CN109092303B - Catalyst for selective hydrogenation of butadiene - Google Patents
Catalyst for selective hydrogenation of butadiene Download PDFInfo
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- CN109092303B CN109092303B CN201710473477.5A CN201710473477A CN109092303B CN 109092303 B CN109092303 B CN 109092303B CN 201710473477 A CN201710473477 A CN 201710473477A CN 109092303 B CN109092303 B CN 109092303B
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- 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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
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- C07C7/148—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound
- C07C7/163—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound by hydrogenation
Abstract
The invention relates to a catalyst for selective hydrogenation of butadiene, which mainly solves the technical problems of high loss of butene-1, higher cost of the catalyst and use of toxic and harmful raw materials in the preparation process in the prior art. The invention adopts butadiene selective hydrogenation catalyst, and comprises the following components in parts by weight: (a) 0.05-0.7 parts of metal palladium or an oxide thereof; (b) 0.1-2 parts of lanthanide metal or its oxide; (c) the technical scheme of 97.3-99.85 parts of carrier alumina well solves the technical problem, and can be used for selective hydrogenation of materials containing butadiene.
Description
Technical Field
The invention relates to a butadiene selective hydrogenation catalyst and a selective hydrogenation method of a material containing butadiene, in particular to a selective hydrogenation catalyst and a hydrogenation method for selectively hydrogenating a carbon four material containing a small amount of butadiene to remove butadiene and reduce the loss of butene-1.
Background
The n-butene is the main component of the byproduct C4 fraction of catalytic cracking, ethylene steam cracking and MTO device in oil refinery, has low price and is mainly consumed in the fields of fuel and chemical industry. The method is used for producing sec-butyl alcohol, methyl ethyl ketone, third monomer of polyethylene and the like. In recent years, new technologies such as olefin cracking and olefin disproportionation are continuously developed successfully for n-butene, the demand of n-butene is increasing day by day, and it is counted that 357 ten thousand t will be reached in 2020, so that the research of separating and utilizing n-butene in mixed C4 becomes one of important development directions of the development of chemical production technology.
Except for main components such as n-butene, isobutene and butane, the FCC, MTO and raffinate or ether carbon four contain diene and alkyne with different quantities (100-20000 PPM), and the existence of the easily polymerized polymers can cause the rapid inactivation of catalysts for n-butene reaction (olefin polymerization, olefin cracking and alkylation), so that the stable operation of the device is influenced, a selective hydrogenation unit is often required to be added to remove the easily polymerized components, and the ratio of butene-1 to butene-2 in the raw material is adjusted according to the product requirement. It is well known that the carbon tetrad hydroisomerization reaction occurs simultaneously with the hydrogenation reaction. Butadiene is hydrogenated to form butene-1, which occurs rapidly on the catalyst (relative rate equal to 1000). In the presence of hydrogen, butene-1 undergoes two reactions, one of which is the hydroisomerization to butene-2 (relative rate 100), which requires the addition of hydrogen to proceed without consuming it. Another reaction is hydrogenation to produce n-butane (relative rate 10). The last reaction is the hydrogenation of butene-2 directly to n-butane, which is the slowest reaction (relative rate 1) and is essentially negligible. Therefore, the development of the high-efficiency selective hydrogenation catalyst and the process play an important role in the utilization process of the carbon four-liter value. The SHP Process (Process hydrocarbons and olefins, Oil Gas J,1988,86(49):40-43) from the U.S. Oil products company (UOP) uses noble metal catalysts with butadiene conversions as high as 99.8% and butene-1 isomerization of 76.1% but normal butane production of 35.7%. U.S. Pat. No. 4,47629,56 (Novel Catalyst and Process for hydrogenation of unreacted Hydrocarbons) reports a palladium-based Catalyst for selective hydrogenation of butadiene, which contains 0.025-1.0% Pd and 0.05-4% Sn or Pb, based on the weight of the Catalyst, and effectively improves the selectivity of butadiene hydrogenation and inhibits the olefin isomerization reaction. The Degussa has provided a high content Pd catalyst for the carbon four selective hydrogenation process, which can effectively convert butadiene and reduce the loss of butene-1 in the hydrogenation process by adopting low temperature and proper hydrogen-hydrocarbon ratio. In recent years, the utilization technology of the domestic n-butene is endlessly diversified, the separated high-purity butene-1 is used as a polyethylene monomer, alkylate, a process for preparing olefin by OCC and OMT, and the like, and QSH-01 selective hydrogenation catalyst developed by Qilu institute is successfully applied to a raw material pretreatment process of the alkylate. But the development of the catalyst and the process with excellent selective hydrogenation performance of diene and low isomerization rate of butene-1 in China still has technical bottlenecks. Resources are available at the upstream, markets are available at the downstream, and for enterprises, the most critical technology for comprehensive utilization of carbon is left. The development of new technology reaches or surpasses the international advanced level, further optimizes the resource utilization and becomes the most effective means for improving the economic benefit and market competitiveness of enterprises.
