CN113209965B - Catalyst for preparing olefin by light alkane dehydrogenation and preparation method and application thereof - Google Patents

Catalyst for preparing olefin by light alkane dehydrogenation and preparation method and application thereof Download PDF

Info

Publication number
CN113209965B
CN113209965B CN202110314642.9A CN202110314642A CN113209965B CN 113209965 B CN113209965 B CN 113209965B CN 202110314642 A CN202110314642 A CN 202110314642A CN 113209965 B CN113209965 B CN 113209965B
Authority
CN
China
Prior art keywords
catalyst
stirring
solution
carrier
magnesium
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202110314642.9A
Other languages
Chinese (zh)
Other versions
CN113209965A (en
Inventor
艾珍
梁衡
潘相米
李南锌
李扬
吴砚会
韩伟
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Southwest Research and Desigin Institute of Chemical Industry
Original Assignee
Southwest Research and Desigin Institute of Chemical Industry
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Southwest Research and Desigin Institute of Chemical Industry filed Critical Southwest Research and Desigin Institute of Chemical Industry
Priority to CN202110314642.9A priority Critical patent/CN113209965B/en
Publication of CN113209965A publication Critical patent/CN113209965A/en
Application granted granted Critical
Publication of CN113209965B publication Critical patent/CN113209965B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • B01J23/005—Spinels
    • 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
    • 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
    • C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
    • C07C5/327—Formation of non-aromatic carbon-to-carbon double bonds only
    • C07C5/333—Catalytic processes
    • C07C5/3335—Catalytic processes with metals
    • C07C5/3337—Catalytic processes with metals of the platinum group
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals
    • C07C2523/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36
    • C07C2523/56—Platinum group metals
    • C07C2523/63—Platinum group metals with rare earths or actinides
    • 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
    • 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
    • Y02P20/584—Recycling of catalysts

Landscapes

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

Abstract

The invention belongs to the technical field of catalyst preparation, and particularly relates to a catalyst for preparing olefin by light alkane dehydrogenation, and a preparation method and application thereof. The catalyst adopts modified spinel as a catalyst carrier, Pt as a main active component of the catalyst, and Sn, Zn, Ca, Ce, Mg, Nb and the like as auxiliary components, controls the physical and chemical properties of the catalyst through the preparation process of the catalyst, improves the wear resistance, improves the reaction activity and the reaction selectivity, and has better service performance adapted to a fluidized bed compared with the conventional catalyst.

