CN117123212A - Propane dehydrogenation catalyst for fixed bed and preparation method thereof - Google Patents

Propane dehydrogenation catalyst for fixed bed and preparation method thereof Download PDF

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CN117123212A
CN117123212A CN202210557315.0A CN202210557315A CN117123212A CN 117123212 A CN117123212 A CN 117123212A CN 202210557315 A CN202210557315 A CN 202210557315A CN 117123212 A CN117123212 A CN 117123212A
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catalyst
nitrate
hours
roasting
salt
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黄剑锋
孔维杰
周金波
李长明
孙世林
曹庚振
杨一青
卜婷婷
苟文甲
马艳捷
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Petrochina Co Ltd
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Petrochina 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • B01J37/0209—Impregnation involving a reaction between the support and a fluid
    • 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
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/24—Chromium, molybdenum or tungsten
    • B01J23/30—Tungsten
    • 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
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/85—Chromium, molybdenum or tungsten
    • B01J23/888—Tungsten
    • 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
    • B01J37/0207—Pretreatment of the support
    • 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
    • C07C5/3332—Catalytic processes with metal oxides or metal sulfides
    • 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)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention relates to a propane dehydrogenation catalyst for a fixed bed, wherein the carrier of the catalyst is Al 2 O 3 The active component is Cr 2 O 3 The catalyst also contains an auxiliary agent WO 3 、ZrO 2 And Ga 2 O 3 Cr is calculated as 100% by weight of the catalyst 2 O 3 The content of (2) is 10-24%, WO 3 The content of (3) is 1-5%, zrO 2 The content of Ga is 0.001% -0.5% 2 O 3 The content of (2) is 0.001-0.5%. The invention also relates to a preparation method of the propane dehydrogenation catalyst for the fixed bedThe preparation method. In the catalyst provided by the invention, zirconium element and gallium element can assist tungsten element to well control the pH value of the catalyst carrier, so that the deposition amount and uniformity of active components in the impregnation process are increased; the zirconium element and the gallium element can also interfere the tungsten element, cr and O to form stable crystals, so that the stability of the catalyst is obviously improved on the premise of improving the performance of the catalyst.

Description

Propane dehydrogenation catalyst for fixed bed and preparation method thereof
Technical Field
The invention relates to the field of propane dehydrogenation catalysts, in particular to a catalyst for preparing propylene by catalytic dehydrogenation of propane for a fixed bed and a preparation method thereof.
Background
Propylene is the second largest basic chemical raw material with the dosage inferior to ethylene in petrochemical industry. In recent years, global propylene production has steadily increased, driven by the ever-increasing downstream demand. According to the well-known IHS analysis of the IHS world petrochemical industry in 2017, the propylene yield is continuously increased in the world in recent years, but the propylene supply and demand gap is still continuously increased. With the start-up construction and the application of new propane dehydrogenation devices, the production capacity of propane dehydrogenation is growing at a high speed, however, the problems of relatively low propane conversion rate, poor stability, low propylene selectivity, small particle strength and the like still exist in the development process of the catalyst for preparing propylene.
For example, chinese patent document CN108654596a discloses a propane dehydrogenation catalyst and a preparation method thereof, wherein the catalyst is prepared by mixing a chromium composite oxide as an active component with a high-performance heat carrier, adding a binder and a modifying element, kneading, extruding strips, drying, and roasting. The weight percentage of each component is as follows: 55-80% of chromium composite oxide, 10-30% of high-performance heat carrier, 0.1-10.0% of modified element and the balance of binder. The propane dehydrogenation catalyst disclosed in this document has a short single-pass life and poor stability.
Chinese patent document CN110180530a discloses a catalyst for preparing olefin by dehydrogenating light alkane and a preparation method thereof. The catalyst comprises 2-8wt% of chromium oxide, 0.5-1.0wt% of auxiliary agent and the balance of modified active carbon carrier. The reaction conditions are as follows: the reaction temperature is 500-650 ℃, the reaction pressure is 0.1-0.5MPa, and the airspeed is 500-5000 h -1 . The bulk specific gravity of the catalyst is 0.6-0.8 g/mL, and the specific surface area is 90-200 m 2 Per g, pore volume of 0.4-0.8 mL/g, average pore diameter of 10-50 nm, and crushing strength of 40-100N cm -1 . The catalyst has small crushing strength, low bulk specific gravity and difficult industrial use.
Chinese patent document CN109331811a discloses a method for preparing a mesoporous chromium-aluminum composite oxide catalyst: dissolving aluminum salt and an auxiliary agent in a solvent, adding a chromium-containing precursor subjected to vacuum treatment, and stirring until the solvent volatilizes to obtain a first precursor; and drying and roasting the first precursor to obtain the mesoporous chromium-aluminum composite oxide catalyst. Wherein the mass percentage of the chromic oxide, the auxiliary agent and the aluminum oxide is 5-20:0.5-2:79.5-93; and/or the pore diameter of the mesoporous chromium-aluminum composite oxide catalyst is 5-20 nm, and the specific surface area is 60-400 m 2 ·g -1 The conversion rate of propane and the selectivity of propylene can reach 37-55% and 85-97%, respectively, and the catalyst has higher selectivity and regeneration stability. The catalyst disclosed in the document is a novel porous material, namely a metal organic framework Material (MOFs), has the characteristics of adjustability, large specific surface area, high porosity, ordered pore channels, higher stability and the like, and is a better exploration direction. However, the MOFs material has severe preparation conditions, and the MOFs material does not have the level of large-scale industrial production application at present.