The butadiene selective hydrogenation catalyst which is most researched in the prior art is a Pd-supported catalyst, so that the technical problem of high n-butene loss exists on one hand; on the other hand, the existing catalyst has higher palladium content and higher bulk density of the catalyst, so that the use cost of the catalyst is improved; or the palladium-based catalyst modified by tin or lead has the advantages of high toxicity of the used auxiliary agent in the preparation process, no safety and environmental protection.
Disclosure of Invention
One of the technical problems to be solved by the invention is the technical problems of high loss of the butene-1, higher cost of the catalyst and use of toxic and harmful raw materials in the preparation process in the prior art, and the invention provides the butadiene selective hydrogenation catalyst which has the characteristics of high butadiene conversion rate, low loss of the butene-1, low cost, relatively safe and environment-friendly use of the raw materials and the like.
The second technical problem to be solved by the present invention is a method for preparing the catalyst.
The third technical problem to be solved by the present invention is the application of the catalyst described in one of the above technical problems.
In order to solve one of the above technical problems, the technical solution of the present invention is as follows: the catalyst for butadiene selective hydrogenation comprises the following components in parts by weight: (a) 0.05-0.7 parts of metal palladium or an oxide thereof; (b) 0.1-2 parts of lanthanide series or its oxide; (c) 97.3-99.85 parts of carrier alumina.
In the technical scheme, the catalyst preferably contains 0.2-0.5 part of metal palladium or oxide thereof in parts by weight.
In the above technical scheme, when the Pd element is in the form of oxide, the skilled person knows that the Pd element should be reduced to metal Pd for use.
In the technical scheme, the catalyst preferably contains 0.3-1 part of lanthanide metal or oxide thereof by weight part;
in the above technical solution, the lanthanide metal is preferably selected from one or two of cerium and lanthanum. More preferably, both cerium and lanthanum are included, which have a synergistic effect in reducing butadiene residue and butene-1 loss.
To solve the second technical problem, the technical solution of the present invention is as follows:
the method for preparing the catalyst according to any of the preceding technical solutions, comprising the steps of:
(1) mixing the carrier with a solution containing a lanthanide metal compound, and roasting to obtain a catalyst precursor I;
(2) and impregnating the catalyst precursor I with a solution containing a palladium compound, and roasting to obtain the catalyst with Pd in a compound state in the catalyst.
The catalyst of the invention can be the catalyst obtained in the step (2) with Pd in a compound state, and the compound Pd is more mainly the oxide of Pd. It is noted that prior to the reaction for selective hydrogenation of butadiene in a butadiene-containing feedstock to butene-1, the combined catalyst needs to be reduced (or called activated) to a reduced catalyst with elemental Pd.
