CN113694941B - Supported metal catalyst and preparation method and application thereof - Google Patents

Supported metal catalyst and preparation method and application thereof Download PDF

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CN113694941B
CN113694941B CN202010428855.XA CN202010428855A CN113694941B CN 113694941 B CN113694941 B CN 113694941B CN 202010428855 A CN202010428855 A CN 202010428855A CN 113694941 B CN113694941 B CN 113694941B
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chlorine
fluorine
metal catalyst
supported metal
catalyst
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CN113694941A (en
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乐毅
毛祖旺
铁锴
杨晨熹
彭晖
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/06—Halogens; Compounds thereof
    • B01J27/128—Halogens; Compounds thereof with iron group metals or platinum group metals
    • B01J27/13—Platinum group metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/06—Halogens; Compounds thereof
    • B01J27/135—Halogens; Compounds thereof with titanium, zirconium, hafnium, germanium, tin or lead
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/63—Pore volume
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
    • C07C5/03—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of non-aromatic carbon-to-carbon double bonds
    • C07C5/05—Partial hydrogenation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
    • C07C5/08—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of carbon-to-carbon triple bonds
    • C07C5/09—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of carbon-to-carbon triple bonds to carbon-to-carbon double bonds

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  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
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  • Chemical Kinetics & Catalysis (AREA)
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Abstract

The invention discloses a supported metal catalyst and a preparation method and application thereof, wherein the supported metal catalyst comprises an alumina carrier, a catalytic component Pd and a co-catalytic component, and the catalytic component Pd and the co-catalytic component are supported on the surface of the alumina carrier; the alumina carrier is added with halogen element, the weight ratio of the halogen element to the alumina carrier is (0.01-3): 100, and the auxiliary catalytic component is at least one selected from Sn, pb, co, ni, IVB groups and VB groups; at least one of La, ce, pr, li, K, ba elements is optionally contained in the alumina support. Wherein halogen-containing organic matters are added in the preparation of the alumina carrier. The supported metal catalyst obtained by the method can be used for the carbon four liquid phase selective hydrogenation reaction, and the selectivity of the catalyst can be obviously improved.

Description

Supported metal catalyst and preparation method and application thereof
Technical Field
The invention belongs to the field of metal catalysts, and particularly relates to a supported metal catalyst and a preparation method thereof, which can be used for removing alkyne through mixed carbon four selective hydrogenation and increasing butadiene yield through selective hydrogenation of butadiene high alkyne tail gas.
Background
The petroleum hydrocarbon cracking ethylene preparing device produces great amount of mixed C4 containing 40-60wt% of 1, 3-butadiene, 0.5-2.0wt% of Vinyl Acetylene (VA) and about 0.2wt% of Ethyl Acetylene (EA), and the rest components are butane, butene and small amount of 1, 2-butadiene, C three and C five. Typically, this portion of 1, 3-butadiene is separated from the mixed carbon four by extractive distillation or the like.
The cracking mixed carbon four is industrially refined by a two-stage solvent extraction rectification process to obtain a butadiene product, and the butadiene yield is usually 97-98.5%. The separated alkyne contains 20-40wt% of VA and EA and 3-40wt% of 1, 3-butadiene, and the materials are called high alkyne tail gas or butadiene tail gas, and in industrial production, the materials are usually diluted by four carbon fractions and then treated by a torch for causing resource waste and environmental pollution due to the consideration of safety factors.
Alkynes in the four-carbon fraction can be removed by adopting a selective hydrogenation method, and can be generally divided into front hydrogenation and rear hydrogenation according to different processes: a selective hydrogenation reactor is arranged before the mixed carbon four raw materials enter a butadiene extraction rectifying device (butadiene extraction device) to be called front hydrogenation, and the selective hydrogenation of butadiene tail gas is called rear hydrogenation; there is also a process of mixing butadiene tail gas with mixed carbon four and then hydrogenating the mixture. The alkyne in the carbon four fraction is removed by the front hydrogenation, so that the carbon four alkyne can be fully utilized, and the separation flow of the carbon four can be simplified. After the hydrogenation, VA in the butadiene tail gas can be hydrogenated to generate 1, 3-butadiene, and the butadiene yield of the device can be improved. The purpose of mixing the butadiene tail gas with the mixed carbon four and then carrying out hydrogenation is to hydrogenate the carbon four alkyne to generate butadiene and butene, thereby reducing or eliminating the tail gas emission and improving the economy of the device. In any of the three processes, a high-selectivity carbon four hydrogenation catalyst is required, alkyne is effectively removed, loss of 1, 3-butadiene is reduced as much as possible for front hydrogenation, and butadiene is generated as much as possible for rear hydrogenation; in addition, high stability is also important for long-term, low-cost operation.
The catalyst using Pd as the catalytic component Pd has high activity on selective hydrogenation alkyne removal reaction, and the selectivity of the catalyst can be greatly different due to different carriers, auxiliary catalytic components and preparation methods.
The US4547600 found that after 720 hours of use of the single Pd catalyst, pd was lost in large amounts, and the amount of alkyne remaining in the latter stages of the reaction was greatly increased, indicating deterioration of the selectivity of the catalyst. The patent found that the addition of Ag to the single Pd catalyst described above effectively prevented Pd loss, but the selectivity of the catalyst after modification was unchanged, leaving the same amount of alkyne as the single Pd catalyst.
The catalyst of the Pd/Al 2O3 is added with auxiliary catalytic components such as Ag, zn, bi and the like in the U.S. patent No. 7288686. The residual alkyne amount of the modified catalyst is greatly reduced and can be as low as 1ppm at the minimum, and the loss of 1, 3-butadiene is reduced compared with that before the modification, so that the improvement effect of the auxiliary agents on Pd catalyst selectivity is shown. It should be noted that, although there is some improvement in selectivity, 1, 3-butadiene is still lost about 7.5% (based on total butadiene), which is still a significant distance from the practically acceptable amount of butadiene lost.
