumina carrier T1.
Nickel nitrate [ Ni (NO) ]3)2·6H2O]156 g potassium nitrate (K NO)3)1.6 g of the catalyst was dissolved in 145 ml of water to prepare an aqueous solution, the solution was adjusted to pH 10 with ammonia water, the alumina carrier was impregnated by the equivalent impregnation method, dried at 120 ℃ for 4 hours, and calcined at 350 ℃ for 4 hours to prepare a Ni-based catalyst Cl so that the final Ni content was 15% by weight of the carrier alumina. The specific composition, specific surface, pore volume and pore distribution of the catalyst are shown in table 1, wherein the content of each component is calculated by the weight of the carrier alumina.
Example 2
200 g of pseudo-boehmite, 75 g of alumina roasted at 1050 ℃ and 5 g of sesbania powder are weighed, mixed, added with 10 g of solution (mass concentration is 2%) containing methylcellulose, 2.0 g of nitric acid, 4.0 g of boric acid, 6.0 g of calcium nitrate and 240 ml of aqueous solution of 3.3 lanthanum nitrate, and extruded intoMillimeter tooth balls are dried at 50 ℃ for 24 hours and then calcined at 1000 ℃ for 4 hours to obtain a modified alumina carrier T2, and the composition of the carrier is shown in Table 1. Nickel nitrate [ Ni (NO) ]3)2·6H2O]229 g potassium nitrate (K NO)3)0.5 g of the catalyst was dissolved in 310 ml of water to prepare an aqueous solution, the pH of the solution was adjusted to 10 with ammonia water, the above alumina carrier was impregnated twice by the equivalent impregnation method, dried at 120 ℃ for 4 hours, and calcined at 350 ℃ for 4 hours to obtain Ni-based catalyst C2 so that the final Ni content was 22% by weight of the carrier alumina. The composition, specific surface, pore volume and pore distribution of the catalyst are shown in table 1, wherein the content of each component is calculated by the weight of the alumina carrier.
Example 3
200 g of pseudo-boehmite, 75 g of alumina roasted at 1200 ℃ and 5 g of sesbania powder are weighed, mixed, 10 g of solution containing methylcellulose (mass concentration is 2%), 8.2 g of acetic acid, 19ml of silica sol with concentration of 0.59g/ml, 2.0 g of barium nitrate and 240 ml of aqueous solution of 3.3 lanthanum nitrate are added, and the mixture is extruded into the mixture
Figure BSA00000164380600063
Millimeter tooth balls are dried at 50 ℃ for 24 hours and then calcined at 1000 ℃ for 4 hours to obtain a modified alumina carrier T3, the preparation method of the carrier is the same as that of example 1, and the composition of the carrier is shown in Table 1. Nickel nitrate [ Ni (NO) ]3)2·6H2O]125 g of the catalyst was dissolved in 300 ml of water to prepare an aqueous solution, and then the alumina carrier was impregnated with ammonia water to adjust the pH of the solution to 8 by an equivalent impregnation method, dried at 120 ℃ for 4 hours, and calcined at 400 ℃ for 4 hours to prepare a Ni-based catalyst C3 so that the final Ni content was 12% by weight of the carrier alumina. Catalyst composition and specific surface and pore volumeThe pore distribution is shown in table 1, wherein the content of each component is calculated by the weight of the alumina carrier.
Example 4
260 g of 5% silicon-containing macroporous pseudo-boehmite, 30 g of alumina and 5 g of sesbania powder which are produced by Taguang chemical engineering Co., Ltd and are roasted at 950 ℃, are weighed, mixed, added with 10 g of solution (mass concentration is 2%) containing methyl cellulose, 3 ml of nitric acid and 240 ml of 13.3 cerium nitrate aqueous solution, and extruded into the mixture
Figure BSA00000164380600071
Millimeter clover, dried at 50 ℃ for 24 hours, calcined at 500 ℃ for 4 hours, sprayed with 0.2M KOH 220 ml, dried at 50 ℃ for 24 hours, and calcined at 1000 ℃ for 4 hours to obtain the modified alumina carrier T4, the composition of which is shown in Table 1. Nickel nitrate [ Ni (NO) ]3)2·6H2O]315 g of the catalyst was dissolved in 310 ml of water to prepare an aqueous solution, the pH of the solution was adjusted to 10 with ammonia, the alumina carrier was impregnated twice by the equivalent impregnation method, dried at 120 ℃ for 4 hours, and calcined at 350 ℃ for 4 hours to prepare a Ni-based catalyst C4, the final Ni content being 30% by weight of the carrier alumina. The composition, specific surface, pore volume and pore distribution of the catalyst are shown in table 1, wherein the content of each component is calculated by the weight of the alumina carrier.
Comparative example
Weighing 200 g of pseudo-boehmite, 5 g of sesbania powder and 15 g of starch, mixing, extruding into a hollow ring shape with the diameter of 4mm multiplied by 2mm multiplied by 4mm, drying wet strips at 120 ℃ for 4 hours, and roasting at 950 ℃ for 4 hours to obtain a carrier Z. Nickel nitrate [ Ni (NO) ]3)2·6H2O]Magnesium nitrate (Mg (NO)3)2·2H2O) is dissolved in water to prepare an aqueous solution, the alumina carrier is impregnated by an equivalent impregnation method, dried at 120 ℃ for 4 hours, and roasted at 350 ℃ for 4 hours to prepare the Ni-based catalyst CZ, so that the final Ni content is 22 percent of the weight of the alumina carrier, and the final Mg content is 1.9 percent of the weight of the alumina carrier. The composition, specific surface, pore volume and pore distribution of the catalyst are shown in Table 1, wherein the contents of all components are calculated by the weight of the alumina carrier。
TABLE 1
Figure BSA00000164380600081
As can be seen from the data in Table 1, the possible pore diameters of the catalysts C1, C2 and C3 are significantly larger than those of the comparative examples, and the possible pore diameters are large and the pore size distribution is reasonable.