In the above technical solution, when preparing the catalyst, the method may further comprise, after the step (2):
(3) the catalyst with Pd in oxidation state is reduced into a reduction state catalyst with Pd as simple substance.
The Pd is the reduction state catalyst of the simple substance, and the Pd does not need to be activated when the Pd is used for the reaction of selectively hydrogenating the butadiene in the butadiene-containing material into the butene-1.
In the technical scheme, the roasting temperature in the steps (1) and/(2) is preferably 450-800 ℃.
In the technical scheme, the roasting time in the steps (1) and/(2) is preferably 3-8 hours.
In the above technical solution, the atmosphere for the firing in the steps (1) and/(2) is preferably an oxidizing atmosphere.
In the above-described embodiment, the oxidizing atmosphere is preferably an air atmosphere. The specific embodiment of the invention is air atmosphere roasting.
In the above technical solutions, in order to obtain a catalyst with better strength, it is preferable to dry the catalyst before calcination in steps (1) and/(2). The conditions for drying are not particularly limited and can be appropriately selected by those skilled in the art. For example, but not limited to, the drying temperature is 80-150 ℃; the drying time is 4-24 hours.
To solve the third problem, the technical scheme of the invention is as follows:
use of a catalyst according to any of the preceding claims for the selective hydrogenation of butadiene in a butadiene-containing feed to butene-1.
The technical key of the invention is the selection of the catalyst, and the reasonable process conditions for the application can be reasonably determined by a person skilled in the art. For example, the specific application method may be: a process for selectively hydrogenating a butadiene-containing material, which comprises contacting a butadiene-containing material as a raw material with hydrogen in the presence of a catalyst according to any one of the above technical problems to selectively hydrogenate butadiene to monoolefins.
In the technical scheme, the reaction pressure is preferably 1.5-3 MPa.
In the technical scheme, the reaction temperature is preferably 30-60 ℃.
In the technical scheme, the preferred volume airspeed of the raw material liquid is 6-20 h-1。
In the technical scheme, the hydrogen/butadiene molar ratio is preferably 1.2-2.
In the technical scheme, most of the material containing the butadiene contains olefin with four carbon atoms in the molecule, wherein the olefin contains butene-1, butene-2 and butadiene.
In the technical scheme, the butadiene-containing material is preferably one or a mixture of more of raffinate carbon four after extracting butadiene from an ethylene cracking device, ether carbon four or a by-product C4 of a device for preparing low-carbon olefin from FCC and methanol.
In the technical scheme, the content of the butadiene is preferably more than 0 and less than or equal to 0.4 percent in percentage by weight of the raw materials.
More specifically, by way of non-limiting example, the material comprises, by weight, 0.01-0.6% of butadiene, 3-25% of butane, 25-55% of butene-1, 2-25% of butene-2, 0-50% of isobutene, and 0-10% of isobutane.
In the technical scheme, the carbon four raw material is preferably selected from one or a mixture of more of ethylene plant ether rear carbon four, raffinate carbon four or selective hydrogenation carbon four, and refinery catalytic cracking carbon four fraction, wherein the carbon four hydrocarbon feed comprises isobutane, normal butane, fumaric-2, butene-1, isobutene, maleic-2 and a small amount of butadiene. Due to the fact that palladium has strong hydrogenation and isomerization activity, olefin is often hydrogenated to alkane, meanwhile, butene-1 is isomerized to butene-2, and the hydrogenation isomerization performance of the palladium catalyst can be effectively regulated and controlled through the effective synergistic effect of the second metal or the third metal and the metal. By adopting the technical scheme of the invention, the hydrogenation treatment is carried out under the conditions of reaction temperature of 40 ℃, pressure of 2.0MPa and hydrogen/dialkene molar ratio of 1.4, the mass content of the outlet butadiene is less than 6ppm, and the loss absolute value of the butene-1 is less than 4.2, thus obtaining better technical effect.
The invention is further illustrated by the following examples, which are not intended to limit the scope of the invention in any way.
