CN111375393A - Alumina carrier and preparation method and application thereof - Google Patents

Alumina carrier and preparation method and application thereof Download PDF

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Publication number
CN111375393A
CN111375393A CN201811633769.1A CN201811633769A CN111375393A CN 111375393 A CN111375393 A CN 111375393A CN 201811633769 A CN201811633769 A CN 201811633769A CN 111375393 A CN111375393 A CN 111375393A
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containing compound
weight
lanthanum
drying
carrier
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Inventor
郑建坡
于维国
尹国海
张新军
崔华
倪明
丁京
钟健
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China Petroleum and Chemical Corp
Sinopec Catalyst Co
Sinopec Catalyst Beijing Co Ltd
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China Petroleum and Chemical Corp
Sinopec Catalyst Co
Sinopec Catalyst Beijing Co Ltd
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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
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
    • B01J21/04—Alumina
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
    • 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
    • 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
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/44—Palladium
    • 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
    • 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
    • B01J23/56—Platinum group metals
    • B01J23/63—Platinum group metals with rare earths or actinides
    • 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
    • B01J35/613—10-100 m2/g
    • 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
    • B01J35/633—Pore volume less than 0.5 ml/g
    • 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
    • B01J35/635—0.5-1.0 ml/g
    • 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
    • B01J35/64—Pore diameter
    • B01J35/647—2-50 nm
    • 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
    • B01J35/64—Pore diameter
    • B01J35/651—50-500 nm
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Catalysts (AREA)

Abstract

The invention relates to the field of catalyst carrier preparation, and discloses an alumina carrier and a preparation method and application thereof. The method comprises the steps of forming, first drying and first roasting a mixture containing an aluminum-containing compound, a binder, an acid, polyethylene oxide, an acrylic resin and optional lanthanum or a lanthanum-containing compound in sequence. The preparation method of the alumina carrier has the advantages of simple process, stable carrier performance, high selective hydrogenation conversion rate and good selectivity of the obtained carbon dioxide three-fraction selective hydrogenation catalyst.

Description

Alumina carrier and preparation method and application thereof
Technical Field
The invention relates to the field of catalyst carrier preparation, in particular to an alumina carrier and a preparation method and application thereof.
Background
The cracked gas generated by cracking the liquid hydrocarbon steam contains 0.2-0.7 mol% of acetylene and 0.2-0.9 mol% of propyne and propadiene (MAPD). In order to obtain polymerization grade ethylene and propylene, acetylene and MAPD must be removed to required indexes. The catalytic hydrogenation method is the most commonly used method, and refers to that acetylene is hydrogenated to generate ethylene and propyne is hydrogenated to generate propylene under certain process operation conditions in the presence of a hydrogenation catalyst, so that the purpose of purification is achieved.
The selective hydrogenation of carbon two and three fractions adopts a multi-metal supported catalyst mainly comprising palladium, mainly comprisingThe carbon dioxide three-fraction selective hydrogenation catalyst carrier is generally a toothed sphere or spherical particle, and its component is mainly α -Al2O3The preparation process mainly comprises the steps of powder mixing, kneading, strip extruding, grain cutting, drying, roasting and the like. The performance of the carrier directly determines the performance of the catalyst, so that the carrier with excellent performance is obtained in a crucial way.
Although the preparation of a catalyst support having excellent physical properties is an important approach to improving the catalyst performance, it is difficult to further improve the support performance today with the development of catalyst preparation technology. In the field of preparation of carbon two three-fraction selective hydrogenation catalyst carriers, no research aiming at carrying out technical improvement on the carbon two three-fraction selective hydrogenation catalyst carriers is seen at present.
Disclosure of Invention
The invention aims to overcome the problems in the prior art and provide the alumina carrier, the preparation method and the application thereof.