Test of
50 ml of each of the catalysts of examples 1 to 4 and comparative example of the present invention were charged in a stainless steel single-tube reactor, and after nitrogen substitution, 0.2MPa of hydrogen was introduced and reduced at 400 ℃ for 4 hours, and then the temperature was lowered to 70 ℃ with nitrogen, and the pressure of hydrogen was raised to 4.0MPa, and the temperature was adjusted to the reaction temperature, and the reaction conditions and results are shown in Table 2.
TABLE 2
Figure BSA00000164380600091
Remarking: selective ═ alcohol (alcohol)Go out-alcoholsInto) /(aldehydes)Into-aldehydesGo out)】*100
As can be seen from the data in Table 2, the catalysts C1, C2, C3 have higher conversion and selectivity than the catalysts of the comparative examples.

Claims (9)

1. An aldehyde hydrogenation catalyst comprises an alumina carrier, and is characterized in that:
according to the weight of the alumina in the carrier being 100 percent, the weight percentages of other components and the alumina in the carrier are as follows:
a) 8-35% of nickel or its oxide;
b) 0.01 to 2.0% of at least one element of group IA or IIA or an oxide thereof;
c) 0.01 to 20.0% of at least one element of IIIA or IVA group or an oxide thereof;
d) 0.01-5% of rare earth elements;
the specific surface area of the alumina carrier is 40-180 m2Per gram, total pore volume of 0.4-1.2 ml/g, pore diameter<The pore volume of 30 nm accounts for 5-50% of the total pore volume, the pore volume of 30-80 nm accounts for 20-50% of the total pore volume, and the pore diameter>The pore volume of 80 nanometers accounts for 20-75% of the total pore volume.
2. The aldehyde hydrogenation catalyst according to claim 1, wherein:
a) 12-30% of nickel or its oxide;
b) 0.2 to 0.8% of at least one element of group IA or IIA or an oxide thereof;
c) 0.2 to 10.0% of at least one element of IIIA or IVA group or an oxide thereof;
d) the rare earth element is 0.1-3.0%.
3. The aldehyde hydrogenation catalyst according to claim 2, wherein:
the IA group in b) is potassium, and the IIA group is at least one of calcium, magnesium or barium;
in the c), IIIA group is boron, IVA group is silicon;
the rare earth element in d) is lanthanum and/or cerium.
4. The aldehyde hydrogenation catalyst according to claim 3, wherein:
the specific surface area of the alumina carrier is 40-165 m2Per gram; the total pore volume is 0.5-1.1 ml/g; diameter of hole<The pore volume of 30 nanometers accounts for 20-40% of the total pore volume; the pore volume of the pores with the diameter of 30-80 nanometers accounts for 20-45% of the total pore volume; diameter of hole>The pore volume of 80 nanometers accounts for 25-60% of the total pore volume.
5. A method for preparing the aldehyde hydrogenation catalyst according to claim 4, characterized in that the method comprises:
preparation of alumina carrier:
a) mixing alumina powder, a modification auxiliary agent, a peptizing agent, an extrusion aid and water, and then extruding into strips for forming; wherein,
the alumina powder is a mixture of pseudo-boehmite and alumina roasted at 900-1200 ℃, and the weight ratio of the pseudo-boehmite to the alumina roasted at 900-1200 ℃ is (1-200): 1;
the modifying assistant is selected from lanthanum or cerium in rare earth elements, salts of calcium, magnesium or barium in IIA group in the periodic table of elements, and acid containing boron in IIIA group in the periodic table of elements;
b) drying the extruded strips obtained in the step a) for 1-24 hours at 50-120 ℃;
c) roasting at 800-1150 ℃ for 1-10 hours to obtain an alumina carrier;
preparation of (di) aldehyde hydrogenation catalyst:
and (2) impregnating the alumina carrier obtained in the step (I) with a nickel-containing salt solution, and washing, drying and roasting the impregnated carrier to obtain the aldehyde hydrogenation catalyst.
6. The method of claim 5, wherein:
in the preparation of the alumina carrier (I), the weight ratio of the pseudo-boehmite to the alumina calcined at 900-1200 ℃ is (9-100): 1.
7. The method of claim 5, wherein:
in the preparation of the (one) alumina carrier,
the peptizing agent is one or more of nitric acid, acetic acid, citric acid and phosphoric acid;
the extrusion aid is one or more of cellulose, attapulgite, sesbania powder and PVP.
8. The method of claim 7, comprising the steps of:
the roasting temperature in the second step (II) is 300-600 ℃.
9. Use of the aldehyde hydrogenation catalyst according to any one of claims 1 to 4 for the hydrogenation of aldehydes.
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CN105080549B (en) * 2014-05-08 2017-11-17 中国石油化工股份有限公司 A kind of ethyl hexanol catalyst of octenal gas phase hydrogenation system 2 and preparation method thereof
CN107365887A (en) * 2017-06-07 2017-11-21 常州豫春化工有限公司 A kind of preparation method of fluxing type slagging agent
CN110038543B (en) * 2018-01-17 2022-07-12 中国石油化工股份有限公司 Alpha-alumina carrier of silver catalyst for ethylene epoxidation, silver catalyst and method for producing ethylene oxide by ethylene epoxidation
CN110981693B (en) * 2019-12-25 2022-11-11 淄博诺奥化工有限公司 Green method for preparing alcohols with high-value of octane by catalytic distillation
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