The composition of the raw materials used in the experiment is shown in table 1.
Detailed Description
[ example 1 ]
1. Catalyst preparation
Weighing 150 g of pseudo-boehmite corresponding to 110 g of alumina, 150 g of alumina and 15 g of sesbania powder, mixing, adding 25.0 g of nitric acid aqueous solution with the mass concentration of 50% and 300 ml of water, and extruding into the mixture
And (3) drying the millimeter cylindrical wet strip at 110 ℃ for 4 hours, and then roasting the dried wet strip at 600 ℃ for 4 hours to obtain the alumina carrier. 99.20 g of the carrier is weighed and mixed with 75 g of cerous nitrate aqueous solution containing 0.30 g of cerium, and the mixture is dried for 8 hours at 110 ℃ and roasted for 4 hours at 450 ℃ to obtain the catalyst precursor I. The catalyst precursor I is mixed with 100 g of chloropalladite acid aqueous solution containing 0.5 g of palladium, dried for 8 hours at 110 ℃, and roasted for 4 hours at 450 ℃ to prepare the palladium-based catalyst. Before use, the mixture is reduced for 4 hours by hydrogen, the reduction temperature is 150 ℃, and the volume space velocity of the hydrogen is 50 hours-1To obtain the low-isomerization selective hydrogenation catalyst, and the specific composition is shown in Table 2.
2. Catalyst evaluation
The hydrogenation was carried out in a fixed bed reactor, which was packed with the catalyst prepared above, and the selective hydrogenation of the C4 fraction after the ether containing a butadiene mass fraction of 0.22% was carried out in a continuous manner.
The operating conditions were as follows:
reaction temperature: 40 deg.C
Reaction pressure: 2.2MPa
Volume space velocity of the raw material liquid: 12h-1
Hydrogen/butadiene molar ratio: 1.40
The specific evaluation results are shown in Table 3.
[ example 2 ]
1. Preparing catalyst 150 g of pseudo-boehmite corresponding to 110 g of alumina, 150 g of alumina and 15 g of sesbania powder are weighed and mixed, then 25.0 g of nitric acid aqueous solution with mass concentration of 50 percent and 300 ml of water are added to be extruded into the catalyst
And (3) drying the millimeter cylindrical wet strip at 110 ℃ for 4 hours, and then roasting the dried wet strip at 600 ℃ for 4 hours to obtain the alumina carrier. 99.2 g of the carrier and 75 g of lanthanum nitrate aqueous solution containing 0.3 g of lanthanum are weighed and mixed, dried for 8 hours at 110 ℃, and roasted for 4 hours at 450 ℃ to obtain the catalyst precursor I. The catalyst precursor I is mixed with 100 g of chloropalladite acid aqueous solution containing 0.5 g of palladium, dried for 8 hours at 110 ℃, and roasted for 4 hours at 450 ℃ to prepare the palladium-based catalyst. Before use, the mixture is reduced for 4 hours by hydrogen, the reduction temperature is 150 ℃, and the volume space velocity of the hydrogen is 50 hours-1To obtain the low-isomerization selective hydrogenation catalyst, and the specific composition is shown in Table 2.
2. Catalyst evaluation
The hydrogenation was carried out in a fixed bed reactor, which was packed with the catalyst prepared above, and the selective hydrogenation of the C4 fraction after the ether containing a butadiene mass fraction of 0.22% was carried out in a continuous manner.
The operating conditions were as follows:
reaction temperature: 40 deg.C
Reaction pressure: 2.2MPa
Volume space velocity of the raw material liquid: 12h-1
Hydrogen/butadiene molar ratio: 1.40
The specific evaluation results are shown in Table 3.