Chinese patent CN1321544A uses Cu, ag, bi, zr as auxiliary agent to modify Pd catalyst, and the result shows that when the total alkyne content is less than 15ppm, the loss of 1, 3-butadiene can be less than 3% (based on total butadiene), and the better alkyne removal selectivity is shown.
However, the selectivity of the metal catalyst disclosed in the prior art in catalytic hydrogenation, especially in selective hydrogenation of acetylenes in the four carbon fractions, is still to be further improved, and thus, there is a need for a metal catalyst having high selectivity.
Disclosure of Invention
In order to overcome the problems in the prior art, a supported metal catalyst is provided, which can be used for selective hydrogenation of alkyne in a carbon four-fraction to generate butadiene and butene.
One of the objects of the present invention is to provide a supported metal catalyst comprising an alumina carrier, a catalytic component Pd and a co-catalytic component, the catalytic component Pd and the co-catalytic component being supported on the surface of the alumina carrier; wherein, halogen element is added in the alumina carrier, the weight ratio of the halogen element to the alumina carrier is (0.01-3) 100, and the auxiliary catalytic component is at least one selected from Sn, pb, co, ni, IVB groups and VB groups; at least one of La, ce, pr, li, K, ba elements is optionally contained in the alumina support.
In a preferred embodiment, the weight ratio of the catalytic component Pd to the alumina support is (0.005-2), preferably (0.05-1): 100, more preferably (0.05-0.5): 100.
In a preferred embodiment, the co-catalytic component is selected from at least one of Sn, pb, co, ni, ti, zr and V.
In a further preferred embodiment, the weight ratio of the co-catalytic component to the alumina support is (0.01 to 10): 100, preferably (0.01 to 6): 100.
In a preferred embodiment, the alumina support has a specific surface area of 5 to 150m 2/g, a bulk density of 0.3 to 0.9g/mL, and a pore volume of 0.25 to 1.00mL/g.
In a further preferred embodiment, the alumina carrier has a specific surface area of 10 to 100m 2/g, a bulk density of 0.55 to 0.85g/mL, a pore volume of 0.35 to 1.00mL/g, and a water absorption of greater than 40%.
The shape of the alumina carrier includes, but is not limited to, powder, granule, sphere, sheet, tooth sphere, bar, or clover.
In a preferred embodiment, the halogen element is fluorine and/or chlorine.
In a further preferred embodiment, the weight ratio of fluorine element to carrier is (0.01-1): 100, and the weight ratio of chlorine element to carrier is (0.01-2): 100.
In a still further preferred embodiment, the weight ratio of fluorine element to carrier is (0.05-0.8): 100, and the weight ratio of chlorine element to carrier is (0.05-1): 100.
In a preferred embodiment, the alumina support optionally contains elemental Si.
In a further preferred embodiment, the weight ratio of Si element to carrier is (0 to 1.5): 100, preferably (0 to 1): 100, more preferably (0 to 0.5): 100.
In a preferred embodiment, the weight ratio of at least one element La, ce, pr, li, K, ba to the support in the alumina support is (0 to 1.5): 100, preferably (0 to 1): 100.
Wherein, la, ce, pr, li, K, ba and other elements can further adjust the parameters of the carrier such as strength, specific surface area, pore volume and the like.
The second object of the present invention is to provide a method for preparing the supported metal catalyst according to one of the objects of the present invention, comprising the steps of:
step 1, mixing powdery raw materials;
Step 2, adding an acidic aqueous solution into the powdery raw materials, and then kneading and forming;
Step 3, adding halogen-containing organic matters, preferably fluorine-containing and/or chlorine-containing organic matters, to the powdery raw material in step 1 and/or to the acidic aqueous solution in step 2 and/or in the kneading molding;
step 4, drying and roasting to obtain an alumina carrier;
And 5, loading the catalytic component Pd and the auxiliary catalytic component on the alumina carrier obtained in the step 3, and drying and roasting to obtain the supported metal catalyst.
In a preferred embodiment, the amount of the fluorine-containing organic is 0.01 to 1wt%, preferably 0.05 to 0.8wt%, more preferably 0.01 to 0.7wt% based on the total amount of the powdery raw materials, wherein the amount of the fluorine-containing organic is based on the weight of fluorine element therein.
In a further preferred embodiment, the chlorine-containing organic is used in an amount of 0.01 to 2wt%, preferably 0.05 to 1wt%, based on the weight of chlorine element therein, of the total amount of the powdery raw material.
In a preferred embodiment, the fluorine-and/or chlorine-containing organic compound is selected from at least one of a fluorine-and/or chlorine-containing polymer, a fluorine-and/or chlorine-containing polymer suspension, and a fluorine-and/or chlorine-containing organic compound.
In a further preferred embodiment, when the fluorine-and/or chlorine-containing organic matter is a fluorine-and/or chlorine-containing polymer powder, it is added to the powdered raw material; when the fluorine-and/or chlorine-containing organic matter is a fluorine-and/or chlorine-containing polymer suspension, it is added to the acidic aqueous solution; when the fluorine-containing and/or chlorine-containing organic matter is a fluorine-containing and/or chlorine-containing organic compound, it is added to the acidic aqueous solution, or the fluorine-containing and/or chlorine-containing organic compound is added at the time of kneading molding.