Description

Catalyst for preparing olefin by light alkane dehydrogenation and preparation method and application thereof
Technical Field
The invention belongs to the technical field of catalyst preparation, and particularly relates to a catalyst for preparing olefin by light alkane dehydrogenation, and a preparation method and application thereof.
Background
The dehydrogenation of light alkane (light alkane and light olefin, mainly including pure and/or mixed ethane, propane, butane and isobutane) to prepare corresponding olefin is an important and economic olefin production process technology.
Commercial dehydrogenation catalysts typically use supported catalysts having noble metal platinum as the active component, with a few chromium-based catalysts. The catalyst support comprises alumina (gamma-Al) 2 O 3 Mesoporous Al 2 O 3 Etc.), molecular sieves (SAPO, HZSM-5, SBA-15, etc.), SiO 2 And the like. Catalytic reaction process technologies include Oleflex process (UOP corporation), Catofin process (abbummus corporation), STAR process (Krupp uhdewng corporation), and the like.
In the above process, except that the Oleflex propane dehydrogenation process adopts a moving bed reactor, the other processes all adopt fixed bed reactors. In a fixed bed reactor, the catalyst is required to have certain crushing strength to prevent the catalyst from being broken due to impact in the filling process; the fixed bed reactor has the advantages of low investment, low design difficulty and the like, but the fixed bed reactor is inconvenient for catalyst regeneration, and particularly needs to be stopped for recharging treatment. The regeneration of the catalyst can be conveniently realized in the fluidized bed reactor, but the catalyst is in a flowing state, so the catalyst has high requirements on the shape, the particle strength, the abrasion resistance index and the like of the catalyst besides good activity and selectivity.
Disclosure of Invention
The invention aims to solve the problems in the prior art and provides a preparation method of a catalyst for preparing olefin by light alkane dehydrogenation.
In order to achieve the above object, the technical solution of the present invention is as follows:
a preparation method of a catalyst for preparing olefin by light alkane dehydrogenation comprises the following steps:
s1, preparing a doped magnesium aluminate spinel carrier;
(1) adding deionized water into the pseudo-boehmite, and stirring in a water bath at a certain temperature to obtain uniform slurry A.
As a preferred embodiment of the present application, the mass ratio of the pseudo-boehmite to the deionized water in S1 is (0.5-1): (2-5), the temperature of the water bath stirring is 50-80 ℃.
(2) And adding the magnesium salt and the auxiliary agent I into deionized water to dissolve to obtain a solution B.
In a preferred embodiment of the present invention, the magnesium salt is any one of magnesium nitrate, magnesium sulfate, magnesium ethoxide and magnesium acetate.
As a better embodiment in the application, the auxiliary agent I is any one or a mixture of several of cerium nitrate, lanthanum nitrate, tin nitrate, gallium nitrate and niobium nitrate.
As a preferred embodiment of the present application, the molar ratio of magnesium to aluminum in solution B is 1: 1-10; the molar ratio of the dosage of the auxiliary agent I to the magnesium to the aluminum is 0.05-0.5: 1.
(3) adding the solution B into the slurry A, adding a proper amount of an auxiliary agent II, uniformly stirring, and adjusting to form gel by using concentrated nitric acid, wherein the pH value range is 2-5.
In a preferred embodiment of the present application, the auxiliary agent ii is any one or a mixture of any two of polyacrylamide, melamine, dicyandiamide, urea and sodium salicylate.
As a preferred embodiment of the present application, the molar ratio of the amount of the auxiliary II to the magnesium and aluminum is 0.001-0.02: 1.
as a better embodiment in the application, the step S1 uses concentrated nitric acid to adjust the gel, and the pH value after adjustment is 3-4.
(4) Spraying the prepared gel by adopting a spray granulation method to obtain a powdery carrier precursor, and roasting at a certain temperature to obtain a carrier for later use; in the step, the roasting temperature of the precursor is 600-900 ℃, and the roasting time is 3-6 h.
S2, loading Pt by a settling-precipitation method;
firstly, uniformly dispersing the carrier in deionized water, then obtaining carrier slurry under the condition of vigorous stirring, and gradually adding H into the carrier slurry 2 PtCl 6 A solution; then adding an additive and a second solvent, stirring at a certain temperature, and dropwise adding an alkaline regulator to adjust the pH value of the solution; adding a reducing agent, continuously stirring, heating the solution, and evaporating the solvent to dryness; then roasting to obtain the catalyst.
As a preferred embodiment of the present application, the additive is any one or a mixture of more of urotropine, malonic acid, succinic acid, adipic acid, citric acid, oxalic acid and tartaric acid.