Chinese patent textThe CN103769078A discloses a propane dehydrogenation catalyst and a preparation method thereof, and Al is used for preparing 2 O 3 The catalyst is prepared from chromium as an active component, alkali metal as a promoter component, wherein the content of chromium oxide in the catalyst is 10% -30%, the content of alkali metal oxide is 0.5% -3.0%, and the balance is aluminum oxide. Wherein the active component chromium is impregnated with 65% -75% of chromium element in two times before and after alkali metal impregnation, and the rest chromium is impregnated in a second time after alkali metal impregnation. The method reduces the strong interaction between the active component chromium, the metal auxiliary agent and the catalyst carrier, can uniformly disperse the active component and the alkali metal auxiliary agent on the surface of the carrier, improves the dispersity and the loading capacity of the active component, avoids the generation of a-chromium oxide, and reduces the occurrence of side reaction, thereby improving the activity and the selectivity of the catalyst. In the preparation method, alkali metal is introduced between the twice impregnated active components, so that only the surface acidity of the catalyst and the dispersity of the active components can be improved, the generation of a-chromium oxide can be prevented, but the generation of a-aluminum oxide in the carrier can not be inhibited, and the stability of the catalyst needs to be further improved and the service life of the catalyst needs to be prolonged.
Chinese patent document CN110560041a discloses a propane dehydrogenation catalyst, which comprises the following components in parts by weight: a) 1 to 25 parts of element Cr and/or W or oxide thereof; b) 0 to 5 parts of at least one element of group IA or an oxide thereof; c) 0.01 to 5 parts of at least one element selected from group IVB of the periodic table or an oxide thereof; d) 69-96 parts of Al 2 O 3 A carrier. The invention adds two elements of W and IA as active components to prepare propane dehydrogenation catalyst based on Cr element, which can improve the PH value of the catalyst to a certain extent to change the performance of the catalyst, but the single W element can form stable crystal with Gr in high temperature aerobic environment, thereby accelerating the deactivation rate of the catalyst and leading to short single-pass service life of the catalyst.
Chinese patent document CN104549388A discloses a catalyst for dehydrogenating light alkane, which comprises the following components in parts by weight: a) 1-30 parts of Cr element or oxide thereof; b) 0.1 to 5 parts of Li, na, K, rb elementAn oxide thereof; c) 0.1 to 10 parts of Cu, co, ni, fe element or oxide thereof; d) 0.001 to 1 part of P element or oxide thereof; e) 0.001 to 1 part of Ga element or oxide thereof; f) 54 to 99 parts of Al 2 O 3 . In the technical scheme disclosed in the document, the primary activity of the catalyst can be improved by adding the P element and the Ga element to modify the catalyst, but P, ga and Cr can generate stable combination under the aerobic condition of high temperature, thereby influencing the performance of the catalyst.
Disclosure of Invention
Based on the above, the invention aims to provide a propane dehydrogenation catalyst for a fixed bed and a preparation method thereof, wherein the catalyst has relatively high propane conversion rate, good stability, high propylene selectivity and relatively high particle pressure measurement intensity, and is suitable for the propane dehydrogenation of the fixed bed.
To achieve the above object, the present invention provides a propane dehydrogenation catalyst for a fixed bed, wherein the carrier of the catalyst is Al 2 O 3 The active component is Cr 2 O 3 The catalyst also contains an auxiliary agent WO 3 、ZrO 2 And Ga 2 O 3 Cr is calculated as 100% by weight of the catalyst 2 O 3 The content of (2) is 10-24%, WO 3 The content of (3) is 1-5%, zrO 2 The content of Ga is 0.001% -0.5% 2 O 3 The content of (2) is 0.001-0.5%.
The propane dehydrogenation catalyst for a fixed bed according to the present invention preferably further comprises at least one of an alkali metal, an alkaline earth metal and a transition metal, more preferably, the oxide content of the alkali metal is about 0.5 to 3%, still more preferably 0.85 to 2.2%, the oxide content of the alkaline earth metal is about 0.01 to 2%, still more preferably 0.3 to 1.2%, the oxide content of the transition metal is 0.5 to 4%, still more preferably 0.8 to 3%, and the balance Al based on 100% by weight of the catalyst 2 O 3 The method comprises the steps of carrying out a first treatment on the surface of the Still more preferably, the alkali metal is at least one selected from sodium and potassium; the alkaline earth metal is at least one of magnesium, calcium and strontium; the transition metal is at least one of molybdenum, cobalt, nickel, copper, zinc and vanadium。
In order to achieve the above purpose, the invention also provides a preparation method of the propane dehydrogenation catalyst for the fixed bed, which comprises the following steps:
(1) Adding a pore-forming agent into the alumina powder to obtain mixed powder;
(2) Adding a tungsten precursor, a zirconium precursor, a gallium precursor, citric acid and nitric acid into water, and uniformly stirring to obtain a mixed solution;
(3) Adding the mixed solution into the mixed powder, kneading, extruding, forming, drying in sections, roasting in sections for the first time, and cooling to obtain a carrier containing an auxiliary agent;
(4) Dissolving chromium salt in water to obtain an impregnating solution;
(5) And uniformly spraying the impregnating solution on the carrier containing the auxiliary agent, curing, vacuum drying, carrying out secondary sectional roasting, and cooling to obtain the propane dehydrogenation catalyst for the fixed bed.
The method for preparing the propane dehydrogenation catalyst for the fixed bed, provided by the invention, preferably further comprises the step of dissolving at least one of alkali metal, alkaline earth metal and transition metal and chromium salt in water to obtain an impregnating solution.
The preparation method of the propane dehydrogenation catalyst for the fixed bed provided by the invention is characterized in that the mass ratio of the alumina powder to the pore-forming agent is preferably 100:1-10.
The preparation method of the propane dehydrogenation catalyst for the fixed bed provided by the invention is characterized in that in the step (2), the mass ratio of citric acid to nitric acid to water is preferably 2-6:3-11:50-100, and the concentration of the nitric acid is preferably 50-68 wt%.
The method for preparing the propane dehydrogenation catalyst for the fixed bed, provided by the invention, is characterized in that in the step (3), the kneading condition is that: the temperature is 10-40 ℃ and the time is 10-60 minutes; the catalyst is cylindrical or clover-shaped after the extrusion molding, and the strips are broken into strips with the length of 4-8 mm; the conditions of the sectional drying are as follows: drying at 60-100 deg.c for 3-24 hr and at 100-140 deg.c for 2-24 hr; the conditions of the first sectional roasting are as follows: roasting for 1-6 hours at 180-240 ℃, 1-4 hours at 460-500 ℃ and 2-6 hours at 750-900 ℃.