[ example 3 ]
1. Preparing catalyst 150 g of pseudo-boehmite corresponding to 110 g of alumina, 150 g of alumina and 15 g of sesbania powder are weighed and mixed, then 25.0 g of nitric acid aqueous solution with mass concentration of 50 percent and 300 ml of water are added to be extruded into the catalyst
And (3) drying the millimeter cylindrical wet strip at 110 ℃ for 4 hours, and then roasting the dried wet strip at 600 ℃ for 4 hours to obtain the alumina carrier. 99.20 g of the carrier, 37.5 g of cerium nitrate aqueous solution containing 0.15 g of cerium and 37.5 g of lanthanum nitrate aqueous solution containing 0.15 g of lanthanum are weighed and mixed, dried for 8 hours at 110 ℃ and roasted for 4 hours at 450 ℃ to obtain a catalyst precursor I. The catalyst precursor I is mixed with 100 g of chloropalladite acid aqueous solution containing 0.5 g of palladium, dried for 8 hours at 110 ℃, and roasted for 4 hours at 450 ℃ to prepare the palladium-based catalyst. Before use, the mixture is reduced for 4 hours by hydrogen, the reduction temperature is 150 ℃, and the volume space velocity of the hydrogen is 50 hours-1To obtain the low-isomerization selective hydrogenation catalyst, and the specific composition is shown in Table 2.
2. Catalyst evaluation
The hydrogenation was carried out in a fixed bed reactor, which was packed with the catalyst prepared above, and the selective hydrogenation of the C4 fraction after the ether containing a butadiene mass fraction of 0.22% was carried out in a continuous manner.
The operating conditions were as follows:
reaction temperature: 40 deg.C
Reaction pressure: 2.2MPa
Volume space velocity of the raw material liquid: 12h-1
Hydrogen/butadiene molar ratio: 1.40
The specific evaluation results are shown in Table 3.
[ example 4 ]
1. Catalyst preparation
Weighing 150 g of pseudo-boehmite corresponding to 110 g of alumina, 150 g of alumina and 15 g of sesbania powder, mixing, adding 25.0 g of nitric acid aqueous solution with the mass concentration of 50% and 300 ml of water, and extruding into the mixture
And (3) drying the millimeter cylindrical wet strip at 110 ℃ for 4 hours, and then roasting the dried wet strip at 600 ℃ for 4 hours to obtain the alumina carrier. 99.20 g of the carrier is weighed and mixed with 75 g of cerous nitrate aqueous solution containing 0.5 g of cerium, and the mixture is dried for 8 hours at 110 ℃ and roasted for 4 hours at 450 ℃ to obtain the catalyst precursor I. The catalyst precursor I is mixed with 100 g of chloropalladite acid aqueous solution containing 0.3 g of palladium, dried for 8 hours at 110 ℃, and roasted for 4 hours at 450 ℃ to prepare the palladium-based catalyst. Before use, the mixture is reduced for 4 hours by hydrogen, the reduction temperature is 150 ℃, and the volume space velocity of the hydrogen is 50 hours-1To obtain the low-isomerization selective hydrogenation catalyst, and the specific composition is shown in Table 2.
2. Catalyst evaluation
The hydrogenation was carried out in a fixed bed reactor, which was packed with the catalyst prepared above, and the selective hydrogenation of the C4 fraction after the ether containing a butadiene mass fraction of 0.22% was carried out in a continuous manner.
The operating conditions were as follows:
reaction temperature: 40 deg.C
Reaction pressure: 2.2MPa
Volume space velocity of the raw material liquid: 12h-1
Hydrogen/butadiene molar ratio: 1.40
The specific evaluation results are shown in Table 3.