As a preferred embodiment of the present application, the second solvent is any one or a mixture of ethanol, propanol, isopropanol and pentanol.
In a preferred embodiment of the present invention, the alkaline modifier is one or a mixture of sodium hydroxide and potassium hydroxide.
As a preferred embodiment in the present application, the reducing agent is any one or a mixture of several of formaldehyde, formic acid, propylene glycol, ethylene glycol and ascorbic acid.
As a preferred embodiment of the present application, the ratio of the carrier to the deionized water in S2 is (0.5-1): (2-5) the temperature condition of vigorous stirring is 50-80 ℃; the stirring temperature after the addition of the additive and the second solvent is 50-80 ℃, and the stirring time is 2-4 h; adding an alkaline regulator to adjust the pH value of the solution to 7-9, adding a reducing agent, stirring for 4-6h, heating the solution to 120 ℃ at the roasting temperature of 400 ℃ and 600 ℃ for 4-6 h.
The catalyst is applied to a fluidized bed reactor for preparing olefin by light alkane dehydrogenation, and has high propane conversion rate and high propylene selectivity.
As a preferred embodiment in this application, the catalystThe catalyst reduction is required before application: before use the catalyst is subjected to H 2 Reducing in gas under the condition of 450-600 ℃ for 2-4 h.
Compared with the prior art, the invention has the following beneficial effects by adopting the technical scheme:
firstly, magnesia-alumina spinel with high wear resistance is used as a main carrier and is compounded with a pseudo-boehmite carrier, and various auxiliary agents are used for reaming in the preparation process to improve the subsequent loading effect.
And (II) a spray drying technology is used in the preparation process to obtain the catalyst carrier with uniform and complete particle size, so that the wear resistance of the catalyst under the fluidized reaction condition is further improved, and the wear index of the catalyst is 2-4%.
And (III) a sedimentation-precipitation method is adopted in the Pt loading process, so that the Pt loading process and the control of the crystal size are facilitated. The invention adopts various reagents, auxiliary agents and process conditions, which can obviously improve the process performance of the catalyst.
Detailed Description
A catalyst for preparing olefin by dehydrogenating light alkane uses modified spinel as catalyst carrier, Pt as main active component of catalyst, Sn, Zn, Ca, Ce, Mg, Nb, etc. as auxiliary components, and features its controllable physical and chemical properties, high antiwear nature, and high reaction activity and selectivity.
The preparation method of the catalyst for preparing olefin by dehydrogenating light alkane comprises the following steps:
s1, preparing a doped magnesium aluminate spinel carrier;
preparing a carrier by adopting a sol-gel method and a spray drying method:
a, adding a proper amount of deionized water into a certain amount of pseudo-boehmite, and stirring in a water bath at a certain temperature to obtain uniform slurry A; wherein the mass ratio of the pseudo-boehmite to the deionized water is (0.5-1): (2-5), the temperature of the water bath stirring is 50-80 ℃.
B, weighing a proper amount of magnesium nitrate, adding a small amount of the auxiliary agent 1, and dissolving in deionized water to obtain a solution B;
and C, uniformly adding the solution B into the slurry A, adding a proper amount of an auxiliary agent II, uniformly stirring, and mixing concentrated nitric acid and water in a volume ratio of 1:1, diluting into nitric acid, adjusting into gel by using the nitric acid, and adjusting the pH value to 2-5;
and D, spraying the prepared gel by adopting a spray granulation method to obtain a powdery carrier precursor, and roasting at a certain temperature to obtain the carrier for later use. In the step, the roasting temperature of the precursor is 600-900 ℃, and the roasting time is 3-6 h.
S2, loading Pt by a settling-precipitation method;
firstly, uniformly dispersing the carrier in deionized water, then obtaining carrier slurry under the condition of vigorous stirring, and gradually adding H into the carrier slurry 2 PtCl 6 A solution; then adding an additive and a second solvent, stirring at a certain temperature, and dropwise adding an alkaline regulator to adjust the pH value of the solution; adding a reducing agent, continuously stirring, heating the solution, and evaporating the solvent to dryness; then roasting to obtain the catalyst.
S3 and catalyst H 2 And (4) reducing.
Before the catalyst is used in H 2 Reducing in gas under the condition of 450-600 ℃ for 2-4 h.
As mentioned above, in step S1, the aid i is preferably one or a combination of several of cerium nitrate, lanthanum nitrate, tin nitrate, gallium nitrate, magnesium nitrate and niobium nitrate;
as mentioned above, in step S1, the assistant ii is preferably one or a combination of two of polyacrylamide, melamine, dicyandiamide, urea and sodium salicylate;