The preparation method of the propane dehydrogenation catalyst for the fixed bed provided by the invention is characterized in that in the step (5), the consumption of the impregnating solution is 1.0-1.2 times of the saturated adsorption capacity of the carrier, and the spraying condition is as follows: the temperature of the carrier is 70-98 ℃, and the carrier rotates at a constant speed of 50-1000 rpm; the curing conditions are as follows: the temperature is 70-98 ℃ and the time is 2-8 hours; the conditions of the vacuum drying are as follows: the relative vacuum degree is-0.01 to-80 KPa, the temperature is 80-140 ℃ and the time is 1-24 hours; the conditions of the second sectional roasting are as follows: roasting for 1-10 hours at 180-240 ℃, 1-8 hours at 460-500 ℃ and 1-24 hours at 560-900 ℃.
The invention provides a preparation method of a propane dehydrogenation catalyst for a fixed bed, wherein the Al is preferably 2 O 3 The powder is at least one of pseudo-boehmite and macroporous alumina; the pore-forming agent is at least one selected from sesbania powder, polyethylene glycol and carboxymethyl cellulose.
The preparation method of the propane dehydrogenation catalyst for the fixed bed provided by the invention is characterized in that the tungsten precursor is preferably soluble tungsten salt, and further preferably ammonium metatungstate; the zirconium precursor is soluble zirconium salt, and zirconium nitrate is further preferred; the gallium precursor is a soluble gallium salt, and preferably, gallium nitrate is further used.
The invention provides a preparation method of a propane dehydrogenation catalyst for a fixed bed, wherein the chromium salt is preferably at least one selected from ammonium dichromate, chromium nitrate and chromium acetate; the alkali metal salt is at least one selected from sodium nitrate and potassium nitrate; the alkaline earth metal salt is at least one selected from magnesium nitrate, calcium nitrate and strontium nitrate; the transition metal salt is at least one selected from molybdenum nitrate, zinc nitrate, cobalt nitrate, nickel nitrate, copper nitrate and vanadium nitrate.
Specifically, the preparation method of the catalyst comprises the following steps:
(1) Mixing the powder evenly: 1 to 10 weight parts of pore-forming agent is added into powder containing 100 weight parts of alumina to be uniformly mixed;
(2) Preparing a solution: weighing appropriate amount of WO 3 Precursor of (C), zrO 2 Precursor of (1), ga 2 O 3 2 to 6 weight parts of citric acid and 3 to 11 weight parts of nitric acid with the mass concentration of 50 to 68 weight percent are added into 50 to 100 weight parts of water at one time, and the solution is stirred to be uniform;
(3) And (3) carrier molding, namely pouring the solution in (2) into the mixed powder in (1), kneading for 10-60 minutes, extruding the mixture to form strips in a cylindrical shape or clover shape, and cutting the strips into strips with the length of 2-8 mm.
(4) Drying and roasting: drying the strip-shaped substance in the step (3) at 60-100 ℃ for 3-24 hours, drying at 100-140 ℃ for 2-24 hours, roasting at 180-240 ℃ for 1-6 hours, roasting at 460-500 ℃ for 1-4 hours, roasting at 750-900 ℃ for 2-6 hours, and cooling to obtain the prepared carrier containing the auxiliary agent.
(5) Heating, spraying and soaking: the method comprises the steps of respectively weighing the mass of chromium salt, alkali metal salt, alkaline earth metal salt and transition metal salt to be impregnated, dissolving the chromium salt, the alkali metal salt, the alkaline earth metal salt and the transition metal salt in a proper amount of water to prepare uniform impregnating solution, and preparing the solution according to 1.0-1.2 times of saturated adsorption quantity. Pouring the carrier containing the auxiliary agent prepared in the step (4) into an impregnating vessel capable of heating, rotating, spraying and vacuumizing, heating the carrier to 70-98 ℃, uniformly spraying the impregnating solution on the carrier in the process that the vessel rotates at a constant speed of 50-1000 rpm, and adsorbing by the carrier. After the spraying of the dipping solution is finished, the dipping container is kept at the original temperature for curing for 2 to 8 hours.
(6) And (3) drying: after the impregnation process is finished, the relative vacuum degree in the impregnation container is between minus 0.01 and minus 80KPa, the temperature is between 80 and 140 ℃, and the vacuum drying is carried out for 1 to 24 hours.
(7) Roasting: the dried catalyst is roasted for 1 to 10 hours at 180 to 240 ℃, for 1 to 8 hours at 460 to 500 ℃, for 1 to 24 hours at 560 to 900 ℃, and the catalyst is prepared after cooling.
In the invention, the spraying and dipping process can also be matched with the vacuum drying and roasting process. When the active components to be loaded of the catalyst are limited by the absorptivity of the carrier and cannot be loaded all at once, spraying a part of impregnating solution, curing and vacuumizing, spraying curing and vacuumizing again, and roasting after all the impregnating solution is sprayed and impregnated. Or spraying a part of the impregnating solution, curing, vacuumizing and roasting, spraying curing, vacuumizing and roasting again, and finishing the impregnation after all the impregnating solution is impregnated.
The beneficial effects of the invention are as follows:
(1) The propane dehydrogenation catalyst for the fixed bed provided by the invention contains 0.001% -0.5% of zirconia, so that the strength of the catalyst is improved to a certain extent, and the tolerance of the catalyst under the high-temperature reaction condition is enhanced. In addition, the zirconium element and the gallium element can assist the tungsten element to well control the pH value of the catalyst carrier, the number of hydroxyl groups on the surface of the catalyst is obviously increased, so that the potential on the surface of the catalyst is increased, and the deposition amount and uniformity of active components in the impregnation process can be increased; the zirconium element and the gallium element can also interfere the tungsten element, cr and O to form stable crystals, so that the stability of the catalyst is obviously improved on the premise of improving the performance of the catalyst.
(2) According to the preparation method of the propane dehydrogenation catalyst for the fixed bed, provided by the invention, as the specific gravity of the active component loaded by the catalyst is high, the active component is easy to agglomerate on the surface or in a pore canal by adopting a conventional impregnation method, so that the catalyst performance is reduced, and the catalyst is prepared by adopting an in-device heating rotary spraying impregnation method, so that the condition can be well improved, and the propane dehydrogenation performance of the catalyst can be effectively improved.