In order to achieve the above objects, according to one aspect of the present invention, there is provided a method for preparing an alumina carrier, which comprises sequentially molding, first drying and first firing a mixture containing an aluminum-containing compound, a binder, an acid, polyethylene oxide, an acrylic resin, and optionally lanthanum or a lanthanum-containing compound.
Preferably, the aluminum-containing compound is aluminum hydroxide and/or pseudo-boehmite.
Preferably, the binder is one or more of sesbania powder, starch and hydroxypropyl methylcellulose.
Preferably, the acid is one or more of nitric acid, citric acid and acetic acid.
Preferably, the acid is used in an amount of 1 to 8% by weight relative to the weight of the aluminum-containing compound calculated as alumina.
Preferably, in the mixture, the weight ratio of the aluminum-containing compound, the binder and the acid is 1: 0.03-0.1: 0.015-0.08.
Preferably, the binder is used in an amount of 5 to 15% by weight relative to the weight of the aluminum-containing compound calculated as alumina.
Preferably, the lanthanum or lanthanum-containing compound is used in an amount of 0.35 to 1% by weight in terms of lanthanum element, relative to the weight of the aluminum-containing compound in terms of alumina.
Preferably, the molecular weight of the polyethylene oxide is 200 to 500 ten thousand, and the molecular weight of the acrylic resin is 100 to 1000 ten thousand.
Preferably, the polyethylene oxide and the acrylic resin are used in an amount of 1 to 10% by weight, preferably 3 to 7% by weight, relative to the weight of the aluminum-containing compound, calculated as alumina.
Preferably, the weight ratio of the polyethylene oxide to the acrylic resin component is 1: 9-9: 1, preferably 2: 8-5: 5.
Preferably, the method comprises mixing an aluminium-containing compound, a binder and an acrylic resin, followed by the addition of an acid and optionally lanthanum or a lanthanum-containing compound.
Preferably, the temperature of the mixing is 5-45 ℃ and the time of the mixing is 15-60 minutes.
Preferably, the conditions of the first drying include: the drying temperature is 80-150 ℃, and the drying time is 2-6 hours.
Preferably, the conditions of the first firing include: the roasting temperature is 400-650 ℃, and the roasting time is 5-15 hours.
Preferably, the method further comprises impregnating the first calcined support with a potassium hydroxide solution, followed by second drying and second calcination.
Preferably, the concentration of the potassium hydroxide solution is 0.01-0.1 mol/L.
Preferably, the potassium hydroxide solution is used in an amount of 30 to 100% by weight of the support after the first calcination.
Preferably, the conditions of the second drying include: the drying temperature is 80-150 ℃, and the drying time is 2-15 hours.
Preferably, the conditions of the second firing include: the roasting temperature is 1050 ℃ and 1300 ℃, and the drying time is 8-25 hours.
In a second aspect, the present invention provides an alumina carrier prepared by the above-described method of the present invention.
The third aspect of the invention provides the application of the alumina carrier in the preparation of a carbon dioxide three-fraction selective hydrogenation catalyst.
The fourth aspect of the present invention provides a selective hydrogenation catalyst for carbon-two three-fraction, which comprises the carrier of the present invention as described above, and an active metal component supported on the carrier.
The inventor of the invention unexpectedly finds in the research process that by treating the alumina carrier with acrylic resin and polyethylene oxide as the modifier in the carrier preparation process, the prepared alumina carrier is very suitable for being used as a carrier of a carbon two three-fraction selective hydrogenation catalyst, and can simultaneously improve the conversion rate and the selectivity of the carbon two-fraction selective hydrogenation catalyst prepared by the alumina carrier. The preparation method has the advantages of simple process, stable carrier performance, no need of adding operation steps, high selective hydrogenation conversion rate and good selectivity of the obtained carbon dioxide three-fraction selective hydrogenation catalyst.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein. In the present invention, the "molecular weights" are all "number average molecular weights".
The method for preparing the alumina carrier comprises the steps of sequentially forming, first drying and first roasting a mixture containing an aluminum-containing compound, a binder, an acid, polyethylene oxide, an acrylic resin and optional lanthanum or a lanthanum-containing compound.
In the present invention, the aluminum-containing compound may be any of various aluminum-containing compounds conventionally used for preparing an alumina carrier, and may be, for example, aluminum hydroxide and/or pseudo-boehmite.
In the present invention, the binder may use various binders that are currently used to prepare the alumina carrier, and may be, for example, one or more of sesbania powder, starch, and hydroxypropylmethylcellulose. Preferably, the binder is used in an amount of 5 to 15 wt.%, preferably 8 to 12 wt.%, more preferably 8 to 10 wt.%, relative to the weight of the aluminum-containing compound, calculated as alumina. According to one embodiment of the present invention, sesbania powder, starch and hydroxypropyl methylcellulose are preferably used together, and more preferably in a weight ratio of 1: 0.5-0.7: 0.1-0.3.
In the present invention, the acid may be one or more of nitric acid, citric acid and acetic acid. Preferably, the acid is used in an amount of 1 to 8 wt.%, preferably 4 to 6 wt.%, relative to the weight of the aluminium-containing compound, calculated as aluminium oxide. As the nitric acid, a commercially available concentrated nitric acid having a mass fraction of about 68%; as the above citric acid, commercially available solid citric acid (e.g., chemically pure or analytically pure citric acid) is preferably used; glacial acetic acid (e.g., 98% by mass) is preferably used as the acetic acid. According to one embodiment of the present invention, nitric acid, citric acid and acetic acid are preferably used as the acid at the same time, and more preferably in a weight ratio of 1: 0.9-1.1: 0.1-0.3.
According to a preferred embodiment of the present invention, in the mixture, the weight ratio of the aluminum-containing compound, the binder and the acid is 1: 0.03-0.1: 0.015 to 0.08, more preferably 1: 0.08-0.1: 0.04-0.06. More preferably, the binder and the lanthanum or lanthanum-containing compound are used in an amount of 2 to 15 wt.%, preferably 8 to 12 wt.%, relative to the weight of the aluminum-containing compound, calculated as alumina.
The inventors of the present invention have surprisingly found that the alumina carrier prepared by using polyethylene oxide, acrylic resin and lanthanum or lanthanum-containing compound in combination during the process of preparing the alumina carrier can simultaneously improve the conversion rate and selectivity of the catalyst in the selective hydrogenation reaction of carbon-two three-fraction.
According to the present invention, the lanthanum or lanthanum-containing compound may be a simple lanthanum or any lanthanum-containing compound capable of being calcined to obtain lanthanum oxide, and from the viewpoint of operability, it is preferable to use simple lanthanum. More preferably, the lanthanum or lanthanum-containing compound is used in an amount of 0.35 to 1 wt.%, preferably 0.4 to 0.6 wt.%, more preferably 0.4 to 0.5 wt.%, calculated as lanthanum element, relative to the weight of the aluminum-containing compound, calculated as alumina.
In order to improve the conversion rate and selectivity of the selective hydrogenation catalyst for the carbon-two carbon three-cut, the molecular weight of the acrylic resin is preferably 100 ten thousand to 1000 ten thousand, more preferably 500 ten thousand to 700 ten thousand, and the molecular weight of the polyethylene oxide is preferably 200 ten thousand to 500 ten thousand, more preferably 300 ten thousand to 400 ten thousand. And in order to further improve the conversion and selectivity of the selective hydrogenation reaction, the polyethylene oxide and the acrylic resin are used in an amount of 1 to 10% by weight, preferably 3 to 7% by weight, more preferably 5 to 7% by weight, and still more preferably 5 to 6% by weight, relative to the weight of the aluminum-containing compound in terms of alumina. More preferably, the weight ratio of the polyethylene oxide to the acrylic resin component is 1:9 to 9:1, further preferably 2:8 to 5:5, more preferably 1: 0.4-0.7.
As a production process of the above-mentioned mixture containing the aluminum-containing compound, the binder, the acid, the acrylic resin and optionally lanthanum or the lanthanum-containing compound, for example, the aluminum-containing compound, the binder and the acrylic resin may be mixed, and then the acid and optionally lanthanum or the lanthanum-containing compound may be added and mixed. Preferably, the aluminum-containing compound, the binder and the acrylic resin are mixed using powder, and then the mixture is mixed with an aqueous solution in which an acid and optionally lanthanum or a lanthanum-containing compound are dissolved. When hydroxypropylmethylcellulose is used as the binder, it is preferably mixed in the form of an aqueous solution.
In order to achieve good mixing effect, the weight ratio of water to the aluminum-containing compound (based on the dry weight of the aluminum hydroxide) added during mixing is preferably 1-4: 1, preferably 1.8 to 2.2: 1.
the mixing can achieve the effect of uniformly mixing the materials, preferably, the mixing temperature can be 5-45 ℃, and the mixing time can be 15-60 minutes.
In the present invention, the molding is used to form the mixed materials into the desired shape of the catalyst, and the molding method is not particularly limited, and may be specifically selected according to the use requirements of the catalyst. The shape of the molding may be, for example, a pellet shape, a clover shape, a cylinder shape, a spherical shape, a porous shape, or the like. From the viewpoint of producing the selective hydrogenation catalyst for the three-carbon fraction, preferred are denticular or spherical particles, generally 1 to 10mm in diameter.
In the present invention, the method of the first drying is not particularly limited, and any conventional method for producing an alumina support may be used. Preferably, the conditions of the first drying include: the drying temperature is 80-150 ℃, and the drying time is 2-6 hours; more preferably, the drying temperature is 80-100 ℃ and the drying time is 3-5 hours. The first drying may be performed using a drying belt heater, for example.
In the present invention, the method of the first calcination is not particularly limited, and any conventional method for producing an alumina support may be used. Preferably, the conditions of the first firing include: the roasting temperature is 400-650 ℃, and the roasting time is 5-15 hours; more preferably, the calcination temperature is 450-550 ℃ and the calcination time is 8-12 hours. The first firing may be performed using, for example, a mesh belt kiln calciner.
In order to further improve the conversion rate and selectivity of the obtained carbo-two three-fraction selective hydrogenation catalyst, more preferably, the method further comprises the steps of impregnating the first calcined carrier with a potassium hydroxide solution, and then carrying out second drying and second calcination.
The potassium hydroxide solution used for impregnation has a concentration of preferably 0.01 to 0.1mol/L, more preferably 0.02 to 0.05mol/L, and is used in an amount of 30 to 100% by weight, more preferably 50 to 80% by weight, of the support after the first calcination.
As the conditions of the second drying, for example, there may be included: the drying temperature is 80-150 ℃, and the drying time is 2-15 hours; preferably, the drying temperature is 110-. The second drying may be performed using a drying belt heater, for example.
The conditions for the second baking include, for example: the roasting temperature is 1050 ℃ and 1300 ℃, and the drying time is 8-25 hours; more preferably, the calcination temperature is 1100-. The second calcination may be performed, for example, using a mesh belt kiln calciner.
By immersing the potassium hydroxide solution under the above conditions, and performing the second drying and the second calcination, the conversion rate and the selectivity of the obtained carbo-dioxide three-fraction selective hydrogenation catalyst can be further improved.
In a second aspect, the present invention provides an alumina carrier prepared by the above-described method of the present invention.
The carrier of the invention has the following physical properties: the bulk density is 0.6-0.9g/mL, the pore volume is 0.3-0.6mL/g, and the specific surface area is 10-70m2Per g, the average pore diameter is 40-300 nm. Preferably, the bulk density of the alumina carrier is 0.65-0.8 g/mL; the pore volume is 0.3-0.6 mL/g; the specific surface area is 35-70m2A/g, more preferably 40 to 60m2(ii)/g; the average pore diameter is 100-300nm, more preferably 150-300 nm.
And the carrier can simultaneously provide high conversion rate and selectivity when preparing the carbon dioxide three-fraction selective hydrogenation catalyst.
The third aspect of the invention provides the application of the alumina carrier in the preparation of a carbon dioxide three-fraction selective hydrogenation catalyst.
In the invention, the alumina carrier can be used for preparing the two-carbon three-fraction selective hydrogenation catalyst by loading an active metal component suitable for the two-carbon three-fraction selective hydrogenation catalyst.
The fourth aspect of the present invention provides a selective hydrogenation catalyst for carbon-two three-fraction, which comprises the carrier of the present invention as described above, and an active metal component supported on the carrier.
As the above active metal component, the active metal component of the existing carbo-two three-cut selective hydrogenation catalyst may be used, preferably comprising palladium and optionally a promoter component. As the promoter component, Ga, Ag, Mn, W, Cu, etc. may be mentioned, and among them, Ag and Mn are preferable. The palladium may be used in an amount of 0.01 to 0.4 wt%, preferably 0.02 to 0.1 wt%, relative to the alumina support; the promoter component may be used in an amount of 0.02 to 0.2 wt%, preferably 0.04 to 0.1 wt%, relative to the alumina support. The loading method can adopt any method which can be used for preparing the supported catalyst, and the active metal component can be loaded on the carrier by adopting the known existing methods such as dipping, spraying and the like, and the loading can be carried out in a step-by-step mode or a synchronous mode. For example, the support may be impregnated with a solution of a salt of the active metal dissolved therein, and then dried and calcined.
The present invention will be described in detail below by way of examples. In the following examples, acrylic resins (molecular weight 500 ten thousand) were used from Shandong Yanggu Longquan chemical plant and polyethylene oxides (molecular weight 400 ten thousand) were used from ZiboKai Yuan Hengchang chemical Co., Ltd.
Example 1
Aluminum hydroxide powder (20000 g calculated by alumina), sesbania powder 1000g, starch 600g and modifier 750g (polyoxyethylene 450g and acrylic resin 300g) are sequentially added into a kneader and uniformly mixed, and then deionized water 41000g dissolved with concentrated nitric acid 400g, citric acid 400g, glacial acetic acid 200g, rare earth element lanthanum 92g and hydroxypropyl methyl cellulose 200g (molecular weight 20 ten thousand) is added into the kneader in a spraying manner, and the kneading time is 25 min. And adding the kneaded material into a bin of a granulator, and starting the granulator to granulate to prepare the toothed sphere particles with the outer diameter of 5 mm.
The drying belt heater, mesh belt kiln roaster and exhaust fan were started, the drying curve was checked, and the carrier particles were poured into the drying belt using the loading hopper. The temperature range of the drying belt is controlled to be 90 ℃, and the drying time is controlled to be 4 hours.
And roasting the dried carrier for 10 hours at 500 ℃ by a mesh belt kiln roasting furnace to obtain the carrier. 20000g of the carrier is immersed in 12000g of potassium hydroxide solution with the concentration of 0.04mol/L, dried at 120 ℃ for 8 hours and then calcined at 1150 ℃ for 15 hours to obtain the catalyst carrier 1.
Example 2
The carrier preparation process was the same as in example 1 except that the addition amounts of polyethylene oxide and acrylic resin were 600g and 400g, respectively, to prepare carrier 2.
Example 3
The carrier preparation process was the same as in example 1 except that the addition amounts of the polyethylene oxide and the acrylic resin were 700g and 300g, respectively, to prepare a carrier 3.
Example 4
The carrier preparation process was the same as in example 1 except that the amounts of polyethylene oxide and acrylic resin added were 780g and 520g, respectively, to prepare a carrier 4.
Example 5
The carrier preparation process was the same as in example 1 except that the rare earth element lanthanum was changed from 92g to 110g, to prepare a carrier 5.
Example 6
The procedure of preparing the carrier was the same as in example 1 except that the calcination temperature of the carrier was changed from 1150 ℃ to 1200 ℃ to prepare a carrier 6.
Comparative example 1
The support preparation process was the same as in example 1, except that 750g of an acrylic resin was used as a modifier, and that support D1 was prepared.
Comparative example 2
The support preparation process was the same as in example 1 except that the modifier was polyethylene oxide 750g, to prepare support D2.
Comparative example 3
An alumina carrier was prepared by the same procedure as in example 1, except that the carrier D1 was prepared without adding polyethylene oxide and an acrylic resin.
Test example 1
The vehicle performance results are listed in table 1.
TABLE 1
Figure BDA0001929557950000101
As shown in Table 1, compared with the prior art, due to the addition of polyethylene oxide and acrylic resin as modifiers in the preparation process of the catalyst carrier, the physical parameters of the catalyst, such as bulk density, pore volume, specific surface area and average pore diameter, are superior to those of the catalyst without addition of polyethylene oxide and acrylic resin.
Test example 2
Preparation of the catalyst:
and taking 30mL of palladium nitrate solution with the concentration of 12mgPd/mL, adding 180mL of deionized water for dilution, spraying the solution on 1000g of the prepared catalyst carrier, drying the solution at 120 ℃ for 7 hours, and roasting the solution at 450 ℃ for 8 hours to obtain the catalyst.
Evaluation of catalyst Performance:
the prepared catalyst is used for the reaction of removing acetylene by selective hydrogenation of carbon-containing fraction.
20mL of catalyst is loaded into a fixed bed reactor, hydrogen is introduced for reduction, then feed gas is switched, the feed gas from the top of the deethanizing tower is introduced into the reactor after being matched with hydrogen, the hydrogen-acetylene ratio is 1.4, the concentration of acetylene at the inlet is 0.45 mol%, and the gas phase volume space velocity is 10000h-1. The composition of the tail gas of the reaction was monitored by gas chromatography, and the acetylene conversion and selectivity of the catalyst were determined and are shown in table 2.
TABLE 2
Catalyst and process for preparing same 1 2 3 4 5 6 D1 D2 D3
Conversion rate% 97 100 100 99 96 95 96 96 88
Selectively, according to 79 82 80 79 72 77 72 77 65
As shown in Table 2, compared with the prior art, because polyethylene oxide and acrylic resin are added as modifiers in the preparation process of the catalyst carrier, the catalyst has higher conversion rate and selectivity when being applied to a selective hydrogenation process of carbon-two three-fraction.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.

Claims (10)

1. The preparation method of the alumina carrier is characterized by comprising the steps of sequentially forming, first drying and first roasting a mixture containing an aluminum-containing compound, a binder, an acid, polyethylene oxide, an acrylic resin and optional lanthanum or a lanthanum-containing compound.
2. The method of claim 1, wherein the aluminum-containing compound is aluminum hydroxide and/or pseudo-boehmite;
preferably, the binder is one or more of sesbania powder, starch and hydroxypropyl methyl cellulose;
preferably, the acid is one or more of nitric acid, citric acid and acetic acid;
preferably, the acid is used in an amount of 1 to 8% by weight relative to the weight of the aluminum-containing compound calculated as alumina.
3. The process according to claim 1 or 2, wherein the binder is used in an amount of 5 to 15% by weight relative to the weight of the aluminium-containing compound calculated as alumina;
preferably, the lanthanum or lanthanum-containing compound is used in an amount of 0.35 to 1% by weight in terms of lanthanum element, relative to the weight of the aluminum-containing compound in terms of alumina.
4. The method of any one of claims 1-3, wherein the polyethylene oxide has a molecular weight of 200-500 ten thousand, and the acrylic resin has a molecular weight of 100-1000 ten thousand;
preferably, the polyethylene oxide and the acrylic resin are used in an amount of 1 to 10% by weight, preferably 3 to 7% by weight, relative to the weight of the aluminum-containing compound, calculated as alumina;
preferably, the weight ratio of the polyethylene oxide to the acrylic resin component is 1: 9-9: 1, preferably 2: 8-5: 5.
5. A process according to any one of claims 1 to 3, wherein the process comprises mixing an aluminium-containing compound, a binder and an acrylic resin, followed by the addition of an acid and optionally lanthanum or a lanthanum-containing compound;
preferably, the temperature of the mixing is 5-45 ℃ and the time of the mixing is 15-60 minutes.
6. The method of any of claims 1-3, wherein the conditions of the first drying comprise: the drying temperature is 80-150 ℃, and the drying time is 2-6 hours;
preferably, the conditions of the first firing include: the roasting temperature is 400-650 ℃, and the roasting time is 5-15 hours.
7. The method of claim 6, further comprising impregnating the first calcined support with a potassium hydroxide solution, followed by a second drying and a second calcination;
preferably, the concentration of the potassium hydroxide solution is 0.01-0.1 mol/L;
preferably, the amount of the potassium hydroxide solution is 30-100% of the weight of the first calcined carrier;
preferably, the conditions of the second drying include: the drying temperature is 80-150 ℃, and the drying time is 2-15 hours;
preferably, the conditions of the second firing include: the roasting temperature is 1050 ℃ and 1300 ℃, and the drying time is 8-25 hours.
8. An alumina support prepared by the method of any one of claims 1 to 7.
9. Use of the alumina support of claim 8 in the preparation of a carbon-dioxide three-fraction selective hydrogenation catalyst.
10. A selective hydrogenation catalyst for carbon-two three-cut, characterized by comprising the carrier of claim 8 and an active metal component supported on the carrier.
CN201811633769.1A 2018-12-29 2018-12-29 Alumina carrier and preparation method and application thereof Pending CN111375393A (en)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102259033A (en) * 2010-05-24 2011-11-30 中国石油化工股份有限公司 Alumina carrier and preparation method thereof as well as hydrogenation catalyst and preparation method thereof
CN103755537A (en) * 2014-01-14 2014-04-30 浙江新化化工股份有限公司 Cogeneration method of methyl isobutyl ketone and diiso butyl ketone
CN108250017A (en) * 2016-12-29 2018-07-06 中国石油天然气股份有限公司 Method for selective hydrogenation of carbon three-fraction
CN108855237A (en) * 2017-05-15 2018-11-23 中国石油化工股份有限公司 Porous alumina carrier and preparation method thereof and silver catalyst and application
CN108855094A (en) * 2017-05-16 2018-11-23 中国石油化工股份有限公司 The method of loaded catalyst and preparation method thereof and methane dry reforming preparing synthetic gas

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102259033A (en) * 2010-05-24 2011-11-30 中国石油化工股份有限公司 Alumina carrier and preparation method thereof as well as hydrogenation catalyst and preparation method thereof
CN103755537A (en) * 2014-01-14 2014-04-30 浙江新化化工股份有限公司 Cogeneration method of methyl isobutyl ketone and diiso butyl ketone
CN108250017A (en) * 2016-12-29 2018-07-06 中国石油天然气股份有限公司 Method for selective hydrogenation of carbon three-fraction
CN108855237A (en) * 2017-05-15 2018-11-23 中国石油化工股份有限公司 Porous alumina carrier and preparation method thereof and silver catalyst and application
CN108855094A (en) * 2017-05-16 2018-11-23 中国石油化工股份有限公司 The method of loaded catalyst and preparation method thereof and methane dry reforming preparing synthetic gas

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