as described above, the molar ratio of magnesium to aluminum in the solution in step S1 is 1: (1-10); the molar ratio of the dosage of the auxiliary agent I to magnesium to aluminum is as follows: (0.05-0.5): 1: (1-10); the molar ratio of the dosage of the auxiliary agent II to magnesium and aluminum is as follows: (0.001-0.02): 1: (1-10).
As mentioned above, in step S2, the additive is preferably one or a combination of several of urotropine, malonic acid, succinic acid, adipic acid, citric acid, oxalic acid, and tartaric acid.
As mentioned above, in step S2, the second solvent is preferably one or a combination of ethanol, propanol, isopropanol and pentanol.
As described above, the alkaline modifier is preferably one or a combination of two of sodium hydroxide and potassium hydroxide in step S2.
As mentioned above, in step S2, the reducing agent is preferably one or a combination of formaldehyde, formic acid, propylene glycol, ethylene glycol, ascorbic acid, and paraformaldehyde.
The proportion relation of the carrier and the deionized water in the step S2 is (0.5-1): (2-5) the temperature condition of vigorous stirring is 50-80 ℃; the stirring temperature after the addition of the additive and the second solvent is 50-80 ℃, and the stirring time is 2-4 h; adding an alkaline regulator to adjust the pH value of the solution to 7-9, adding a reducing agent, stirring for 4-6h, heating the solution to 120 ℃ at the roasting temperature of 400 ℃ and 600 ℃ for 4-6 h.
In order to make the objects, technical solutions and advantages of the present invention more clearly apparent, the present invention is further described in detail with reference to the following embodiments. All of the features disclosed in this specification, or all of the steps in any method or process so disclosed, may be combined in any combination, except combinations of features and/or steps that are mutually exclusive.
Example 1:
a preparation method of a catalyst for preparing olefin by light alkane dehydrogenation comprises the following steps:
s1, preparing a doped magnesium aluminate spinel carrier;
a, taking 0.2mol of pseudo-boehmite, adding a proper amount of deionized water, and stirring in a water bath at 65 ℃ to obtain uniform slurry A; the mass ratio of the pseudo-boehmite to the deionized water is 1: 3.
b, weighing 0.1mol of magnesium nitrate, adding 0.05mol of gallium nitrate, and adding deionized water to dissolve to obtain a solution B;
c, uniformly adding the solution B into the slurry A, adding 0.002mol of polyacrylamide, uniformly stirring, diluting with concentrated nitric acid and water according to the volume ratio of 1:1, adding the diluted solution into the mixture, adjusting the diluted solution into gel, and adjusting the pH value to be about 3;
and D, spraying the prepared gel by adopting a spray granulation method to obtain a powdery carrier precursor, and then roasting at 700 ℃ for 4 hours to serve as a carrier for later use.
S2, loading Pt by a settling-precipitation method;
dispersing 10g of the carrier in deionized water, stirring vigorously at 70 ℃, and adding H into the slurry dropwise 2 PtCl 6 Solution (Pt loading 0.5%); adding 0.02g of urotropin and 0.5g of isopropanol, stirring at 70 ℃ for more than 3h, and dropwise adding an alkaline regulator to adjust the pH value of the solution to 8; adding 0.05g of formaldehyde, stirring for 5 hours, heating the solution to 110 ℃, and evaporating the solvent to dryness. Then calcined at 500 ℃ for 4h as a catalyst for standby.
S3 and catalyst H 2 And (4) reducing.
Before the catalyst is used in H 2 Reducing in gas. Reducing at 500 ℃ for 2 h.
Example 2:
a preparation method of a catalyst for preparing olefin by light alkane dehydrogenation comprises the following steps:
s1, preparing a doped magnesium aluminate spinel carrier;
a, taking 0.2mol of pseudo-boehmite, adding a proper amount of deionized water, and stirring in a water bath at 65 ℃ to obtain uniform slurry A;
b, weighing 0.1mol of magnesium sulfate, adding 0.05mol of gallium nitrate, and adding deionized water to dissolve to obtain a solution B;
c, uniformly adding the solution B into the slurry A, adding 0.001mol of melamine, uniformly stirring, diluting with concentrated nitric acid according to the volume ratio of 1:1, adding the diluted solution into the mixed solution, and adjusting the pH value to be about 4;
and D, spraying the prepared gel by adopting a spray granulation method to obtain a powdery carrier precursor, and then roasting at 700 ℃ for 4 hours to serve as a carrier for later use.
S2, loading Pt by a settling-precipitation method;
dispersing 10g of the carrier in deionized water, stirring vigorously at 70 ℃, and adding H into the slurry dropwise 2 PtCl 6 Solution (Pt loading 0.3%); then, 0.02g of citric acid and 0.5g of ethanol were addedStirring at 70 ℃ for more than 3h, and dropwise adding an alkaline regulator to adjust the pH value of the solution to 8; 0.01g of paraformaldehyde is added, stirred for 5 hours, the temperature of the solution is raised to 110 ℃, and the solvent is evaporated to dryness. Then calcined at 500 ℃ for 4h as a catalyst for standby.
S3 and catalyst H 2 And (4) reducing.
Before the catalyst is used in H 2 Reducing in gas. Reducing at 500 ℃ for 2 h.