Detailed Description
The following describes embodiments of the present invention in detail: the present example is carried out on the premise of the technical scheme of the present invention, and detailed implementation modes and processes are given, but the protection scope of the present invention is not limited to the following examples, and the experimental methods of specific conditions are not noted in the following examples, and generally, the% is weight% according to conventional conditions.
In the raw materials adopted for preparing the catalyst in the embodiment, pseudo-boehmite, macroporous alumina and sesbania powder are all of industrial grade, the other materials are all commercial chemical pure reagents, and water is deionized distilled water.
The particle pressure measurement intensity is measured by using a DL-3 type particle intensity measuring instrument.
In the evaluation of the catalyst, the evaluation device used was an adiabatic fixed bed, and the catalyst loading was 5 g. The specific operation steps are as follows: firstly, 7.5L/h of nitrogen is introduced into a reactor, the temperature of a catalyst bed layer is increased to 610 ℃, then propane enters the reactor for reaction at a feed rate of 7.5L/h, the product is taken and analyzed every 5 minutes, and the analysis result of a cumulative sample of 5-10 minutes is used for calculating data which are taken as data of the conversion rate of the propane and the selectivity of the propylene in the examples.
The propane feed used in the catalyst evaluation was a commercially available steel cylinder gas having a propane content of greater than 99.5 wt%.
In each example, the calculation method of the propane conversion and the propylene yield is as follows:
propane conversion = 100-mass content of propane in reaction product 100
Propylene selectivity = mass content of propylene in reaction product x 100/propane conversion x 100
The single-pass service life of the catalyst is calculated by the accumulated reaction time of propylene yield more than or equal to 40 weight percent.
In the example catalyst composition formula, a represents an alkali metal oxide, B represents an alkaline earth metal oxide, and C represents other transition metal oxides.
Example 1
(Al 2 O 3 ) 74.66 (Cr 2 O 3 ) 19.7 (WO 3 ) 1.4 (Ga 2 O 3 ) 0.003 (ZrO 2 ) 0.037 A 1.1 B 0.1 C 3.0
(1) Weighing 174 g of pseudo-boehmite powder, and fully and uniformly mixing with 4 g of sesbania powder;
(2) Respectively weighing 2 g of ammonium metatungstate, 0.011 g of gallium nitrate, 0.21 g of 5-water zirconium nitrate, 7 g of nitric acid with the mass concentration of 68%, and 3 g of citric acid, adding into 60 g of water, and stirring to make the solution uniform;
(3) Pouring the solution in the step (2) into the mixed powder in the step (1), kneading for 30 minutes at 10 ℃, extruding to form strips, so that the strips become cylindrical and are broken into strips with the length of 4 mm;
(4) Drying the strip-shaped object in the step (3) at 80 ℃ for 5 hours, drying the strip-shaped object at 110 ℃ for 5 hours, roasting the strip-shaped object at 240 ℃ for 3 hours, roasting the strip-shaped object at 480 ℃ for 2 hours, roasting the strip-shaped object at 850 ℃ for 6 hours, and cooling the strip-shaped object to obtain a prepared carrier containing an auxiliary agent;
(5) 43.94 g of ammonium dichromate, 4.04 g of sodium nitrate, 2.02 g of calcium nitrate and 9.86 g of nickel nitrate are respectively weighed and dissolved in 100 g of water (1.0 times of saturated impregnation amount) to prepare uniform solution, the carrier containing the auxiliary agent prepared in the step (4) is put into an impregnation tank, put into an oil bath, and heated at a speed of 100 revolutions per minute, when the temperature in the tank reaches 90 ℃, the prepared solution is uniformly sprayed from two ends of the impregnation tank by using a peristaltic pump, after the spraying is finished, the temperature in the tank is kept at 90 ℃, and the impregnation tank is continuously rotated for 2 hours at a speed of 100 revolutions per minute.
(6) Drying the carrier sprayed in the step (5) in a drying tank at 120 ℃ under the vacuum-0.3 KPa for 6 hours, and roasting at 220 ℃ for 3 hours, 480 ℃ for 2.5 hours and 600 ℃ for 4 hours. The catalyst prepared had a particle pressure measurement of 234N/cm, a propane conversion of 55.0wt%, a propylene selectivity of 86.2wt% and a catalyst single pass life of 35min.
Comparative example 1:
step (2) was modified as in example 1 without adding ammonium metatungstate. The prepared catalyst has the particle pressure measurement intensity of 220N/cm, the propane conversion rate of 54.2wt percent, the propylene selectivity of 86.0wt percent and the single-pass service life of 15min.
Comparative example 2:
step (5) was modified as in example 1: and (3) directly pouring the carrier containing the auxiliary agent prepared in the step (4) into the prepared solution to finish impregnation. The final catalyst had a particle pressure of 232N/cm, a propane conversion of 48.1wt%, a propylene selectivity of 84.7wt% and a catalyst single pass life of 13min.
Comparative example 3:
as in example 1, the procedure (2) was modified without adding nitric acid. The final catalyst had a particle pressure of 216N/cm, a propane conversion of 52.1wt%, a propylene selectivity of 86.3wt% and a catalyst single pass life of 18min.
Comparative example 4:
step (2) was modified as in example 1 without adding zirconium nitrate 5 in water. The final catalyst had a particle pressure of 186N/cm, a propane conversion of 52.8wt%, a propylene selectivity of 87.1wt% and a catalyst single pass life of 19min.
Example 2:
the difference is that sodium nitrate is not added in step (5) as in example 1. The prepared catalyst has the particle pressure measurement intensity of 220N/cm, the propane conversion rate of 54.3wt percent, the propylene selectivity of 65wt percent and the single-pass service life of 34min.
Example 3:
the difference is that in step (5) calcium nitrate is not added as in example 1. The catalyst prepared had a particle pressure measurement of 223N/cm, a propane conversion of 53.1wt%, a propylene selectivity of 77.6wt% and a catalyst single pass life of 33 minutes.