In the invention, the pore structure of the alumina carrier can be effectively adjusted by adding the halogen-containing organic matters. (1) Under the high temperature condition, part of fluorine and chlorine can form gas phase compounds to diffuse and separate from the carrier, part of fluorine and chlorine are tightly combined with alumina and can be reserved on the carrier, and carbon and hydrogen in organic matters are gasified and decomposed during roasting to form a large number of micro-pores, so that the pore structure of the alumina carrier is increased; (2) Halogen enters an alumina skeleton, alumina microcrystal grains are more easily converted into a sheet shape during high-temperature roasting, so that the pore structure of the alumina is influenced, the increase of pore volume, the increase of specific surface area and the reduction of bulk density are generally promoted; (3) In addition, the electronegativity of halogen is strong, the acidity of the surface of the prepared alumina carrier can be influenced, the halogen (especially fluorine atoms and chlorine atoms) on the alumina carrier can pull electrons on aluminum atoms, and the electrons of hydroxyl groups around the aluminum atoms are attracted, so that hydrogen protons on the hydroxyl groups are easier to ionize, and a Bronsted acid site is formed.
And the organic matters can act with fluorine and/or chlorine elements simultaneously in the high-temperature roasting process of the alumina, so that the alumina carrier with good comprehensive performance is prepared, the addition times of auxiliary agents are reduced, and the forming method is simplified.
In a preferred embodiment, the fluorine-and/or chlorine-containing polymer is selected from, but not limited to, one or more of polytetrafluoroethylene, tetrafluoroethylene/hexafluoropropylene copolymer, tetrafluoroethylene/ethylene copolymer, polyvinylidene fluoride, polyvinyl fluoride, polytrifluoroethylene, chlorotrifluoroethylene/ethylene copolymer, polyvinyl chloride, polyvinylidene chloride, chlorinated polypropylene, chlorinated polyethylene, vinyl chloride/vinylidene chloride copolymer.
In a further preferred embodiment, the fluorine-and/or chlorine-containing polymer is selected from one or more of polytetrafluoroethylene powder, tetrafluoroethylene/hexafluoropropylene copolymer, tetrafluoroethylene/ethylene copolymer, polyvinylidene fluoride, polyvinyl chloride, chlorinated polypropylene, chlorinated polyethylene.
In a still further preferred embodiment, the particle diameter of the fluorine-and/or chlorine-containing polymer is less than 100 μm, preferably less than 50 μm, which facilitates a uniform mixing with the alumina powder.
In a preferred embodiment, the fluorine-and/or chlorine-containing polymer suspension is selected from, but is not limited to, polytetrafluoroethylene suspensions.
In a further preferred embodiment, the fluorine-and/or chlorine-containing polymer suspension has a weight concentration of 20 to 90wt%, preferably 40 to 70wt%.
In a preferred embodiment, the fluorine-and/or chlorine-containing organic compound is a fluorine-and/or chlorine-containing elemental water-soluble organic compound.
In a further preferred embodiment, the fluorine-containing and/or chlorine-containing organic compound is selected from, but is not limited to, at least one of tetrafluoropropanol, trifluoroethanol, trifluoroacetaldehyde, chloroacetic acid, dichloroacetic acid, trichloroacetic acid, and trichloroethanol.
In a preferred embodiment, in step 1, the powdered raw material comprises an alumina powder, optionally a Si-containing compound, and optionally a shaped pore former, wherein the alumina powder is selected from pseudoboehmite powder and optionally other alumina powders.
In a further preferred embodiment, the mass content of Na and Fe in the pseudo-boehmite powder is less than 0.1%, the mass reduction after high-temperature roasting is not more than 40% by weight, and the particle size of the powder is less than 200 mu m.
In a still further preferred embodiment, the other alumina powder is selected from at least one of alumina trihydrate, fast deoxidizing alumina powder, and composite phase alumina powder.
In a preferred embodiment, the alumina trihydrate is selected from at least one of gibbsite, bayerite, and nordstrandite.
In a further preferred embodiment, the alumina trihydrate is present in an amount of from 0 to 30% by weight, preferably from 0 to 20% by weight, based on the total amount of the alumina powder.
In a preferred embodiment, the fast deoxidizing aluminum powder is obtained by fast dehydration of aluminum hydroxide, wherein the weight content of Na and Fe is less than 0.1wt%.
In a further preferred embodiment, the amount of the fast deoxidizing aluminum powder is 0 to 30wt%, preferably 0 to 20wt% of the total amount of the aluminum oxide powder.
In a preferred embodiment, the composite phase alumina is obtained by high temperature calcination of aluminum hydroxide selected from the group consisting of alumina trihydrate or alumina monohydrate (e.g., gibbsite, bayerite, boehmite, etc.).
In a further preferred embodiment, the amount of the composite phase alumina is 0 to 30wt%, preferably 0 to 20wt% based on the total amount of the alumina powder.
In a preferred embodiment, the Si-containing compound is a water-insoluble Si-containing compound, preferably at least one selected from, but not limited to, dry silica gel, nano silica, silicon carbide.
In a further preferred embodiment, the average particle size of the nano-silica and dry silica gel is less than 120nm.
In a still further preferred embodiment, the Si-containing compound is used in an amount of 0 to 1.5wt%, preferably 0 to 1wt%, more preferably 0 to 0.5wt% based on the weight of Si element therein, based on the total amount of the alumina powder.
In a preferred embodiment, the molding pore-forming agent is selected from at least one of sesbania powder, starch, cellulose, high molecular polymer and decomposable alkaline substance.
In a further preferred embodiment, the cellulose is selected from at least one of methylcellulose, hydroxypropyl methylcellulose, sodium hydroxymethyl cellulose; the high molecular polymer is at least one selected from polyethylene microspheres, polystyrene, polyethylene oxide, polyethylene glycol, polyvinyl alcohol, sodium polyacrylate, polyethylene glycol and polyacrylate acrylic acid; the decomposable alkaline substance is at least one selected from urea, methylamine, ethylenediamine, ammonium carbonate and ammonium bicarbonate.
In a still further preferred embodiment, the shaped pore former is present in an amount of 0 to 20wt%, preferably 0 to 10wt% based on the total amount of the alumina powder.