[ example 5 ]
1. Catalyst preparation
Weighing 150 g of pseudo-boehmite corresponding to 110 g of alumina, 150 g of alumina and 15 g of sesbania powder, mixing, adding 25.0 g of nitric acid aqueous solution with the mass concentration of 50% and 300 ml of water, and extruding into the mixture
Millimeter cylindrical, wet strips dried at 110 ℃ for 4 hours and then calcined at 600 ℃ for 4 hoursAnd obtaining the alumina carrier. Weighing 98.5 g of the carrier and 75 g of cerous nitrate aqueous solution containing 1.0 g of cerium, mixing, drying at 110 ℃ for 8 hours, and roasting at 450 ℃ for 4 hours to obtain the catalyst precursor I. The catalyst precursor I is mixed with 100 g of chloropalladite acid aqueous solution containing 0.5 g of palladium, dried for 8 hours at 110 ℃, and roasted for 4 hours at 450 ℃ to prepare the palladium-based catalyst. Before use, the mixture is reduced for 4 hours by hydrogen, the reduction temperature is 150 ℃, and the volume space velocity of the hydrogen is 50 hours-1To obtain the low-isomerization selective hydrogenation catalyst, and the specific composition is shown in Table 2.
2. Catalyst evaluation
The hydrogenation was carried out in a fixed bed reactor, which was packed with the catalyst prepared above, and the selective hydrogenation of the C4 fraction after the ether containing a butadiene mass fraction of 0.22% was carried out in a continuous manner.
The operating conditions were as follows:
reaction temperature: 40 deg.C
Reaction pressure: 2.2MPa
Volume space velocity of the raw material liquid: 12h-1
Hydrogen/butadiene molar ratio: 1.40
The specific evaluation results are shown in Table 3.
[ example 6 ]
1. Catalyst preparation
Weighing 150 g of pseudo-boehmite corresponding to 110 g of alumina, 150 g of alumina and 15 g of sesbania powder, mixing, adding 25.0 g of nitric acid aqueous solution with the mass concentration of 50% and 300 ml of water, and extruding into the mixture
And (3) drying the millimeter cylindrical wet strip at 110 ℃ for 4 hours, and then roasting the dried wet strip at 600 ℃ for 4 hours to obtain the alumina carrier. 97.5 g of the carrier and 75 g of a cerium nitrate aqueous solution containing 2.0 g of cerium were weighed and mixed, dried at 110 ℃ for 8 hours, and calcined at 450 ℃ for 4 hours. 100 g of chloropalladate acid aqueous solution with 0.5 g of palladium contained in the carrier is mixed, dried for 8 hours at 110 ℃, and roasted for 4 hours at 450 ℃ to prepare the palladium-based catalyst. Before use, the mixture is reduced for 4 hours by hydrogen, the reduction temperature is 150 ℃, and the volume space velocity of the hydrogen is 50 hours-1To obtain the low-isomerization selective hydrogenation catalyst, and the specific composition is shown in Table 2.
2. Catalyst evaluation
The hydrogenation was carried out in a fixed bed reactor, which was packed with the catalyst prepared above, and the selective hydrogenation of the C4 fraction after the ether containing a butadiene mass fraction of 0.22% was carried out in a continuous manner.
The operating conditions were as follows:
reaction temperature: 40 deg.C
Reaction pressure: 2.2MPa
Volume space velocity of the raw material liquid: 15h-1
Hydrogen/butadiene molar ratio: 1.40
The specific evaluation results are shown in Table 3.
[ example 7 ]
1. Catalyst preparation
Weighing 150 g of pseudo-boehmite corresponding to 110 g of alumina, 150 g of alumina and 15 g of sesbania powder, mixing, adding 25.0 g of nitric acid aqueous solution with the mass concentration of 50% and 300 ml of water, and extruding into the mixture
And (3) drying the millimeter cylindrical wet strip at 110 ℃ for 4 hours, and then roasting the dried wet strip at 600 ℃ for 4 hours to obtain the alumina carrier. 98.5 g of the carrier and 75 g of lanthanum nitrate aqueous solution containing 1.0 g of lanthanum are weighed and mixed, dried for 8 hours at 110 ℃ and roasted for 4 hours at 450 ℃. 100 g of chloropalladate acid aqueous solution with 0.5 g of palladium contained in the carrier is mixed, dried for 8 hours at 110 ℃, and roasted for 4 hours at 450 ℃ to prepare the palladium-based catalyst. Before use, the mixture is reduced for 4 hours by hydrogen, the reduction temperature is 150 ℃, and the volume space velocity of the hydrogen is 50 hours-1To obtain the low-isomerization selective hydrogenation catalyst, and the specific composition is shown in Table 2.