Example 3:
a preparation method of a catalyst for preparing olefin by light alkane dehydrogenation comprises the following steps:
s1, preparing a doped magnesium aluminate spinel carrier;
a, taking 0.1mol of pseudo-boehmite, adding a proper amount of deionized water, and stirring in a water bath at 65 ℃ to obtain uniform slurry A;
b, weighing 0.1mol of magnesium nitrate, adding 0.08mol of gallium nitrate, and dissolving in deionized water to obtain a solution B;
c, uniformly adding the solution B into the slurry A, adding 0.002mol of sodium salicylate, uniformly stirring, diluting with concentrated nitric acid according to the volume ratio of 1:1, adding the diluted solution into the solution, and adjusting the pH value to be about 4;
and D, spraying the prepared gel by adopting a spray granulation method to obtain a powdery carrier precursor, and then roasting at 700 ℃ for 4 hours to serve as a carrier for later use.
S2, loading Pt by a settling-precipitation method;
dispersing 10g of the carrier in deionized water, stirring vigorously at 70 ℃, and adding H into the slurry dropwise 2 PtCl 6 Solution (Pt loading 0.5%); then adding 0.03g of citric acid and 0.4g of ethanol, stirring at 70 ℃ for more than 3h, and dropwise adding an alkaline regulator to adjust the pH value of the solution to 8; 0.05g of ascorbic acid is added and stirred for 5 hours, then the temperature of the solution is raised to 110 ℃, and the solvent is evaporated to dryness. Then calcined at 500 ℃ for 4h as a catalyst for standby.
S3 and catalyst H 2 And (4) reducing.
Before the catalyst is used in H 2 Reducing in gas. Reducing at 500 ℃ for 2 h.
Example 4:
a preparation method of a catalyst for preparing olefin by light alkane dehydrogenation comprises the following steps:
s1, preparing a doped magnesia-alumina spinel carrier;
a, taking 0.3mol of pseudo-boehmite, adding a proper amount of deionized water, and stirring in a water bath at 65 ℃ to obtain uniform slurry A;
b, weighing 0.1mol of magnesium nitrate, adding 0.05mol of gallium nitrate, and adding deionized water to dissolve to obtain a solution B;
c, uniformly adding the solution B into the slurry A, adding 0.002mol of polyacrylamide, uniformly stirring, diluting with concentrated nitric acid according to the volume ratio of 1:1, adding the diluted solution into the mixture, and adjusting the pH value to be about 4;
and D, spraying the prepared gel by adopting a spray granulation method to obtain a powdery carrier precursor, and then roasting at 700 ℃ for 4 hours to serve as a carrier for later use.
S2, loading Pt by a settling-precipitation method;
dispersing 10g of the carrier in deionized water, stirring vigorously at 70 ℃, and adding H into the slurry dropwise 2 PtCl 6 Solution (Pt loading 0.5%); then adding 0.01g of citric acid and 0.5g of propanol, stirring at 70 ℃ for more than 3h, and dropwise adding an alkaline regulator to adjust the pH value of the solution to 8; adding 0.03g of formic acid, stirring for 5 hours, heating the solution to 110 ℃, and evaporating the solvent to dryness. Then calcined at 500 ℃ for 4h as a catalyst for standby.
S3 and catalyst H 2 And (4) reducing.
Before the catalyst is used in H 2 Reducing in gas. Reducing at 500 ℃ for 2 h.
Comparative example 1:
s1, preparing a doped magnesia-alumina spinel carrier;
a, taking 0.2mol of pseudo-boehmite, adding a proper amount of deionized water, and stirring in a water bath at 65 ℃ to obtain uniform slurry A;
b, weighing 0.1mol of magnesium nitrate, adding 0.05mol of gallium nitrate, and adding deionized water to dissolve to obtain a solution B;
and C, uniformly adding the solution B into the slurry A, adding 0.002mol of polyacrylamide, uniformly stirring, and mixing the mixture by using a mixing ratio of 1:1, adjusting concentrated nitric acid to form gel, and adjusting the pH value to be about 3;
and D, spraying the prepared gel by adopting a spray granulation method to obtain a powdery carrier precursor, and then roasting at 700 ℃ for 4 hours to serve as a carrier for later use.
S2, loading Pt by an immersion method;
uniformly dispersing the carrier in deionized water, violently stirring at 70 ℃, and dropwise adding H into the slurry 2 PtCl 6 The solution (Pt loading 0.5%) was immersed for 4h and the solvent evaporated to dryness. Then calcined at 500 ℃ for 4h as a catalyst for standby.
S3 and catalyst H 2 And (4) reducing.
Before the catalyst is used in H 2 Reducing in gas. Reducing at 500 ℃ for 2 h.
60g of the catalyst with the particle size of 20-150 microns is arbitrarily selected from examples 1-4 and comparative example 1, the performance evaluation is carried out on a fluidized bed reactor device, pure propane is used as raw material, the reaction temperature is 600 ℃, and the mass space velocity is 3h -1 . The activity evaluation data are shown in table 1.
Table 1 table of activity evaluation data of catalyst
Catalyst and process for preparing same Conversion of propane Propylene selectivity
Comparative example 1 36.5% 89.3%
Example 1 48.4% 93.6%
Example 2 47.5% 94.8%
Example 3 47.9% 95.2%
Example 4 46.8% 94.6%
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.