In the step 1, the powder mixing can be performed in a special mixer, or the powder can be added into a kneader and dry-mixed for a certain time without adding solution. The time required for mixing can be determined empirically by those skilled in the art. Powder mixing is an important step of carrier preparation, and uniform powder mixing can be ensured by optimizing a mixer structure, prolonging mixing time and other methods.
In a preferred embodiment, in step 2, the acidic aqueous solution is selected from at least one of aqueous hydrochloric acid, aqueous nitric acid, aqueous sulfuric acid, aqueous acetic acid, aqueous oxalic acid, aqueous citric acid, aqueous phosphoric acid and aqueous ammonium dihydrogen phosphate, preferably from at least one of aqueous nitric acid, aqueous acetic acid, aqueous oxalic acid and aqueous citric acid.
In a further preferred embodiment, the concentration of the acidic aqueous solution is 0.1 to 10 wt.%, preferably 0.1 to 5 wt.%.
In a still further preferred embodiment, in step 2, the weight ratio of the acidic aqueous solution to the powdery raw material is (0.5 to 5): 1, preferably (0.6 to 2): 1.
The amount of acid in the acidic aqueous solution can be adjusted by those skilled in the art based on the plasticity of the kneaded dough and the specific surface area, strength, bulk density and the like of the carrier after high-temperature firing.
In a preferred embodiment, in step 2, a soluble auxiliary agent selected from inorganic substances of at least one of La, ce, pr, li, K and Ba is added to the acidic aqueous solution.
In a further preferred embodiment, the soluble auxiliary is selected from at least one nitric acid compound and/or oxide of La, ce, pr, li, K and Ba.
In a still further preferred embodiment, the soluble auxiliary is present in an amount of 0 to 1.5wt%, preferably 0 to 1wt%, based on the total amount of the alumina powder, wherein the soluble auxiliary is present in an amount of La, ce, pr, li, K or Ba.
In the step 2, the kneading and forming is to add acidic aqueous solution into the uniformly mixed powder, continuously mix and knead, react part of alumina powder with acid to form a plastic blank, and extrude and form the blank into the required shape and size. The kneading molding time, extrusion molding pressure, and the like are related to the size of the apparatus used, the composition of the alumina powder, the composition of the acid solution, and the like, and can be determined empirically by one skilled in the art.
In a preferred embodiment, in step 4, the drying is carried out at a temperature of 60 to 150 ℃ and for a time of 3 to 48 hours.
In a further preferred embodiment, in step 4, the drying is carried out at a temperature of 80 to 150 ℃ for a time of 5 to 25 hours.
In a preferred embodiment, in step 4, the firing is carried out at a temperature of 800 to 1200 ℃ for a time of 3 to 48 hours.
In a further preferred embodiment, in step 4, the firing temperature is 1000 to 1200 ℃ and the firing time is 4 to 10 hours.
In a further preferred embodiment, the temperature rise rate is 30 to 150 ℃/hr (preferably 50 to 120 ℃/hr) when the firing is performed at 600 ℃ or lower, and the temperature rise rate is 100 to 280 ℃/hr (preferably 150 to 250 ℃/hr) when the firing is performed at 600 ℃ or higher.
The drying and roasting step is to dry, knead and mold the moisture in the green embryo, and the high temperature roasting process generates solid phase reaction, and the alumina particles are adhered together to form the alumina carrier with certain strength.
In a preferred embodiment, in step 5, the catalytic component Pd comprises from 0.005 to 2wt%, preferably from 0.05 to 1wt%, more preferably from 0.05 to 0.5wt% of the total weight of the alumina support.
In a preferred embodiment, in step 5, the co-catalytic component is selected from at least one of group Sn, pb, co, ni, IVB and VB, preferably from at least one of Sn, pb, co, ni, ti, zr and V.
In a further preferred embodiment, the co-catalytic component comprises from 0.01 to 10wt% of the total weight of the alumina support.
In step 5, the manner of loading is not particularly required as long as loading is successful, and the alumina carrier may be loaded by impregnation methods commonly used in catalyst preparation, such as spraying, isovolumetric impregnation, supersaturation impregnation, etc. When the supersaturation impregnation method is used, if the active component precursor in the impregnation liquid cannot be completely adsorbed by the carrier, the volume of the impregnation liquid and the concentration of the active component are determined according to the adsorption proportion so as to ensure that the content of the active component loaded on the carrier meets the preset requirement.
When two or more catalytic components are contained in the catalyst, a one-step impregnation method or a step-wise impregnation method may be employed. The support may be impregnated using a one-step impregnation process in which several active component precursors are dissolved in the same solution. For active ingredient precursors that cannot be formulated into the same solution, a step-wise impregnation method may be used, where several active ingredient precursors are separately formulated into solutions to impregnate the support, and the support may need to be dried after each impregnation.
In a preferred embodiment, in step 5, the drying is carried out at 50 to 200 ℃ for 5 to 48 hours.
In a further preferred embodiment, in step 5, the drying is carried out at 50 to 120 ℃ for 5 to 24 hours.
In a preferred embodiment, in step 5, the calcination is carried out at 300 to 600 ℃ for 2 to 10 hours.
In a further preferred embodiment, in step 5, the calcination is carried out at 400 to 500 ℃ for 4 to 8 hours.
The support after supporting the catalytic component is calcined at a high temperature to decompose the metal active component precursor into an oxide.
The third object of the present invention is to provide a supported metal catalyst obtained by the second object of the present invention.
It is a fourth object of the present invention to provide a supported catalyst for use in a carbon four liquid phase selective hydrogenation alkyne removal reaction in accordance with one or more of the objects of the present invention.