2. Catalyst evaluation
The hydrogenation was carried out in a fixed bed reactor, which was packed with the catalyst prepared above, and the selective hydrogenation of the C4 fraction after the ether containing a butadiene mass fraction of 0.22% was carried out in a continuous manner.
The operating conditions were as follows:
reaction temperature: 40 deg.C
Reaction pressure: 2.2MPa
Volume space velocity of the raw material liquid: 15h-1
Hydrogen/butadiene molar ratio: 1.40
The specific evaluation results are shown in Table 3.
[ COMPARATIVE EXAMPLE 1 ]
1. Catalyst preparation
Weighing 150 g of pseudo-boehmite corresponding to 110 g of alumina, 150 g of alumina and 15 g of sesbania powder, mixing, adding 25.0 g of nitric acid aqueous solution with the mass concentration of 50% and 300 ml of water, and extruding into the mixture
And (3) drying the millimeter cylindrical wet strip at 110 ℃ for 4 hours, and then roasting the dried wet strip at 600 ℃ for 4 hours to obtain the alumina carrier. 99.5 g of the carrier is weighed and mixed with 100 g of chloropalladite acid aqueous solution containing 0.5 g of palladium, and the mixture is dried for 8 hours at 110 ℃ and roasted for 4 hours at 450 ℃ to prepare the palladium-based catalyst. Before use, the mixture is reduced for 4 hours by hydrogen, the reduction temperature is 150 ℃, and the volume space velocity of the hydrogen is 50 hours-1To obtain the low-isomerization selective hydrogenation catalyst, and the specific composition is shown in Table 2.
2. Catalyst evaluation
The hydrogenation was carried out in a fixed bed reactor, which was packed with the catalyst prepared above, and the selective hydrogenation of the C4 fraction after the ether containing a butadiene mass fraction of 0.22% was carried out in a continuous manner.
The operating conditions were as follows:
reaction temperature: 40 deg.C
Reaction pressure: 2.2MPa
Volume space velocity of the raw material liquid: 10h-1
Hydrogen/butadiene molar ratio: 1.40
The specific evaluation results are shown in Table 3.
[ COMPARATIVE EXAMPLE 2 ]
1. Catalyst preparation
Weighing 150 g of pseudoboehmite corresponding to 110 g of alumina, 150 g of alumina and 15 g of fieldMixing the green powder, adding 25.0 g of nitric acid aqueous solution with the mass concentration of 50% and 300 ml of water, and extruding into the green powder
And (3) drying the millimeter cylindrical wet strip at 110 ℃ for 4 hours, and then roasting the dried wet strip at 600 ℃ for 4 hours to obtain the alumina carrier. 99.2 g of the carrier is weighed and mixed with 75 g of cerous nitrate aqueous solution containing 0.8 g of cerium, and the mixture is dried for 8 hours at 110 ℃ and roasted for 4 hours at 450 ℃ to prepare the cerium-based catalyst. Before use, the mixture is reduced for 4 hours by hydrogen, the reduction temperature is 150 ℃, and the volume space velocity of the hydrogen is 50 hours-1To obtain the low-isomerization selective hydrogenation catalyst, and the specific composition is shown in Table 2.
2. Catalyst evaluation
The hydrogenation was carried out in a fixed bed reactor, which was packed with the catalyst prepared above, and the selective hydrogenation of the C4 fraction after the ether containing a butadiene mass fraction of 0.22% was carried out in a continuous manner.