Claims (9)

1. A preparation method of a catalyst for preparing olefin by light alkane dehydrogenation is characterized by comprising the following steps:
s1, preparing a doped magnesium aluminate spinel carrier;
(1) adding deionized water into pseudo-boehmite, and stirring in a water bath at a certain temperature to obtain uniform slurry A;
(2) adding a magnesium salt and an auxiliary agent I into deionized water to be dissolved to obtain a solution B, wherein the auxiliary agent I is any one or a mixture of more of cerium nitrate, lanthanum nitrate, tin nitrate, gallium nitrate and niobium nitrate;
(3) adding the solution B into the slurry A, adding a proper amount of an auxiliary agent II, uniformly stirring, adjusting the pH value to 2-5 by using concentrated nitric acid to form gel, wherein the auxiliary agent II is any one or a mixture of any two of melamine, dicyanodiamide, urea and sodium salicylate;
(4) spraying the prepared gel by adopting a spray granulation method to obtain a powdery carrier precursor, and then roasting at a certain temperature to be used as a carrier for later use;
the molar ratio of magnesium to aluminum in the S1 solution B is 1: 1-10; the molar ratio of the dosage of the auxiliary agent I to the magnesium to the aluminum is 0.05-0.5: 1; the molar ratio of the dosage of the auxiliary agent II to magnesium and aluminum is 0.001-0.02: 1;
s2, loading Pt by a settling-precipitation method;
firstly, uniformly dispersing the carrier in deionized water, then violently stirring at a certain temperature to obtain carrier slurry, and gradually adding H into the carrier slurry 2 PtCl 6 A solution; then adding an additive and a second solvent, stirring at a certain temperature, and dropwise adding an alkaline regulator to adjust the pH value of the solution; adding a reducing agent, continuously stirring, heating the solution, and evaporating the solvent to dryness; then roasting to obtain a catalyst; the additive is any one or a mixture of more of urotropine, malonic acid, succinic acid, adipic acid, citric acid, oxalic acid and tartaric acid; the second solvent is any one or a mixture of ethanol, propanol, isopropanol and pentanol.
2. The process for preparing a catalyst for the dehydrogenation of light alkanes to olefins according to claim 1, wherein: in the step (1) of S1, the mass ratio of the pseudo-boehmite to the deionized water is 0.5-1: 2-5, the temperature of water bath stirring is 50-80 ℃.
3. The process for preparing a catalyst for the dehydrogenation of light alkanes to olefins according to claim 1, wherein: and step S1, using concentrated nitric acid to adjust the mixture into gel, and adjusting the pH value to 3-4.
4. The process for preparing a catalyst for the dehydrogenation of light alkanes to olefins according to claim 1, wherein: the magnesium salt is any one of magnesium nitrate, magnesium sulfate, magnesium ethoxide and magnesium acetate.
5. The process for preparing a catalyst for the dehydrogenation of light alkanes to olefins according to claim 1, wherein: the roasting temperature of the precursor in the step (4) of S1 is 600-900 ℃, and the roasting time is 3-6 h.
6. The process for preparing a catalyst for the dehydrogenation of light alkanes to olefins according to claim 1, wherein: the alkaline regulator in S2 is one or a mixture of sodium hydroxide and potassium hydroxide; the reducing agent is any one or a mixture of more of formaldehyde, formic acid, propylene glycol, ethylene glycol and ascorbic acid.
7. The process for preparing a catalyst for the dehydrogenation of light alkanes to olefins according to claim 1, wherein: the mass ratio of the carrier to the deionized water in the S2 is 0.5-1: 2-5, wherein the temperature condition of vigorous stirring is 50-80 ℃; the stirring temperature after the addition of the additive and the second solvent is 50-80 ℃, and the stirring time is 2-4 h; adding an alkaline regulator to adjust the pH value of the solution to 7-9, adding a reducing agent, stirring for 4-6h, heating the solution to 120 ℃ at the roasting temperature of 400 ℃ and 600 ℃ for 4-6 h.
8. Use of a light alkane dehydrogenation to olefin catalyst prepared according to any one of claims 1-7, wherein: the catalyst is used for a fluidized bed reactor in olefin preparation by light alkane dehydrogenation, and has high propane conversion rate and high propylene selectivity.
9. The use of a light alkane dehydrogenation catalyst to produce olefins according to claim 7, wherein the catalyst requires a catalyst reduction prior to use: before use the catalyst is subjected to H 2 The reduction is carried out under the conditions of 450 ℃ and 600 ℃ for 2-4 h.
CN202110314642.9A 2021-03-24 2021-03-24 Catalyst for preparing olefin by light alkane dehydrogenation and preparation method and application thereof Active CN113209965B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202110314642.9A CN113209965B (en) 2021-03-24 2021-03-24 Catalyst for preparing olefin by light alkane dehydrogenation and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202110314642.9A CN113209965B (en) 2021-03-24 2021-03-24 Catalyst for preparing olefin by light alkane dehydrogenation and preparation method and application thereof