Example 4:
the difference is that nickel nitrate is not added in step (5) as in example 1. The catalyst prepared had a particle pressure measurement of 214N/cm, a propane conversion of 44.3wt%, a propylene selectivity of 88.4wt% and a catalyst single pass life of 31min.
Example 5
(Al 2 O 3 ) 79.492 (Cr 2 O 3 ) 12.3 (WO 3 ) 4 (Ga 2 O 3 ) 0.007 (ZrO 2 ) 0.001 A 2.7 B 0.5 C 1
(1) Weighing 140 g of macroporous alumina powder, and fully and uniformly mixing with 3 g of polyethylene glycol;
(2) Respectively weighing 5.74 g of ammonium metatungstate, 0.026 g of gallium nitrate, 0.006 g of 5-water zirconium nitrate, 8g of nitric acid with the mass concentration of 50%, and 6 g of citric acid, adding into 80 g of water, and stirring to make the solution uniform;
(3) And pouring the solution in the step (2) into the mixed powder in the step (1), kneading at 40 ℃ for 40 minutes, extruding and molding to form a cylindrical strip with the length of 4 mm.
(4) Drying the strip-shaped object in the step (3) at 90 ℃ for 4 hours, drying the strip-shaped object at 120 ℃ for 6 hours, roasting the strip-shaped object at 230 ℃ for 4 hours, roasting the strip-shaped object at 470 ℃ for 1 hour, roasting the strip-shaped object at 900 ℃ for 5 hours, and cooling the strip-shaped object to obtain the prepared carrier containing the auxiliary agent;
(5) 90.96 g of chromium nitrate nonahydrate, 7.8 g of potassium nitrate, 2.48 g of magnesium nitrate and 3.28 g of cobalt nitrate are respectively weighed and dissolved in 120 g of water (1.05 times of saturated impregnation amount) to prepare uniform solution, the carrier containing the auxiliary agent prepared in the step (4) is put into an impregnation tank, put into an oil bath, and heated at a speed of 500 revolutions per minute, when the temperature in the tank reaches 70 ℃, the prepared solution is uniformly sprayed from two ends of the impregnation tank by using a peristaltic pump, after the spraying is finished, the temperature in the tank is kept at 70 ℃, and the impregnation tank is continuously rotated for 2 hours at a speed of 500 revolutions per minute.
(6) Drying the carrier sprayed in the step (5) in a drying tank at 100 ℃ under the vacuum-80 KPa for 12 hours, and roasting at 220 ℃ for 5 hours, 510 ℃ for 1.5 hours and 850 ℃ for 2 hours. The catalyst prepared had a particle pressure measurement of 234N/cm, a propane conversion of 57.0wt%, a propylene selectivity of 85.8wt% and a catalyst single pass life of 30min.
Example 6
(Al 2 O 3 ) 68.852 (Cr 2 O 3 ) 24 (WO 3 ) 2.1 (Ga 2 O 3 ) 0.035 (ZrO 2 ) 0.013 A 0.5 B 2 C 2.5
(1) Weighing 182 g of boehmite powder and fully and uniformly mixing with 2 g of carboxymethyl cellulose;
(2) Respectively weighing 3.26 g of ammonium metatungstate, 0.14 g of gallium nitrate, 0.08 g of 5-water zirconium nitrate, 9 g of nitric acid with the mass concentration of 55%, and 4 g of citric acid, adding into 60 g of water, and stirring to make the solution uniform;
(3) Pouring the solution in the step (2) into the mixed powder in the step (1), kneading for 50 minutes at 30 ℃, extruding to form strips, so that the strips become cylindrical and are broken into strips with the length of 4 mm;
(4) Drying the strip-shaped object in the step (3) at 100 ℃ for 3 hours, drying the strip-shaped object at 130 ℃ for 4 hours, roasting the strip-shaped object at 220 ℃ for 5 hours, roasting the strip-shaped object at 460 ℃ for 1 hour, roasting the strip-shaped object at 800 ℃ for 4 hours, and cooling the strip-shaped object to obtain the prepared carrier containing the auxiliary agent;
(5) Respectively weighing 105 g of chromium acetate, 1.99 g of sodium nitrate, 5.92 g of strontium nitrate and 7.13 g of molybdenum nitrate, dissolving in 110 g of water (1.2 times of saturated impregnation amount) to prepare uniform solution, placing the carrier containing the auxiliary agent prepared in the step (4) into an impregnation tank, placing the impregnation tank into an oil bath, heating at a speed of 50 revolutions per minute, uniformly spraying the prepared solution from two ends of the impregnation tank by using a peristaltic pump until the temperature in the tank reaches 80 ℃, keeping the temperature in the tank at 80 ℃ after spraying, and continuously rotating the impregnation tank at a speed of 50 revolutions per minute for 4 hours;
(6) Drying the carrier sprayed in the step (5) in a drying tank at 80 ℃ under the vacuum-40 KPa for 24 hours, and roasting at 210 ℃ for 3 hours, 500 ℃ for 1 hour and 750 ℃ for 2.5 hours. The catalyst prepared had a particle pressure measurement of 253N/cm, a propane conversion of 66.0wt%, a propylene selectivity of 85.9wt% and a catalyst single pass life of 35min.
Example 7
(Al 2 O 3 ) 70.719 (Cr 2 O 3 ) 20.7 (WO 3 ) 3.4 (Ga 2 O 3 ) 0.001 (ZrO 2 ) 0.18 A 2.5 B 1 C 1.5
(1) Weighing 174 g of pseudo-boehmite powder, and fully and uniformly mixing with 1 g of sesbania powder;
(2) 8.94 g of ammonium metatungstate, 0.001 g of gallium nitrate, 1.87 g of 5-water zirconium nitrate, 10 g of nitric acid with the mass concentration of 60% and 5 g of citric acid are respectively weighed, added into 100 g of water, and stirred to make the solution uniform;
(3) Pouring the solution in the step (2) into the mixed powder in the step (1), kneading for 60 minutes at 30 ℃, extruding to form strips, so that the strips are formed into strips with the length of 4mm and the strips are broken;
(4) Drying the strip-shaped object in the step (3) at 70 ℃ for 10 hours, drying the strip-shaped object at 140 ℃ for 10 hours, roasting the strip-shaped object at 210 ℃ for 6 hours, roasting the strip-shaped object at 490 ℃ for 3 hours, roasting the strip-shaped object at 750 ℃ for 3 hours, and cooling the strip-shaped object to obtain the prepared carrier containing the auxiliary agent;
(5) Respectively weighing 84.67 g of ammonium dichromate, 8.22 g of sodium nitrate, 6.77 g of potassium nitrate, 7.2 g of calcium nitrate and 8.7 g of copper nitrate, dissolving in 103 g of water (1.2 times of saturated impregnation amount) to prepare uniform solution, loading the carrier containing the auxiliary agent prepared in the step (4) into an impregnation tank, putting into an oil bath, heating at a speed of 1000 revolutions per minute, uniformly spraying the prepared solution from two ends of the impregnation tank by using a peristaltic pump until the temperature in the tank reaches 90 ℃, keeping the temperature in the tank at 90 ℃ after spraying, and continuously rotating the impregnation tank at a speed of 1000 revolutions per minute for 5 hours;
(6) Drying the carrier sprayed in the step (5) in a drying tank at 90 ℃ under the vacuum-20 KPa for 18 hours, and roasting at 260 ℃ for 4 hours, 480 ℃ for 2 hours and 650 ℃ for 3 hours. The prepared catalyst has the particle pressure measurement intensity of 245N/cm, the propane conversion rate of 52.0wt percent, the propylene selectivity of 91.4wt percent and the single-pass service life of 30min.
Example 8
(Al 2 O 3 ) 79.117 (Cr 2 O 3 ) 11.4 (WO 3 ) 2.7 (Ga 2 O 3 ) 0.083 (ZrO 2 ) 0.5 A 0.8 B 1.4 C 4
(1) Weighing 174 g of pseudo-boehmite powder, and fully and uniformly mixing with 10 g of sesbania powder;
(2) Respectively weighing 3.65 g of ammonium metatungstate, 0.29 g of gallium nitrate, 2.67 g of 5-water zirconium nitrate, 11 g of 65% nitric acid and 2 g of citric acid, adding into 75 g of water, and stirring to make the solution uniform;
(3) Pouring the solution in the step (2) into the mixed powder in the step (1), kneading for 20 minutes at 30 ℃, extruding to form strips, so that the strips become cylindrical and are broken into strips with the length of 4 mm;
(4) Drying the strip-shaped object in the step (3) at 60 ℃ for 6 hours, drying the strip-shaped object at 100 ℃ for 6 hours, roasting the strip-shaped object at 200 ℃ for 5 hours, roasting the strip-shaped object at 500 ℃ for 1.5 hours, roasting the strip-shaped object at 830 ℃ for 1 hour, and cooling the strip-shaped object to obtain the prepared carrier containing the auxiliary agent;
(5) 75.93 g of chromium nitrate nonahydrate, 2.18 g of potassium nitrate, 6.55 g of magnesium nitrate, 6.84 g of copper nitrate and 7.49 g of nickel nitrate are respectively weighed and dissolved in 143 g of water (1.15 times of saturated impregnation amount) to prepare uniform solution, the carrier containing the auxiliary agent prepared in the step (4) is put into an impregnation tank, put into an oil bath, and heated at a speed of 600 revolutions per minute, after the temperature in the tank reaches 75 ℃, the prepared solution is uniformly sprayed from two ends of the impregnation tank by using a peristaltic pump, after the spraying is finished, the temperature in the tank is kept at 75 ℃, and the impregnation tank is continuously rotated for 5 hours at a speed of 600 revolutions per minute.
(6) Drying the carrier sprayed in the step (5) in a drying tank at 110 ℃ under the vacuum-10 KPa for 18 hours, and roasting at 180 ℃ for 6 hours, 460 ℃ for 4 hours and 900 ℃ for 1 hour. The prepared catalyst has the particle pressure measurement of 261N/cm, the propane conversion rate of 55.4wt percent, the propylene selectivity of 88.4wt percent and the single-pass service life of 20 minutes.
Example 9
(Al 2 O 3 ) 82.354 (Cr 2 O 3 ) 10.0 (WO 3 ) 3.8 (Ga 2 O 3 ) 0.201 (ZrO 2 ) 0.095 A 3.0 B 0.05 C 0.5
(1) Weighing 174 g of pseudo-boehmite powder, and fully and uniformly mixing with 8g of sesbania powder;
(2) Respectively weighing 4.93 g of ammonium metatungstate, 0.67 g of gallium nitrate, 0.49 g of 5-water zirconium nitrate, 3 g of nitric acid with the mass concentration of 68%, and 2.5 g of citric acid, adding into 65 g of water, and stirring to make the solution uniform;
(3) Pouring the solution in the step (2) into the mixed powder in the step (1), kneading for 10 minutes at 30 ℃, extruding to form strips, so that the strips become cylindrical and are broken into strips with the length of 4 mm;
(4) Drying the strip-shaped object in the step (3) at 85 ℃ for 24 hours, drying the strip-shaped object at 125 ℃ for 24 hours, roasting the strip-shaped object at 180 ℃ for 6 hours, roasting the strip-shaped object at 500 ℃ for 1.5 hours, roasting the strip-shaped object at 830 ℃ for 1 hour, and cooling the strip-shaped object to obtain the prepared carrier containing the auxiliary agent;
(5) Respectively weighing 36.86 g of ammonium dichromate, 9.98 g of sodium nitrate, 1.07 g of strontium nitrate, 1.18 g of copper nitrate and 0.22 g of molybdenum nitrate, dissolving in 136 g of water (1.08 times of saturated adsorption quantity) to prepare uniform solution, loading the carrier containing the auxiliary agent prepared in the step (4) into an impregnation tank, putting into an oil bath, heating at a speed of 800 revolutions per minute, uniformly spraying the prepared solution from two ends of the impregnation tank by using a peristaltic pump until the temperature in the tank reaches 85 ℃, keeping the temperature in the tank at 85 ℃ after spraying, and continuously rotating the impregnation tank at a speed of 800 revolutions per minute for 7 hours;
(6) Drying the carrier sprayed in the step (5) in a drying tank at 100 ℃ under the vacuum-0.01 KPa for 4 hours, and roasting at 190 ℃ for 5 hours, 470 ℃ for 3 hours and 560 ℃ for 3.5 hours. The particle pressure measurement was 234N/cm, the propane conversion was 58.4wt%, the propylene selectivity was 84.8wt% and the catalyst single pass life was 40min.
Example 10
(Al 2 O 3 ) 75.866 (Cr 2 O 3 ) 15.4 (WO 3 ) 1.9 (Ga 2 O 3 ) 0.5 (ZrO 2 ) 0.034 A 2.0 B 0.8 C 3.5
(1) Weighing 174 g of pseudo-boehmite powder, and fully and uniformly mixing with 7 g of sesbania powder;
(2) 2.68 g of ammonium metatungstate, 1.80 g of gallium nitrate, 0.19 g of 5-water zirconium nitrate, 5 g of nitric acid with the mass concentration of 64% and 3.5 g of citric acid are respectively weighed, added into 95 g of water, and stirred to make the solution uniform;
(3) Pouring the solution in the step (2) into the mixed powder in the step (1), kneading for 45 minutes at 30 ℃, extruding and molding to form a cylindrical strip with the length of 4 mm;
(4) Drying the strip-shaped substance in the step (3) at 95 ℃ for 16 hours, drying the strip-shaped substance at 135 ℃ for 17 hours, roasting the strip-shaped substance at 190 ℃ for 4 hours, roasting the strip-shaped substance at 480 ℃ for 4 hours, roasting the strip-shaped substance at 820 ℃ for 2 hours, and cooling the strip-shaped substance to obtain a prepared carrier containing an auxiliary agent;
(5) Respectively weighing 33.74 g of ammonium dichromate, 5.67 g of potassium nitrate, 7.13 g of calcium nitrate, 1.13 g of strontium nitrate and 11.28 g of nickel nitrate, dissolving in 230 g of water (2.2 times of saturated adsorption quantity) to prepare uniform solution, loading the prepared carrier containing the auxiliary agent in the step (4) into an impregnating tank, placing the impregnating tank into an oil bath, heating at a speed of 800 revolutions per minute, uniformly spraying the prepared solution from two ends of the impregnating tank by using a peristaltic pump until the temperature in the tank reaches 85 ℃, keeping the temperature in the tank at 85 ℃ after 140ml of impregnating solution is sprayed, and continuously rotating the impregnating tank at a speed of 800 revolutions per minute for 2 hours;
(6) Drying the carrier sprayed in the step (5) in a drying tank at 140 ℃ under the condition of vacuum-40 KPa for 2 hours, continuously spraying the rest impregnating solution, continuously maintaining the temperature in the tank at 85 ℃, continuously rotating the impregnating tank at 800 revolutions per minute for 6 hours, maintaining the temperature in the drying tank at 140 ℃ under the condition of vacuum-20 KPa, drying for 4 hours, roasting at 240 ℃ for 1 hour, roasting at 500 ℃ for 4 hours, and roasting at 800 ℃ for 6 hours. The catalyst prepared had a particle pressure measurement of 258N/cm, a propane conversion of 63.2wt%, a propylene selectivity of 87.8wt% and a catalyst single pass life of 50min.
Example 11
(Al 2 O 3 ) 77.269 (Cr 2 O 3 ) 17.4 (WO 3 ) 1.0 (Ga 2 O 3 ) 0.381 (ZrO 2 ) 0.25 A 1.1 B 1.6 C 1.0
(1) Weighing 174 g of pseudo-boehmite powder, and fully and uniformly mixing with 5 g of sesbania powder;
(2) 1.36 g of ammonium metatungstate, 1.33 g of gallium nitrate, 1.35 g of 5-water zirconium nitrate, 6 g of 58% nitric acid and 4.5 g of citric acid are respectively weighed, added into 85 g of water, and stirred to make the solution uniform;
(3) Pouring the solution in the step (2) into the mixed powder in the step (1), kneading for 35 minutes at 30 ℃, extruding to form strips, so that the strips become cylindrical and are broken into strips with the length of 4 mm;
(4) Drying the strip-shaped object in the step (3) at 75 ℃ for 18 hours, drying the strip-shaped object at 100 ℃ for 10 hours, roasting the strip-shaped object at 220 ℃ for 1 hour, roasting the strip-shaped object at 470 ℃ for 2.5 hours, roasting the strip-shaped object at 820 ℃ for 3 hours, and cooling the strip-shaped object to obtain the prepared carrier containing the auxiliary agent;
(5) Respectively weighing 36.91 g of ammonium dichromate, 3.85 g of sodium nitrate, 2.04 g of strontium nitrate, 3.85 g of magnesium nitrate and 2.0 g of zinc nitrate, dissolving in 239 g of water (2.3 times of saturated adsorption quantity) to prepare uniform solution, loading the carrier containing the auxiliary agent prepared in the step (4) into an impregnating tank, putting into an oil bath, heating at a speed of 500 revolutions per minute, uniformly spraying the prepared solution from two ends of the impregnating tank by using a peristaltic pump until the temperature in the tank reaches 95 ℃, keeping the temperature in the tank at 95 ℃ after 138ml of impregnating solution is sprayed, and continuously rotating the impregnating tank at a speed of 500 revolutions per minute for 3 hours. Drying in a drying tank at 120 deg.C under vacuum-30 KPa for 2 hr, and roasting at 230 deg.C for 2 hr, 490 deg.C for 3.5 hr, and 700 deg.C for 5 hr;
(6) And (3) loading the catalyst precursor subjected to primary roasting in the step (5) into an impregnation tank, putting the impregnation tank into an oil bath, heating the impregnation tank in a rotating way at a speed of 500 revolutions per minute, continuously using a peristaltic pump to uniformly spray the rest impregnation solution from the two ends of the impregnation tank to the temperature in the tank, continuously maintaining the temperature in the tank at 95 ℃, and continuously rotating the impregnation tank at the speed of 500 revolutions per minute for 4 hours. Drying the drying pot at 120 ℃ under vacuum-30 KPa for 2 hours, and roasting at 230 ℃ for 2 hours, 490 ℃ for 3.5 hours and 700 ℃ for 5 hours. The prepared catalyst has the particle pressure measurement intensity of 245N/cm, the propane conversion rate of 62.8wt percent, the propylene selectivity of 86.7wt percent and the single-pass service life of 45min.
Of course, the present invention is capable of other various embodiments and its several details are capable of modification and variation in light of the present invention by one skilled in the art without departing from the spirit and scope of the invention.

Claims (10)

1. Propane dehydrogenation catalyst for fixed bed, wherein carrier of catalyst is Al 2 O 3 The active component is Cr 2 O 3 The method is characterized in that: the catalyst also contains an auxiliary agent WO 3 、ZrO 2 And Ga 2 O 3 Cr is calculated as 100% by weight of the catalyst 2 O 3 The content of (2) is 10-24%, preferably 18-22%, WO 3 The content of (2) is 1 to 5%, preferably 2.5 to 4%, zrO 2 The content of (C) is 0.001-0.5%, preferably 0.05-0.25%, ga 2 O 3 The content of (C) is 0.001-0.5%, preferably 0.03-0.15%.
2. The propane dehydrogenation catalyst for fixed bed according to claim 1, further comprising at least one of an alkali metal, an alkaline earth metal and a transition metal, preferably, based on 100% by weight of the catalyst, the oxide content of the alkali metal is about 0.5 to 3%, more preferably 0.85 to 2.2%, the oxide content of the alkaline earth metal is about 0.01 to 2%, more preferably 0.3 to 1.2%, the oxide content of the transition metal is 0.5 to 4%, more preferably 0.8 to 3%, and the balance Al 2 O 3 The method comprises the steps of carrying out a first treatment on the surface of the More preferably, the alkali metal is at least one selected from sodium and potassium; the alkaline earth metal is at least one of magnesium, calcium and strontium; the transition metal is at least one selected from molybdenum, cobalt, nickel, copper, zinc and vanadium.
3. A process for preparing the propane dehydrogenation catalyst for a fixed bed as defined in claim 1 or 2, characterized by comprising the steps of:
(1) Adding a pore-forming agent into the alumina powder to obtain mixed powder;
(2) Adding a tungsten precursor, a zirconium precursor, a gallium precursor, citric acid and nitric acid into water, and uniformly stirring to obtain a mixed solution;
(3) Adding the mixed solution into the mixed powder, kneading, extruding, forming, drying in sections, roasting in sections for the first time, and cooling to obtain a carrier containing an auxiliary agent;
(4) Dissolving chromium salt in water to obtain an impregnating solution;
(5) And uniformly spraying the impregnating solution on the carrier containing the auxiliary agent, curing, vacuum drying, carrying out secondary sectional roasting, and cooling to obtain the propane dehydrogenation catalyst for the fixed bed.
4. The method according to claim 3, further comprising the step of dissolving at least one of an alkali metal, an alkaline earth metal and a transition metal in water together with a chromium salt to obtain an impregnation liquid.
5. The method according to claim 3, wherein the mass ratio of the alumina powder to the pore-forming agent is 100:1 to 10.
6. The method according to claim 3, wherein in the step (2), the mass ratio of citric acid, nitric acid and water is 2-6:3-11:50-100, and the concentration of nitric acid is 50-68 wt%.
7. The method according to claim 3, wherein in the step (3), the kneading conditions are: the temperature is 10-40 ℃ and the time is 10-60 minutes; the catalyst is cylindrical or clover-shaped after the extrusion molding, and the strips are broken into strips with the length of 4-8 mm; the conditions of the sectional drying are as follows: drying at 60-100 deg.c for 3-24 hr and at 100-140 deg.c for 2-24 hr; the conditions of the first sectional roasting are as follows: roasting for 1-6 hours at 180-240 ℃, 1-4 hours at 460-500 ℃ and 2-6 hours at 750-900 ℃.
8. The method according to claim 3, wherein in the step (5), the amount of the impregnating solution is 1.0 to 1.2 times the saturated adsorption amount of the carrier, and the spraying conditions are as follows: the temperature of the carrier is 70-98 ℃, and the carrier rotates at a constant speed of 50-1000 rpm; the curing conditions are as follows: the temperature is 70-98 ℃ and the time is 2-8 hours; the conditions of the vacuum drying are as follows: the relative vacuum degree is-0.01 to-80 KPa, the temperature is 80-140 ℃ and the time is 1-24 hours; the conditions of the second sectional roasting are as follows: roasting for 1-10 hours at 180-240 ℃, 1-8 hours at 460-500 ℃ and 1-24 hours at 560-900 ℃.
9. The method according to claim 3, wherein the Al is 2 O 3 The powder is at least one of pseudo-boehmite and macroporous alumina; the pore-forming agent is at least one selected from sesbania powder, polyethylene glycol and carboxymethyl cellulose; and/or
The tungsten precursor is soluble tungsten salt, preferably ammonium metatungstate; the zirconium precursor is soluble zirconium salt, preferably zirconium nitrate; the gallium precursor is a soluble gallium salt, preferably gallium nitrate.
10. A method of preparing according to claim 3, wherein the chromium salt is selected from at least one of ammonium dichromate, chromium nitrate, chromium acetate; the alkali metal salt is at least one selected from sodium nitrate and potassium nitrate; the alkaline earth metal salt is at least one selected from magnesium nitrate, calcium nitrate and strontium nitrate; the transition metal salt is nitrate and/or ammonium salt of transition metal, preferably at least one selected from molybdenum nitrate, zinc nitrate, cobalt nitrate, nickel nitrate, copper nitrate and vanadium nitrate.
CN202210557315.0A 2022-05-20 2022-05-20 Propane dehydrogenation catalyst for fixed bed and preparation method thereof Pending CN117123212A (en)

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