The operating conditions were as follows:
reaction temperature: 40 deg.C
Reaction pressure: 2.2MPa
Volume space velocity of the raw material liquid: 10h-1
Hydrogen/butadiene molar ratio: 1.40
The specific evaluation results are shown in Table 3.
[ COMPARATIVE EXAMPLE 3 ]
1. Catalyst preparation
Weighing 150 g of pseudo-boehmite corresponding to 110 g of alumina, 150 g of alumina and 15 g of sesbania powder, mixing, adding 25.0 g of nitric acid aqueous solution with the mass concentration of 50% and 300 ml of water, and extruding into the mixture
And (3) drying the millimeter cylindrical wet strip at 110 ℃ for 4 hours, and then roasting the dried wet strip at 600 ℃ for 4 hours to obtain the alumina carrier. 98.7 g of the carrier and 75 g of copper nitrate aqueous solution containing 0.8 g of copper are weighed and mixed, dried for 8 hours at 110 ℃ and roasted for 4 hours at 450 ℃ to obtain the catalyst precursor I. The catalyst precursor I was mixed with palladium chloride aqueous solution containing 0.5 g of palladium100 g of the solution is mixed, dried for 8 hours at 110 ℃ and roasted for 4 hours at 450 ℃ to prepare the palladium-based catalyst. Before use, the mixture is reduced for 4 hours by hydrogen, the reduction temperature is 150 ℃, and the volume space velocity of the hydrogen is 50 hours-1To obtain the low-isomerization selective hydrogenation catalyst, and the specific composition is shown in Table 2.
2. Catalyst evaluation
The hydrogenation was carried out in a fixed bed reactor, which was packed with the catalyst prepared above, and the selective hydrogenation of the C4 fraction after the ether containing a butadiene mass fraction of 0.22% was carried out in a continuous manner.
The operating conditions were as follows:
reaction temperature: 40 deg.C
Reaction pressure: 2.2MPa
Volume space velocity of the raw material liquid: 12h-1
Hydrogen/butadiene molar ratio: 1.40
The specific evaluation results are shown in Table 2.
TABLE 1
| Composition of raw materials | The weight percentage is w% |
| Butane | 14.84 |
| Isobutane | 0.68 |
| Butene-1 | 53.34 |
| Butene-2 | 30.50 |
| Isobutene | 0.52 |
| Butadiene | 0.12 |
TABLE 2
Note: the unit of the absolute value of the loss of butene-1 is butene-1 percent before reaction-butene-1 percent after reaction.
Claims (8)
1. The catalyst for butadiene selective hydrogenation comprises the following components in parts by weight:
(a) 0.2-0.50 parts of metal palladium or an oxide thereof;
(b) 0.3-1 part of lanthanide metal or oxide thereof; the lanthanide metal is cerium and lanthanum;
(c) 97.3-99.85 parts of carrier alumina.
2. A process for preparing the catalyst of claim 1, comprising the steps of:
(1) mixing the carrier with a solution containing a lanthanide metal compound, and roasting to obtain a catalyst precursor I;
(2) and impregnating the catalyst precursor I with a solution containing a palladium compound, and roasting to obtain the catalyst with Pd in a compound state in the catalyst.
3. The method of claim 2, further comprising, after step (2):
(3) the Pd is reduced to a reduction catalyst with the Pd as a simple substance.
4. The method according to claim 2, wherein the firing temperature in the steps (1) and/(2) is 450 to 800 ℃.
5. The method according to claim 2, wherein the calcination time in steps (1) and/(2) is 3 to 8 hours.
6. The method according to claim 2, wherein the atmosphere for the calcination in the steps (1) and/(2) is an oxidizing atmosphere.
7. The method according to claim 6, wherein the oxidizing atmosphere is an air atmosphere.
8. Use of a catalyst according to claim 1 for the selective hydrogenation of butadiene in a butadiene-containing feed to butene-1.
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