Publications (2)

Publication Number Publication Date
CN113209965A CN113209965A (en) 2021-08-06
CN113209965B true CN113209965B (en) 2022-08-09

Family

ID=77083930

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202110314642.9A Active CN113209965B (en) 2021-03-24 2021-03-24 Catalyst for preparing olefin by light alkane dehydrogenation and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN113209965B (en)

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0409355A1 (en) * 1989-07-20 1991-01-23 The Dow Chemical Company Process of oxidizing aliphatic hydrocarbons in the presence of a solid heterogeneous catalyst and catalyst
CN103212411A (en) * 2013-05-07 2013-07-24 北京化工大学 High-performance catalyst for preparing olefin through dehydrogenation of light alkane and preparation method thereof
CN104525195A (en) * 2014-12-30 2015-04-22 中国石油天然气股份有限公司 Catalyst used for preparing isobutene through isobutane dehydrogenation and preparation method and application thereof
CN104588008A (en) * 2013-11-01 2015-05-06 中国石油化工股份有限公司 Saturated alkane dehydrogenation catalyst and preparation method thereof
CN105642264A (en) * 2014-11-21 2016-06-08 中国科学院大连化学物理研究所 Preparation method of magnesium aluminate spinel for catalyst carrier
CN107051434A (en) * 2017-01-15 2017-08-18 北京化工大学 The propane dehydrogenation catalyst and preparation method and application of a kind of stable high dispersive
CN108325523A (en) * 2018-02-02 2018-07-27 华东理工大学 A kind of propane dehydrogenation catalyst and preparation method thereof

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1069226C (en) * 1996-01-24 2001-08-08 中国科学院大连化学物理研究所 Preparation of low carbon alkane dehydrogenating catalyst

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0409355A1 (en) * 1989-07-20 1991-01-23 The Dow Chemical Company Process of oxidizing aliphatic hydrocarbons in the presence of a solid heterogeneous catalyst and catalyst
CN103212411A (en) * 2013-05-07 2013-07-24 北京化工大学 High-performance catalyst for preparing olefin through dehydrogenation of light alkane and preparation method thereof
CN104588008A (en) * 2013-11-01 2015-05-06 中国石油化工股份有限公司 Saturated alkane dehydrogenation catalyst and preparation method thereof
CN105642264A (en) * 2014-11-21 2016-06-08 中国科学院大连化学物理研究所 Preparation method of magnesium aluminate spinel for catalyst carrier
CN104525195A (en) * 2014-12-30 2015-04-22 中国石油天然气股份有限公司 Catalyst used for preparing isobutene through isobutane dehydrogenation and preparation method and application thereof
CN107051434A (en) * 2017-01-15 2017-08-18 北京化工大学 The propane dehydrogenation catalyst and preparation method and application of a kind of stable high dispersive
CN108325523A (en) * 2018-02-02 2018-07-27 华东理工大学 A kind of propane dehydrogenation catalyst and preparation method thereof