Compared with the prior art, the invention has the following beneficial effects:
(1) The aluminum oxide carrier adopted by the invention is added with halogen-containing organic matters during preparation, so that various performances of the aluminum oxide carrier, including high specific surface area, high pore volume, low bulk density and the like, are effectively improved;
(2) The supported metal catalyst is used for hydrogenation reaction, especially for carbon four liquid phase selective hydrogenation alkyne removal reaction, and can obviously improve the selectivity of the catalyst.
Detailed Description
The present invention is described in detail below with reference to specific embodiments, and it should be noted that the following embodiments are only for further description of the present invention and should not be construed as limiting the scope of the present invention, and some insubstantial modifications and adjustments of the present invention by those skilled in the art from the present disclosure are still within the scope of the present invention.
The raw materials used in examples and comparative examples, if not particularly limited, are all as disclosed in the prior art, and are, for example, available directly or prepared according to the preparation methods disclosed in the prior art.
[ Example 1]
1.00G of concentrated nitric acid, 3.00g of oxalic acid was weighed and added to 210g of deionized water to prepare a mixed solution. 200 pseudo-boehmite powder, 6g sesbania powder, 5g starch and 3g crosslinked polyethylene microspheres with the particle size of about 40 mu m are weighed, uniformly mixed in a mixer and transferred into a kneader. Slowly adding the mixed solution, kneading for 20 minutes, then dripping 1.25g of trifluoroethanol, continuously kneading for 10 minutes, and extruding, molding and granulating to obtain the granules with the particle size of 4-6 mm. Oven drying at 120deg.C for 12hr, and calcining at 1080 deg.C for 6hr to obtain alumina carrier with F loading of about 0.5%.
12ML of PdCl 2 solution with a concentration of 25mgPd/mL was measured, diluted to 50mL with deionized water, the pH was adjusted to 3.0 with Na 2CO3, and the solution was diluted to 65mL. 100g of the Al 2O3 carrier was weighed and sprayed with the prepared PdCl 2 solution. The sample was dried at 120℃for 6 hours and then decomposed in a tube furnace with air at 450℃for 6 hours to give an intermediate sample having a Pd content of 0.3wt%.
Pb (NO 3)2 0.16.16 g, dissolved in 65mL deionized water, sprayed onto the above 100g intermediate sample, dried at 120deg.C for 6h, and decomposed in a tube furnace at 450deg.C for 6h with air to obtain catalyst A1 with Pd content of 0.3wt% and Pb content of 0.1wt%.
[ Example 2]
2.00G of concentrated nitric acid, 0.195g of potassium nitrate was weighed and added to 190g of deionized water to prepare a mixed solution. 200g of pseudo-boehmite powder, 8g of sesbania powder, 10g of starch and 0.48g of polyvinylidene fluoride powder are weighed, uniformly mixed in a mixer and transferred into a kneader. Slowly adding the mixed solution, fully kneading, extruding, forming and granulating to obtain particles with the particle size of 4-6 mm. Oven drying at 120deg.C for more than 12hr, and calcining at 1150 deg.C for 4hr to obtain alumina carrier with F load of about 0.2% and K load of about 0.05%.
Pd (NO 3)2 solution 12 mL) with the concentration of 25mgPd/mL is measured, co (NO 3)2 solution 5mL with the concentration of 20mgAg/mL is added, deionized water is used for diluting to 65mL. 100g of the Al 2O3 carrier is weighed, the prepared solution is sprayed on the Al 2O3 carrier, a sample is dried at 120 ℃ for 6 hours, air is introduced into a tubular furnace for decomposition at 450 ℃ for 6 hours, and the catalyst A2 with the Pd content of 0.3wt% and the Co content of 0.1wt% is obtained.
[ Example 3]
1.00G of concentrated nitric acid, 2.00g of citric acid and 0.15g of a 60% polytetrafluoroethylene concentrated dispersion were weighed and added to 190g of deionized water to prepare a mixed solution. 200g of pseudo-boehmite powder, 6g of sesbania powder and 6g of starch are weighed, uniformly mixed in a mixer and transferred into a kneader. Slowly adding the mixed solution, fully kneading, extruding, forming and granulating to obtain particles with the particle size of 4-6 mm. Oven drying at 120deg.C for more than 12hr, and roasting at 1120 deg.C for 6hr to obtain alumina carrier with fluorine loading of about 0.05%.
12ML of PdCl 2 solution with the concentration of 25mgPd/mL is measured, the solution is diluted to 50mL by deionized water, the pH value of the solution is adjusted to 5.0 by using 2mol/L ammonia water solution, and the solution is diluted to 65mL. 100g of the Al 2O3 carrier was weighed and the prepared solution was sprayed thereon. The sample was dried at 120℃for 6 hours and then decomposed in a tube furnace with air at 450℃for 6 hours to give an intermediate sample having a Pd content of 0.3wt%.
Pb (NO 3)2 0.48.48 g, dissolved in 65mL deionized water, sprayed onto the above 100g intermediate sample, dried at 120deg.C for 6h, and decomposed in a tube furnace at 450deg.C for 6h with air to obtain catalyst A3 with Pd content of 0.3wt% and Pb content of 0.3wt%.
[ Example 4]
Pd (NO 3)2 solution 12 mL) was measured at a concentration of 25mgPd/mL, diluted to 65mL with deionized water, pb (NO 3)2 0.48.48 g, 100g of the Al 2O3 carrier prepared as in example 3 was weighed, and the prepared solution was sprayed thereon, the sample was dried at 120℃for 6 hours, and then decomposed in a tube furnace at 450℃for 6 hours with air introduced, to obtain catalyst A4 having a Pd content of 0.3wt% and a Pb content of 0.3wt%.
[ Example 5]
2.00G of concentrated nitric acid, 2.00g of acetic acid, 0.30g of 60% polytetrafluoroethylene concentrated dispersion, 3.03g of lanthanum nitrate hexahydrate and 180g of deionized water were weighed out to prepare a mixed solution. 190g of pseudo-boehmite powder, 10g of alumina trihydrate powder, 8g of sesbania powder, 2g of hydroxymethyl cellulose and 3g of ammonium carbonate are weighed, uniformly mixed in a mixer and transferred into a kneader. Slowly adding the mixed solution, fully kneading, extruding, forming and granulating to obtain particles with the particle size of 4-6 mm. Oven drying at 140deg.C for more than 9hr, and roasting at 1135 deg.C for 6hr to obtain alumina carrier with fluorine load of about 0.1% and La load of about 0.7%.
12ML of PdCl 2 solution with the concentration of 25mgPd/mL is measured, the solution is diluted to 50mL by deionized water, the pH value of the solution is regulated to 3.0 by NaOH solution with the concentration of 1mol/L, and then the solution is diluted to 62mL. 100g of the Al 2O3 carrier was weighed and sprayed with the prepared PdCl 2 solution. The sample was dried at 120℃for 6 hours and then decomposed in a tube furnace with air at 450℃for 6 hours to give catalyst A5 having a Pd content of 0.3% by weight.
Pb (NO 3)2, 0.48g, dissolved in 65mL deionized water, sprayed onto the above 100g intermediate sample, dried at 120deg.C for 6h, and decomposed in a tube furnace at 450deg.C for 6h with air to obtain catalyst A5 with Pd content of 0.3wt% and Pb content of 0.3wt%.
[ Example 6]
3.00G of concentrated nitric acid and 0.73g of potassium nitrate are weighed and added into 200g of deionized water to prepare a mixed solution. 200g of pseudo-boehmite powder, 6g of sesbania powder, 6g of starch and 1.04g of K-value 72-71 polyvinyl chloride powder are weighed, uniformly mixed in a mixer and transferred into a kneader. Slowly adding the mixed solution, fully kneading, extruding, forming and granulating to obtain particles with the particle size of 4-6 mm. Oven drying at 120deg.C for more than 12hr, and roasting at 1135deg.C for 6hr, wherein the heating rate is controlled at 100deg.C/hr below 600deg.C, and the heating rate is controlled at 200deg.C/hr above 600deg.C, and naturally cooling to room temperature to obtain alumina carrier S6 with chlorine load of about 0.4% and K load of about 0.2%.
8ML of PdCl 2 solution with the concentration of 25mgPd/mL is measured, the solution is diluted to 50mL by deionized water, the pH value of the solution is regulated to 3.0 by using 2mol/L ammonia water solution, and then the solution is diluted to 58mL. 100g of the Al 2O3 carrier was weighed and sprayed with the prepared PdCl 2 solution. The sample was dried at 120℃for 6 hours and then decomposed in a tube furnace with air at 450℃for 6 hours to give catalyst A6 having a Pd content of 0.2% by weight.
Pb (NO 3)2, 0.16g, dissolved in 65mL deionized water, sprayed onto the above 100g intermediate sample, dried at 120deg.C for 6h, and decomposed in a tube furnace at 450deg.C for 6h with air to obtain catalyst A6 with Pd content of 0.2wt% and Pb content of 0.1wt%.
Comparative example 1
3.00G of concentrated nitric acid was weighed and added to 190g of deionized water to prepare a mixed solution. 200g of pseudo-boehmite powder, 8g of sesbania powder and 4g of starch are weighed, uniformly mixed in a mixer and transferred into a kneader. Slowly adding the mixed solution, fully kneading, extruding, forming and granulating to obtain particles with the particle size of 4-6 mm. Oven drying at 120deg.C for more than 12hr, baking at 1195 deg.C for 6hr, controlling heating rate to 300 deg.C/hr, and naturally cooling to room temperature to obtain alumina carrier.
12ML of PdCl 2 solution with the concentration of 25mgPd/mL is measured, diluted to 35mL by deionized water, the pH value of the solution is regulated to 3.0 by NaOH solution with the concentration of 1mol/L, and then the solution is diluted to 45mL. 100g of the Al 2O3 carrier was weighed and the prepared solution was sprayed thereon. The sample was dried at 120℃for 6 hours and then decomposed in a tube furnace with air at 450℃for 6 hours to give an intermediate sample having a Pd content of 0.3wt%.
Pb (NO 3)2, 0.16g, dissolved in 45mL deionized water, sprayed onto the above 100g intermediate sample, dried at 120deg.C for 6h, and decomposed in a tube furnace at 450deg.C for 6h with air to obtain catalyst B1 with Pd content of 0.3wt% and Pb content of 0.1wt%.
Comparative example 2
The procedure of example 1 was repeated, except that: the catalyst was obtained in the same manner as in the process of supporting the catalytic component under the same conditions except that 1.25g of trifluoroethanol was not used in the preparation of the alumina carrier.
[ Comparative example 3]
The procedure of example 1 was repeated except that: 2.24g of potassium fluoride was used instead of 1.25g of trifluoroethanol (both of which have the same fluorine content), and the catalyst was obtained in the same manner as in the process of supporting the catalytic component under the same conditions.
[ Comparative example 4]
The procedure of example 1 was repeated except that 1.25g of trifluoroethanol (having the same fluorine content) was replaced with (2.24 g of potassium fluoride and 1.7g of ethyl acetate), and the procedure of supporting the catalytic component was the same under the same conditions, to obtain a catalyst.
Comparative example 5
The procedure of example 1 was repeated except that 1.427g of ammonium fluoride was used instead of 1.25g of trifluoroethanol (both of which have the same fluorine content), and the procedure of supporting the catalytic component was the same under the same conditions, to obtain a supported metal catalyst.
[ Experimental example ]
The catalyst was evaluated by a mixed carbon four selective hydrogenation alkyne removal reaction under the following conditions:
A fixed bed reactor, a catalyst loading of 200mL, a reaction pressure of 1.2MPaG, and a reactor inlet temperature of 40 ℃. The composition (mole fraction) of the reaction raw materials was 1.85% of Vinylacetylene (VA), 0.20% of Ethylacetylene (EA), 51.23% (BD) of 1, 3-butadiene, and the remaining components were butane/butene and a small amount of 1, 2-butadiene. The space velocity of the experimental liquid was 16h -1. The reaction results after 8hr are shown in Table 1 below.
Experimental results show that the catalyst prepared by the method is used for the selective hydrogenation reaction of the carbon tetraalkyne, and the selectivity of the generated 1, 3-butadiene is far higher than that of the comparative example.
TABLE 1 catalytic reaction Performance
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Claims (32)

1. The supported metal catalyst is characterized by comprising an alumina carrier, a catalytic component Pd and a co-catalytic component, wherein the catalytic component Pd and the co-catalytic component are supported on the surface of the alumina carrier; the alumina carrier is an organic matter containing fluorine element and/or chlorine element; the weight ratio of fluorine element to alumina carrier is (0.01-1) 100, the weight ratio of chlorine element to alumina carrier is (0.01-2) 100, the auxiliary catalytic component is at least one selected from Sn, pb, co, ni, IVB family and VB family; optionally containing at least one element La, ce, pr, li, K, ba in the alumina carrier, wherein the mass ratio of the element La, ce, pr, li, K, ba to the alumina carrier is (0-1.5): 100;
the alumina carrier is prepared by the following method:
step 1, mixing powdery raw materials;
Step 2, adding an acidic aqueous solution into the powdery raw materials, and then kneading and forming;
step 3, adding fluorine-containing and/or chlorine-containing organic matters into the powdery raw material in the step1 and/or into the acidic aqueous solution in the step 2 and/or in the kneading and molding process;
step 4, drying and roasting to obtain the alumina carrier;
The drying is carried out for 3 to 48 hours at the temperature of 60 to 150 ℃;
The roasting is carried out for 3 to 48 hours at the temperature of 800 to 1200 ℃.
2. The supported metal catalyst of claim 1, wherein the catalyst comprises,
The weight ratio of the catalytic component Pd to the alumina carrier is (0.005-2) 100; and/or
The promoting component is selected from at least one of Sn, pb, co, ni, ti, zr and V.
3. The supported metal catalyst of claim 1, wherein the catalyst comprises,
The specific surface area of the alumina carrier is 5-150 m 2/g, the bulk density is 0.3-0.9 g/mL, and the pore volume is 0.25-1.00 mL/g; and/or
The alumina carrier optionally contains Si element, and the weight ratio of the Si element to the carrier is (0-1.5): 100.
4. The supported metal catalyst of claim 2, wherein the catalyst is,
The weight ratio of the auxiliary catalytic component to the alumina carrier is (0.01-10): 100.
5. The supported metal catalyst according to claim 1, wherein in step4,
The drying is carried out for 5 to 25 hours at the temperature of 80 to 150 ℃; and/or
The roasting is carried out for 4 to 10 hours at the temperature of 1000 to 2000 ℃.
6. The supported metal catalyst of claim 1, wherein the catalyst comprises,
The catalytic component Pd accounts for 0.005-2wt% of the total weight of the alumina carrier;
the auxiliary catalytic component accounts for 0.01-10wt% of the total weight of the alumina carrier.
7. The supported metal catalyst according to claim 1, wherein in step 3,
The dosage of the fluorine-containing organic matters is 0.01-1 wt% of the total dosage of the powdery raw materials, wherein the dosage of the fluorine-containing organic matters is calculated by the weight of fluorine elements; and/or
The dosage of the chlorine-containing organic matters is 0.01-2 wt% of the total dosage of the powdery raw materials, wherein the dosage of the chlorine-containing organic matters is calculated by the weight of chlorine elements.
8. The supported metal catalyst according to claim 7, wherein in step 3,
The dosage of the fluorine-containing organic matters is 0.05 to 0.8 weight percent of the total dosage of the powdery raw materials, wherein the dosage of the fluorine-containing organic matters is calculated by the weight of fluorine elements; and/or
The dosage of the chlorine-containing organic matters is 0.01-1 wt% of the total dosage of the powdery raw materials, wherein the dosage of the chlorine-containing organic matters is calculated by the weight of chlorine elements.
9. The supported metal catalyst according to claim 8, wherein in step 3,
The dosage of the chlorine-containing organic matters is 0.05-1 wt% of the total dosage of the powdery raw materials, wherein the dosage of the chlorine-containing organic matters is calculated by the weight of chlorine elements.
10. The supported metal catalyst according to claim 1, wherein in step 3,
The fluorine-containing and/or chlorine-containing organic compound is selected from at least one of fluorine-containing and/or chlorine-containing polymers, fluorine-containing and/or chlorine-containing polymer suspensions, and fluorine-containing and/or chlorine-containing organic compounds.
11. The supported metal catalyst of claim 10, wherein the catalyst is,
When the fluorine-and/or chlorine-containing organic matter is a fluorine-and/or chlorine-containing polymer, it is added to the powdered raw material;
when the fluorine-and/or chlorine-containing organic matter is a fluorine-and/or chlorine-containing polymer suspension, it is added to the acidic aqueous solution;
when the fluorine-and/or chlorine-containing organic compound is a fluorine-and/or chlorine-containing organic compound, it is added to the acidic aqueous solution.
12. The supported metal catalyst of claim 10, wherein the catalyst is,
The fluorine-containing and/or chlorine-containing polymer is selected from one or more of polytetrafluoroethylene, tetrafluoroethylene/hexafluoropropylene copolymer, tetrafluoroethylene/ethylene copolymer, polyvinylidene fluoride, polyvinyl fluoride, polytrifluoroethylene, chlorotrifluoroethylene/ethylene copolymer, polyvinyl chloride, polyvinylidene chloride, chlorinated polypropylene, chlorinated polyethylene and vinyl chloride/vinylidene chloride copolymer; and/or
The fluorine-containing and/or chlorine-containing polymer suspension is selected from polytetrafluoroethylene suspensions; and/or
The fluorine-containing and/or chlorine-containing organic compound is a water-soluble organic compound containing fluorine and/or chlorine elements.
13. The supported metal catalyst of claim 12, wherein the catalyst is,
The particle diameter of the fluorine-containing and/or chlorine-containing polymer is less than 100 μm.
14. The supported metal catalyst of claim 13, wherein the catalyst is,
The particle diameter of the fluorine-containing and/or chlorine-containing polymer is less than 50 μm.
15. The supported metal catalyst of claim 12, wherein the catalyst is,
The fluorine-containing and/or chlorine-containing organic compound is selected from at least one of tetrafluoropropanol, trifluoroethanol, trifluoroacetaldehyde, chloroacetic acid, dichloroacetic acid, trichloroacetic acid and trichloroethanol.
16. The supported metal catalyst according to claim 1, wherein in step 1,
The powdered raw material comprises alumina powder, optional Si-containing compound and optional forming pore-forming agent, wherein the alumina powder is selected from pseudo-boehmite powder and optional other alumina powder.
17. The supported metal catalyst of claim 16, wherein the catalyst is,
The other alumina powder is at least one selected from the group consisting of alumina trihydrate, fast deoxidizing alumina powder and composite phase alumina powder.
18. The supported metal catalyst of claim 17, wherein the catalyst is,
The usage amount of the alumina trihydrate accounts for 0-30wt% of the total usage amount of the alumina powder; and/or
The usage amount of the quick deoxidized aluminum powder is 0-30wt% of the total usage amount of the aluminum oxide powder; and/or
The amount of the composite phase alumina is 0 to 30wt% of the total amount of the alumina powder.
19. The supported metal catalyst of claim 16, wherein the catalyst is,
The usage amount of the forming pore-forming agent accounts for 0-20wt% of the total usage amount of the alumina powder.
20. The supported metal catalyst of claim 16, wherein the catalyst is,
The forming pore-forming agent is at least one selected from sesbania powder, starch, cellulose, high molecular polymer and decomposable alkaline substances.
21. The supported metal catalyst of claim 20, wherein the catalyst is,
The cellulose is at least one selected from methyl cellulose, hydroxypropyl methyl cellulose and sodium hydroxymethyl cellulose; and/or the number of the groups of groups,
The high molecular polymer is at least one selected from polyethylene microspheres, polystyrene, polyethylene oxide, polyethylene glycol, polyvinyl alcohol, sodium polyacrylate and polyacrylate acrylic acid; and/or the number of the groups of groups,
The decomposable alkaline substance is at least one selected from urea, methylamine, ethylenediamine, ammonium carbonate and ammonium bicarbonate.
22. The supported metal catalyst of claim 16, wherein the catalyst is,
The Si-containing compound is a water-insoluble Si-containing compound.
23. The supported metal catalyst of claim 22, wherein the catalyst is,
The Si-containing compound is at least one selected from dry silica gel, nano silicon oxide and silicon carbide.
24. The supported metal catalyst of claim 22, wherein the catalyst is,
The Si-containing compound is used in an amount of 0 to 1.5wt% based on the total amount of the alumina powder, wherein the Si-containing compound is used in an amount based on the weight of Si element therein.
25. The supported metal catalyst according to claim 1, wherein in step2,
The acidic aqueous solution is at least one selected from hydrochloric acid aqueous solution, nitric acid aqueous solution, sulfuric acid aqueous solution, acetic acid aqueous solution, oxalic acid aqueous solution, citric acid aqueous solution, phosphoric acid aqueous solution and monoammonium phosphate aqueous solution; and/or
The weight ratio of the acidic aqueous solution to the powdery raw material is (0.5-5): 1; and/or
And adding a soluble auxiliary agent to the acidic aqueous solution, wherein the soluble auxiliary agent is an inorganic substance selected from at least one of La, ce, pr, li, K and Ba.
26. The supported metal catalyst of claim 25, wherein the catalyst is,
The acidic aqueous solution is at least one selected from nitric acid aqueous solution, acetic acid aqueous solution, oxalic acid aqueous solution and citric acid aqueous solution; and/or
The weight ratio of the acidic aqueous solution to the powdery raw material is (0.6-2) 1; and/or
The soluble auxiliary agent is selected from at least one nitric acid compound and/or oxide in La, ce, pr, li, K and Ba.
27. The supported metal catalyst of claim 25, wherein the catalyst is,
The amount of the soluble auxiliary agent is 0-1.5wt% of the total amount of the alumina powder, wherein the amount of the soluble auxiliary agent is La, ce, pr, li, K or Ba.
28. A process for preparing a supported metal catalyst according to any one of claims 1 to 27, comprising the steps of:
And 5, loading the catalytic component Pd and the auxiliary catalytic component on an alumina carrier, and drying and roasting to obtain the supported metal catalyst.
29. The method of claim 28, wherein in step 5,
The drying is carried out for 5 to 48 hours at the temperature of 50 to 200 ℃; and/or
The roasting is carried out for 2 to 10 hours at the temperature of 300 to 600 ℃.
30. The method of claim 29, wherein in step 5,
The drying is carried out for 5 to 24 hours at the temperature of 50 to 120 ℃; and/or
The roasting is carried out for 4 to 8 hours at the temperature of 400 to 500 ℃.
31. A supported metal catalyst obtainable by the process of any one of claims 28 to 30.
32. A supported metal catalyst according to any one of claims 1 to 27 or 31 for use in a carbon four liquid phase selective hydrogenation alkyne removal reaction.
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