Non-Patent Citations (6)

* Cited by examiner, † Cited by third party
Title
Effects of steam on the structure of Pt-Sn/ZnAl2O4 catalysts;Dong, WS et al;《ACTA PHYSICO-CHIMICA SINICA》;19990430;第15卷(第4期);第289-292页 *
Na2CO3处理制备复合孔ZSM-5分子筛及其丙烷脱氢制丙烯的催化性能;韩伟 等;《化工进展》;20170108;第35卷;第174-178页 *
The influence of the synthesis routes of MgAl2O4 on its properties and behavior as support of dehydrogenation catalysts;Bocanegra, SA et al;《MATERIALS CHEMISTRY AND PHYSICS 1》;20081015;第111卷(第2-3期);第534-541页 *
丙烷及乙苯氧化脱氢反应的新型催化剂研究;许杰;《中国博士学位论文全文数据库 工程科技Ⅰ辑》;20101115(第11期);全文 *
丙烷脱氢高热稳定性催化剂Pt-Sn/MgAl2O4研究;王婷;《中国优秀博硕士学位论文全文数据库(硕士)工程科技Ⅰ辑》;20170515(第5期);全文 *
混合低碳烷烃脱氢工艺及催化剂研究;申燕芝;《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》;20180615(第6期);全文 *

Also Published As

Publication number Publication date
CN113209965A (en) 2021-08-06

Similar Documents

Publication Publication Date Title
JP4970634B2 (en) Supported catalysts that can be used in organic compound conversion reactions
CN104209123B (en) A kind of argentiferous and boron catalyst for dehydrogenation of low-carbon paraffin and preparation method thereof
CN108218718B (en) Method for efficiently preparing N, N-dibenzyl ethylenediamine through catalytic hydrogenation
CN109126792B (en) Synthesis and application of Cu-Silicate-1 catalyst
CN113042044B (en) TiO doped with ZnO 2 -SiO 2 Preparation and application of platinum catalyst as carrier
CN105642324B (en) A kind of base metal selective hydrocatalyst and its preparation method and application
EP3892369A1 (en) Alkali metal and/or alkaline earth metal-doped transition metal-hydrogen active metal composite oxide catalyst and process for preparing butadiene using the same
CN107486197B (en) Preparation method of low-carbon alkane dehydrogenation microspherical catalyst
WO2024008164A1 (en) Modified zinc aluminate carrier, low-carbon alkane dehydrogenation catalyst, preparation method for low-carbon alkane dehydrogenation catalyst, and use of low-carbon alkane dehydrogenation catalyst
EP3083038B1 (en) Method for making a heterogeneous alkane dehydrogenation catalyst
CN113209965B (en) Catalyst for preparing olefin by light alkane dehydrogenation and preparation method and application thereof
CN109289831A (en) The catalyst of preparing propylene by dehydrogenating propane and preparation method thereof with high anti-carbon
CN113509950A (en) Preparation method of gallium-based catalyst taking alumina modified by non-metallic elements as carrier
CN104148070B (en) A kind of catalyst for dehydrogenation of low-carbon paraffin containing skeleton silver and its preparation method
CN101148395B (en) Method for preparing 1,1,1,2,3,3-hexafluoropropane from 1,1,1,2,3,3-hexafluoropropylene and hydrogen gas
CN111790384B (en) Pt-based multi-component catalyst for preparing propylene by propane dehydrogenation and preparation method thereof
CN112058255B (en) Alkane dehydrogenation catalyst and preparation method thereof
CN111437813B (en) Isobutane dehydrogenation catalyst and preparation method and application thereof
JP7144208B2 (en) Catalyst for producing cumene and its application
CN110560055B (en) Alkane dehydrogenation catalyst, preparation method and application thereof
WO2016152796A1 (en) Method for producing conjugated diene
CN112717920A (en) N-butane dehydrogenation catalyst and preparation method thereof
CN115634678B (en) Ethane dehydrogenation catalyst and method for simultaneously preparing ethylene and hydrogen through ethane dehydrogenation
CN111054383A (en) Catalyst for dehydrogenation reaction of organic liquid hydrogen storage material and preparation method thereof
CN107973682B (en) Method for preparing propylene by propane dehydrogenation

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant