CN115501871B - Propane dehydrogenation catalyst and preparation method and application thereof - Google Patents

Propane dehydrogenation catalyst and preparation method and application thereof Download PDF

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Publication number
CN115501871B
CN115501871B CN202110700054.9A CN202110700054A CN115501871B CN 115501871 B CN115501871 B CN 115501871B CN 202110700054 A CN202110700054 A CN 202110700054A CN 115501871 B CN115501871 B CN 115501871B
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catalyst
roasting
group
carrier
drying
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CN115501871A (en
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吴省
洪学思
缪长喜
宋磊
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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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
    • 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
    • B01J23/26—Chromium
    • 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
    • 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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  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention discloses a propane dehydrogenation catalyst and a preparation method and application thereof. The catalyst comprises: taking alumina containing IVB group elements as a carrier, cr or oxide thereof as an active component, and IA group and/or IIA group elements or oxide thereof as an auxiliary component; wherein, the catalyst passes TPR test, and alloy peaks of IVB group element and active component Cr element appear in the range of 380-580 ℃. The catalyst is suitable for propane dehydrogenation reaction, and mainly solves the problems of low activity and stability of the catalyst prepared by the prior art.

Description

Propane dehydrogenation catalyst and preparation method and application thereof
Technical Field
The invention belongs to the field of petrochemical industry, and particularly relates to a catalyst for preparing propylene by propane dehydrogenation, a preparation method thereof and application of the catalyst in preparing propylene by propane dehydrogenation.
Background
Propylene is used as an important chemical raw material and can be used for producing polypropylene, acrylonitrile, epoxypropane, acrylic acid, isopropanol and the like. Propylene is mainly derived from steam cracking and catalytic cracking byproducts, but is limited by the main production of ethylene and gasoline and diesel oil, and the yield is limited to increase, and meanwhile, the demand of polypropylene is still in a continuously rising trend, so that a method for preparing propylene by dehydrogenation reaction by taking propane as a raw material is greatly developed in various countries of the world. The propane dehydrogenation reaction is a strong endothermic reaction, is limited by thermodynamic equilibrium, can obtain more ideal propylene yield under the conditions of low pressure and high temperature, and the excessive reaction temperature can aggravate the propane cracking reaction and deep dehydrogenation, so that the catalyst performance is poor, the selectivity is lower, and the like.
The catalyst system adopted in the propane dehydrogenation technology is mainly Pt-based catalyst and Cr-based catalyst. The Pt-based catalyst is used for dehydrogenating low-carbon alkane, has the advantages of environmental friendliness, higher activity and the like, but has higher price, more complex preparation and higher requirement on the purity of reaction raw materials. The Cr-based catalyst has low price, relatively high activity and lower requirement on raw material purity, but has certain influence on the environment, the reaction process needs frequent regeneration, the regeneration and other conditions are harsh, and the performance requirement on each aspect of the Cr-based catalyst is higher.
CN103769156a uses ammonia gas treated alumina as carrier, cr as active component, and potassium, manganese, cobalt, iron, nickel, etc. as auxiliary agents. The preparation method of the dehydrogenation catalyst comprises the steps of adopting ammonia gas to pretreat an alumina carrier; potassium and auxiliary agents are loaded by a co-impregnation method, and then the active component chromium is impregnated. The catalyst has better selectivity, but relatively low activity. CN101940922B discloses a low-carbon alkane dehydrogenation catalyst and a preparation method thereof, wherein chromium is used as an active metal component, a part of chromium is mixed with pseudo-boehmite to prepare a chromium-containing alumina carrier, and a part of chromium and an auxiliary agent alkali metal are impregnated and loaded on the chromium-containing alumina carrier to prepare the dehydrogenation catalyst. The catalyst prepared by the method has low content of active components on the outer surface of the carrier, low activity and low utilization rate of the active components in the carrier, and the overall stability of the catalyst is reduced after the active components on the outer surface migrate. CN103769078A discloses a catalyst for preparing olefin by dehydrogenating light alkane, a preparation method and application thereof. The catalyst is prepared by using Al 2 O 3 The catalyst is a carrier, takes chromium as an active component and takes alkali metal as a promoting component, wherein the active component chromium is impregnated on the alumina carrier step by step before the alkali metal promoting component is impregnated and after the alkali metal promoting component is impregnated. The stability of the catalyst is still to be further improved.
At present, although the existing Cr-based dehydrogenation catalysts have been greatly developed, the problems of low catalyst activity, poor stability and the like still exist.
Disclosure of Invention
The invention provides a propane dehydrogenation catalyst, a preparation method and application thereof, and aims to solve the problems of low activity and poor stability of Cr dehydrogenation catalysts in the prior art. The catalyst is used in the propylene preparing process of propane dehydrogenation, and has good activity and outstanding stability effect.
The first aspect of the present invention provides a propane dehydrogenation catalyst comprising: taking alumina containing IVB group elements as a carrier, cr or oxide thereof as an active component, and IA group and/or IIA group elements or oxide thereof as an auxiliary component; wherein, the catalyst passes TPR test, and alloy peaks of IVB group element and active component Cr element appear in the range of 380-580 ℃.
Further, the catalyst passes the TPR test, and obvious alloy peaks of IVB element and active component Cr element appear in the range of 380-580 ℃.
Further, the catalyst comprises the following components in parts by weight:
a) 10-30 parts of Cr element or oxide thereof;
b) 0.1 to 5 parts of auxiliary components, namely at least one element or oxide thereof selected from elements of group IA and/or group IIA;
c) 60-90 parts of carrier;
the carrier contains 0.1-5 parts of an element selected from group IVB or an oxide thereof.
Further, the group IVB element is selected from any one or two of Ti and Zr.
Further, the carrier preferably contains 0.5 to 3.0 parts of an element selected from group IVB or an oxide thereof.
Further, the group IA element is selected from any one or more of Li, na, K, cs, preferably Na and/or K.
Further, the group IIA element is selected from any one or two of Mg and Ca.
Further, the content of the auxiliary component in the catalyst is preferably 0.1 to 3.0 parts, more preferably 0.1 to 2.0 parts.
Further, the alumina carrier containing the IVB group element is prepared by adopting a mixing method, and the specific preparation process is as follows: the alumina precursor and the compound containing the IVB group element are made into a molded body, and the molded body is dried and roasted to obtain the alumina carrier containing the IVB group element.
Further, the catalyst is obtained by loading part of active component Cr on an alumina carrier containing IVB element, carrying out first roasting, loading the rest part of active component Cr and auxiliary component, and carrying out second roasting. The load is an impregnation method, wherein the IVB element is introduced into the carrier by a mixing method.
The second aspect of the present invention provides a method for preparing the propane dehydrogenation catalyst, comprising:
(1) Preparing an alumina carrier containing IVB group elements, wherein the IVB group elements are introduced into the carrier by adopting a mixing method;
(2) Preparing a first Cr-containing compound and an acidic substance into an impregnating solution I, and preparing a second Cr-containing compound and an auxiliary agent-containing compound into an impregnating solution II;
(3) Impregnating the carrier in the step (1) by using the impregnating solution I, and obtaining a catalyst intermediate through first drying and first roasting;
(4) And (3) impregnating the catalyst intermediate in the step (3) with the impregnating solution II, and obtaining the propane dehydrogenation catalyst through second drying and second roasting.
Further, the carrier in the step (1) is prepared by introducing elements of IVB group into the carrier by adopting a mixing method, and the specific preparation process is as follows: the alumina precursor (such as one or more of gibbsite, bayerite, pseudo-boehmite, diaspore, etc.) and compound containing IVB group element are made into shaped body, and then dried and roasted to obtain the alumina carrier containing IVB group element. The group IVB-containing compound may be a soluble compound such as a nitrate. The molding may be performed by a conventional molding method such as extrusion molding, screw extrusion molding, or the like. In the molding process, molding aids (such as sesbania powder, hydroxymethyl cellulose, peptizing agent, binder and the like) can be added. The molding may be of conventional shape, such as bar, column, etc. The drying and roasting are carried out under an oxygen-containing atmosphere (such as air), and the drying conditions are as follows: the drying temperature is 80-180 ℃ and the drying time is 2-24 h. The roasting conditions are as follows: the roasting temperature is 500-900 ℃ and the roasting time is 2-12 h.
Further, in step (2), the first Cr-containing compound and the second Cr-containing compound are each independently selected from at least one of soluble compounds such as nitrate, sulfate, chromate.
Further, in the step (2), the acidic substance is at least one selected from nitric acid, formic acid, acetic acid, adipic acid, oxalic acid, maleic acid and the like.
Further, in the step (2), the auxiliary-containing compound is selected from soluble compounds, wherein the group IA element-containing compound may be selected from at least one of nitrate, chloride or sulfate, and the group IIA element-containing compound may be selected from at least one of nitrate, chloride.
Further, in the step (2), the first Cr-containing compound and the acidic substance are prepared into the impregnating solution I, wherein the mass concentration of the acidic substance is 1.5% -10%, and the mass concentration of Cr is 7% -30%. The impregnating solution is preferably an aqueous solution.
Further, in the step (2), the second Cr-containing compound and the auxiliary agent-containing compound are prepared into an impregnating solution II, wherein the mass concentration of the auxiliary agent in terms of elements is 0.4% -3.5%, and the mass concentration of Cr is 5% -20%. The impregnating solution is preferably an aqueous solution.
Further, the mass ratio of the amount of Cr introduced into the catalyst through the immersion liquid I to the amount of Cr introduced into the catalyst through the immersion liquid II is 1 to 3:1.
further, the impregnation in the step (3) may be a conventional impregnation method, preferably an isovolumetric impregnation method.
Further, the drying and calcining in step (3) is performed under an oxygen-containing atmosphere (such as air), and the first drying conditions are as follows: the drying temperature is 80-160 ℃, the drying time is 2-24 h, and the first roasting condition is as follows: the roasting temperature is 550-800 ℃ and the roasting time is 1-10 h.
Further, the impregnation in the step (4) may be a conventional impregnation method, preferably an isovolumetric impregnation method.
Further, the drying and firing in step (4) is performed under an oxygen-containing atmosphere (such as air), and the second drying conditions are as follows: the drying temperature is 80-150 ℃, the drying time is 1-16 h, and the second roasting condition is as follows: the roasting temperature is 600-800 ℃ and the roasting time is 2-15 h.
The third aspect of the invention provides an application of the propane dehydrogenation catalyst in preparing propylene by propane dehydrogenation.
Further, the application process is as follows: and (3) contacting propane with the catalyst to react to obtain propylene.
Further, the reaction conditions were as follows: the reaction temperature is 550-620 ℃, the reaction pressure is 0.05-0.1 MPa, and the volume space velocity of propane is 0.4-1.0 h -1 。
Compared with the prior art, the invention has the following beneficial effects:
1. the inventor has found through a great deal of research that when the IVB element and part of Cr exist in an alloy form in the propane dehydrogenation catalyst, the IVB element and the rest Cr and the auxiliary agent are matched, so that the propane dehydrogenation catalyst has outstanding activity and stability. The invention relates to a propane dehydrogenation catalyst, which comprises the steps of firstly introducing IVB elements into a carrier by adopting a mixing method to prepare an alumina carrier containing the IVB elements, loading an active component Cr part and an impregnating solution I prepared from acidic substances on the carrier to obtain a catalyst intermediate, loading the rest active component Cr and an auxiliary component into the impregnating solution II on the catalyst intermediate, and fully contacting the active component Cr in the catalyst intermediate with the IVB elements in the carrier to form an alloy peak under high-temperature roasting; the re-impregnated small amount of active component Cr is distributed on the outer surface of the catalyst, so that the existence of the alloy prevents the transformation or migration of part of active component Cr crystal phase to stabilize the catalyst.
2. The propane dehydrogenation catalyst is used in the propylene preparation process of propane dehydrogenation, the conversion rate and the selectivity are basically unchanged after the reaction is carried out for 1 hour, and the conversion rate and the selectivity are basically unchanged after repeated regeneration and the total evaluation of the catalyst is 200 hours.
Drawings
FIG. 1 is a TPR chart of a catalyst sample 1 obtained in example 1;
FIG. 2 is a TPR chart of catalyst sample 5 obtained in example 5;
FIG. 3 is a TPR chart of a catalyst sample 8 obtained in comparative example 1;
FIG. 4 is a TPR chart of a catalyst sample 9 obtained in comparative example 2.
Detailed Description
In the invention, TPR test is carried out by adopting AUTOCHEM II 2920 of America microphone company, and the temperature range is as follows: room temperature to 1100 ℃; rate of temperature rise: 50 ℃/min (< 500 ℃), 30 ℃/min (500 ℃ to 750 ℃); gas: h 2 The method comprises the steps of carrying out a first treatment on the surface of the Flow rate: 0.5-100 mL/min. In the present invention, the peak height value of the alloy peak (denoted as peak 1) in which zirconium and the Cr element as an active component appear in the range of 380 to 580 ℃ in the catalyst sample 1 obtained in example 1 was set to 100%. In the invention, no peak with a peak height value of 5% larger than the peak 1 in the range of 380-580 ℃ is an alloy peak with no obvious IVB group element and active component Cr element in the range of 380-580 ℃, and a peak with a peak height value of 5% larger than the peak 1 in the range of 380-580 ℃ is an alloy peak with obvious IVB group element and active component Cr element in the range of 380-580 ℃.
In the examples of the present invention and the comparative examples,
conversion (%) of propane= (mass of propane in reactant-mass of propane in reaction product)/(mass of propane in reactant x 100%;
selectivity (%) of propylene=actual yield of propylene +.theoretical yield of propylene x 100% by mass.
In the examples and comparative examples of the present invention, analysis of the gas composition in the propane dehydrogenation reaction was performed on a gas chromatograph available from Agilent company under the model number 7890A.
The following describes the technical scheme of the present invention in detail by referring to examples, but the scope of the present invention is not limited by the examples.
Example 1
Extrusion molding of a carrier and preparation of a catalyst:
(1) 300g of pseudo-boehmite and 10.5g of zirconium nitrate are weighed, and meanwhile, the weight ratio of the pseudo-boehmite to nitric acid, sesbania powder and deionized water is 300:9:9:220, weighing corresponding raw materials, adding the raw materials into a kneader, and kneading for 30min at a rotational speed of 300 rpm to obtain dough. The materials are put into a sleeve of a single screw extruder, and a strip cylinder with the diameter phi of 3mm is extruded under the pressure of 10 MPa. Placing the extruded material at room temperature for 24 hours, drying for 8 hours in a drying oven at 100 ℃, and then transferring into a muffle furnace at 600 ℃ for roasting for 2 hours to obtain a cylindrical carrier (the mass content of zirconia in the carrier is 1%) with Zr modification, phi 2.9-3 mm and length of 4-6 mm.
(2) 52.65g of chromium nitrate, 2g of nitric acid, was weighed and dissolved in 50g of deionized water to obtain an impregnating solution I. In addition, 26.3g of chromium nitrate, 1.71g of sodium carbonate was weighed and dissolved in 50g of deionized water to obtain an impregnating solution II.
(3) And (3) immersing the impregnating solution I in the step (2) into 100g of the cylindrical carrier after roasting in the step (1), roasting for 4 hours in a 100 ℃ oven, and then transferring into a 600 ℃ muffle furnace for roasting for 1 hour to obtain the catalyst intermediate.
(4) And (3) impregnating the catalyst intermediate in the step (3) by using the impregnating solution II in the step (2), putting the impregnated sample into a baking oven at 150 ℃ for 4 hours, and then transferring the impregnated sample into a muffle furnace at 600 ℃ for baking for 8 hours to obtain a catalyst sample 1.
The TPR test results of catalyst sample 1 are shown in FIG. 1, and obvious alloy peaks of zirconium and active component Cr element appear in the range of 380-580 ℃.
Evaluation of the catalyst sample 1 performance:
the propane dehydrogenation reaction of sample 1 was performed by the following method, and the content of each component was analyzed by gas chromatography on the gas before and after the reaction. The method comprises the steps of regulating flow of pure propane gas through a mass flowmeter, preheating the pure propane gas in a preheating zone, then entering a reaction zone, heating a heating section and a reaction section of a reactor by adopting electric heating wires to enable the pure propane gas to reach a preset temperature, and enabling the inside diameter of the reactor to be a quartz tube with the diameter phi 12mm and the outside diameter phi 20mm and the length of the reactor to be 600mm. The reacted gas was passed through a condensing tank and then subjected to gas chromatography to analyze its composition. Isothermal fixed bed reactorThe medium catalyst evaluation conditions were as follows: 10g of catalyst is filled into the isothermal fixed bed reactor, the reaction pressure is normal pressure, and the gas mass space velocity is 0.7h -1 The reaction temperature was 580 ℃. The contents of the components were analyzed by gas chromatography for the gases reacted for 10min and 1h, respectively, and the conversion of propane and the selectivity of propylene were calculated. The evaluation results of the catalyst are shown in Table 1. After the catalyst is reacted for 1 hour, the reaction is stopped, and then the catalyst is regenerated by high-temperature roasting at 650 ℃ for 2 hours. The regenerated catalyst was evaluated under the same evaluation conditions as described above. The above regeneration process and evaluation process were repeated. The catalyst was evaluated for 200 hours in total, and the results of the conversion of propane and the selectivity for propylene at 200h after regeneration are shown in Table 1.
Example 2
Extrusion molding of a carrier and preparation of a catalyst:
(1) 300g of gibbsite and 31.5g of zirconium nitrate are weighed, and meanwhile, the weight ratio of the gibbsite to nitric acid, sesbania powder and deionized water is 300:12:12:230, weighing corresponding raw materials, adding the raw materials into a kneader, wherein the rotation speed of the kneader is 300 revolutions per minute, and the kneading time is 20 minutes, so that the dough is formed. The materials are put into a sleeve of a single screw extruder, and a strip cylinder with the diameter phi of 3mm is extruded under the pressure of 10 MPa. Placing the extruded material at room temperature for 24 hours, drying for 8 hours in an oven at 80 ℃, and then transferring into a muffle furnace at 600 ℃ for roasting for 4 hours to obtain a cylindrical carrier (the mass content of zirconia in the carrier is 3%) with Zr modification, phi 2.9-3 mm and length of 4-6 mm.
(2) 35.1g of chromium nitrate, 3g of nitric acid, was weighed and dissolved in 50g of deionized water to obtain an impregnating solution I. In addition, 17.55g of chromium nitrate, 5.13g of sodium carbonate was weighed and dissolved in 50g of deionized water to obtain an impregnating solution II.
(3) And (3) immersing the impregnating solution I in the step (2) into 100g of the cylindrical carrier after roasting in the step (1), roasting for 2 hours in a baking oven at 150 ℃, and then transferring into a muffle furnace at 600 ℃ for roasting for 2 hours to obtain the catalyst intermediate.
(4) And (3) impregnating the catalyst intermediate in the step (3) by using the impregnating solution II in the step (2), putting the impregnated sample into a baking oven at 150 ℃ for treatment for 1h, and then transferring the impregnated sample into a muffle furnace at 600 ℃ for baking for 12h to obtain a catalyst sample 2.
From the TPR test results of the catalyst sample 2, it was found that distinct alloy peaks of zirconium and Cr element as an active component appear in the range of 380 to 580 ℃.
Evaluation of catalyst sample 2 performance: the catalyst evaluation device and the evaluation conditions were the same as in example 1 by the regeneration method, and the catalyst evaluation results are shown in table 1.
Example 3
Extrusion molding of a carrier and preparation of a catalyst:
(1) 300g of pseudo-boehmite and 5.3g of zirconium nitrate are weighed, and meanwhile, the weight ratio of the pseudo-boehmite to nitric acid, sesbania powder and deionized water is 300:12:9:230, weighing corresponding raw materials, adding the raw materials into a kneader, wherein the rotation speed of the kneader is 300 revolutions per minute, and the kneading time is 10 minutes, so that the dough is formed. The materials are put into a sleeve of a single screw extruder, and a strip cylinder with the diameter phi of 3mm is extruded under the pressure of 10 MPa. The extruded material is placed at room temperature for 24 hours, then is dried for 8 hours in an oven at 80 ℃, and is then transferred into a muffle furnace at 600 ℃ for roasting for 4 hours, thus obtaining a cylindrical carrier (the mass content of zirconia in the carrier is 0.5%) with Zr modification, phi 2.9-3 mm and length of 4-6 mm.
(2) 70.2g of chromium nitrate, 5g of nitric acid, was weighed and dissolved in 50g of deionized water to obtain an impregnating solution I. In addition, 35.1g of chromium nitrate, 1.37g of sodium nitrate was weighed and dissolved in 50g of deionized water to obtain an immersion liquid II.
(3) And (3) immersing the impregnating solution I in the step (2) into 100g of the cylindrical carrier after roasting in the step (1), roasting in a baking oven at 100 ℃ for 2 hours, and then transferring into a muffle furnace at 650 ℃ for roasting for 2 hours to obtain the catalyst intermediate.
(4) And (3) impregnating the catalyst intermediate in the step (3) by using the impregnating solution II in the step (2), putting the impregnated sample into a baking oven at 150 ℃ for treatment for 1h, and then transferring the impregnated sample into a muffle furnace at 750 ℃ for roasting for 6h to obtain a catalyst sample 3.
From the TPR test result of the catalyst sample 3, it was found that distinct alloy peaks of zirconium and Cr element as an active component appear in the range of 380 to 580 ℃.
Evaluation of catalyst sample 3 performance: the catalyst evaluation device and the evaluation conditions were the same as in example 1 by the regeneration method, and the catalyst evaluation results are shown in table 1.
Example 4
Extrusion molding of a carrier and preparation of a catalyst:
(1) 300g of Bayer stone and 1.1g of zirconium nitrate are weighed, and meanwhile, the weight ratio of the Bayer stone to nitric acid, sesbania powder and deionized water is 300:12:15:210, weighing corresponding raw materials, adding the raw materials into a kneader, and kneading for 30min at a rotational speed of 300 rpm to obtain dough. The materials are put into a sleeve of a single screw extruder, and a strip cylinder with the diameter phi of 3mm is extruded under the pressure of 10 MPa. Placing the extruded material at room temperature for 24 hours, drying the extruded material in a drying oven at 100 ℃ for 12 hours, and then transferring the dried material into a muffle furnace at 800 ℃ for roasting for 8 hours to obtain a cylindrical carrier (the mass content of zirconia in the carrier is 0.1%) with Zr modification, phi 2.9-3 mm and length of 4-6 mm.
(2) 105.3g of chromium nitrate, 5g of nitric acid, was weighed and dissolved in 60g of deionized water to obtain an impregnating solution I. 52.65g of chromium nitrate, 8.55g of sodium carbonate was weighed and dissolved in 50g of deionized water to obtain an immersion liquid II.
(3) And (3) immersing the impregnating solution I in the step (2) into 100g of the cylindrical carrier after roasting in the step (1), roasting for 6 hours in a 140 ℃ oven, and then transferring into a 700 ℃ muffle furnace for roasting for 3 hours to obtain the catalyst intermediate.
(4) And (3) impregnating the catalyst intermediate in the step (3) by using the impregnating solution II in the step (2), putting the impregnated sample into a baking oven at 150 ℃ for treatment for 1h, and then transferring the impregnated sample into a muffle furnace at 800 ℃ for baking for 12h to obtain a catalyst sample 4.
From the TPR test result of the catalyst sample 4, it was found that distinct alloy peaks of zirconium and Cr element as an active component appear in the range of 380 to 580 ℃.
Evaluation of catalyst sample 4 performance: the catalyst evaluation device and the evaluation conditions were the same as in example 1 by the regeneration method, and the catalyst evaluation results are shown in table 1.
Example 5
Extrusion molding of a carrier and preparation of a catalyst:
(1) 300g of pseudo-boehmite and 9.0g of titanium nitrate are weighed, and meanwhile, the weight ratio of the pseudo-boehmite to nitric acid, sesbania powder and deionized water is 300:9:9:220, weighing corresponding raw materials, adding the raw materials into a kneader, and kneading for 30min at a rotational speed of 300 rpm to obtain dough. The materials are put into a sleeve of a single screw extruder, and a strip cylinder with the diameter phi of 3mm is extruded under the pressure of 10 MPa. Placing the extruded material at room temperature for 24 hours, drying for 6 hours in a drying oven at 100 ℃, and then transferring into a muffle furnace at 600 ℃ for roasting for 4 hours to obtain the cylindrical carrier (the mass content of titanium oxide in the carrier is 1%) with Ti modified, phi 2.9-3 mm and length of 4-6 mm.
(2) 35.1g of chromium nitrate, 4g of nitric acid was weighed and dissolved in 50g of deionized water to obtain an impregnating solution I. In addition, 17.55g of chromium nitrate, 5.13g of sodium carbonate was weighed and dissolved in 50g of deionized water to obtain an impregnating solution II.
(3) And (3) immersing the impregnating solution I in the step (2) into 100g of the cylindrical carrier after roasting in the step (1), roasting for 2 hours in a baking oven at 150 ℃, and then transferring into a muffle furnace at 600 ℃ for roasting for 2 hours to obtain the catalyst intermediate.
(4) And (3) impregnating the catalyst intermediate in the step (3) by using the impregnating solution II in the step (2), putting the impregnated sample into a baking oven at 150 ℃ for treatment for 1h, and then transferring the impregnated sample into a muffle furnace at 600 ℃ for baking for 12h to obtain a catalyst sample 5.
From the TPR test result of the catalyst sample 5, it was found that distinct alloy peaks of titanium and Cr element as an active component appear in the range of 380 to 580 ℃.
Evaluation of the catalyst sample 5 performance: the catalyst evaluation device and the evaluation conditions were the same as in example 1 by the regeneration method, and the catalyst evaluation results are shown in table 1.
Example 6
Extrusion molding of a carrier and preparation of a catalyst:
(1) 300g of pseudo-boehmite and 10.5g of zirconium nitrate are weighed, and meanwhile, the weight ratio of the pseudo-boehmite to nitric acid, sesbania powder and deionized water is 300:9:9:220, weighing corresponding raw materials, adding the raw materials into a kneader, and kneading for 30min at a rotational speed of 300 rpm to obtain dough. The materials are put into a sleeve of a single screw extruder, and a strip cylinder with the diameter phi of 3mm is extruded under the pressure of 10 MPa. Placing the extruded material at room temperature for 24 hours, drying for 8 hours in a baking oven at 120 ℃, and then transferring into a muffle furnace at 600 ℃ for roasting for 4 hours to obtain a cylindrical carrier (the mass content of zirconia in the carrier is 1%) with Zr modification, phi 2.9-3 mm and length of 4-6 mm.
(2) 35.1g of chromium nitrate, 2g of nitric acid was weighed and dissolved in 50g of deionized water to obtain an impregnating solution I. In addition, 17.55g of chromium nitrate, 2.15g of potassium nitrate was weighed and dissolved in 50g of deionized water to obtain an immersion liquid II.
(3) And (3) immersing the impregnating solution I in the step (2) into 100g of the cylindrical carrier after roasting in the step (1), roasting for 2 hours in a 100 ℃ oven, and then transferring into a 550 ℃ muffle furnace for roasting for 2 hours to obtain the catalyst intermediate.
(4) And (3) impregnating the catalyst intermediate in the step (3) by using the impregnating solution II in the step (2), putting the impregnated sample into a 100 ℃ oven for treatment for 4 hours, and then transferring the impregnated sample into a 750 ℃ muffle furnace for roasting for 6 hours to obtain a catalyst sample 6.
From the TPR test result of the catalyst sample 6, it was found that distinct alloy peaks of zirconium and Cr element as an active component appear in the range of 380 to 580 ℃.
Evaluation of catalyst sample 6 performance: the catalyst evaluation device and the evaluation conditions were the same as in example 1 by the regeneration method, and the catalyst evaluation results are shown in table 1.
Example 7
Extrusion molding of a carrier and preparation of a catalyst:
(1) 300g of pseudo-boehmite and 10.5g of zirconium nitrate are weighed, and meanwhile, the weight ratio of the pseudo-boehmite to acetic acid, sesbania powder and deionized water is 300:15:9:220, weighing corresponding raw materials, adding the raw materials into a kneader, and kneading for 30min at a rotational speed of 300 rpm to obtain dough. The materials are put into a sleeve of a single screw extruder, and a strip cylinder with the diameter phi of 3mm is extruded under the pressure of 10 MPa. Placing the extruded material at room temperature for 24 hours, drying for 8 hours in a baking oven at 120 ℃, and then transferring into a muffle furnace at 600 ℃ for roasting for 4 hours to obtain a cylindrical carrier (the mass content of zirconia in the carrier is 1%) with Zr modification, phi 2.9-3 mm and length of 4-6 mm.
(2) 35.1g of chromium nitrate, 2g of nitric acid was weighed and dissolved in 50g of deionized water to obtain an impregnating solution I. In addition, 17.55g of chromium nitrate, 2.93g of calcium nitrate was weighed and dissolved in 50g of deionized water to obtain an immersion liquid II.
(3) And (3) immersing the impregnating solution I in the step (2) into 100g of the cylindrical carrier after roasting in the step (1), roasting for 4 hours in a 110 ℃ oven, and then transferring into a 650 ℃ muffle furnace for roasting for 3 hours to obtain the catalyst intermediate.
(4) And (3) impregnating the catalyst intermediate in the step (3) by using the impregnating solution II in the step (2), putting the impregnated sample into a 100 ℃ oven for treatment for 4 hours, and then transferring the impregnated sample into a 750 ℃ muffle furnace for roasting for 6 hours to obtain a catalyst sample 7.
From the TPR test result of the catalyst sample 7, it was found that distinct alloy peaks of zirconium and Cr element as an active component appear in the range of 380 to 580 ℃.
Evaluation of the catalyst sample 7 performance: the catalyst evaluation device and the evaluation conditions were the same as in example 1 by the regeneration method, and the catalyst evaluation results are shown in table 1.
Comparative example 1
Coprecipitation preparation, molding and catalyst preparation of a carrier:
(1) 1000g of aluminum sol with 30% of solid content and 10.5g of zirconium nitrate are mixed to prepare a mixture I, the mixture I and ammonia water are subjected to concurrent precipitation, the pH value is controlled to be 9, and after the precipitation is finished, the mixture I is washed and dried in a drying oven at 100 ℃ for 8 hours to obtain a dried product. The dried product, nitric acid, sesbania powder and deionized water are added into a kneader according to the proportion of the embodiment 1, the rotating speed of the kneader is 300 revolutions per minute, and the kneading time is 30 minutes, so that the dough shape is formed. The materials are put into a sleeve of a single screw extruder, and a strip cylinder with the diameter phi of 3mm is extruded under the pressure of 10 MPa. Placing the extruded material at room temperature for 24 hours, drying for 8 hours in a drying oven at 100 ℃, and then transferring into a muffle furnace at 600 ℃ for roasting for 2 hours to obtain a cylindrical carrier (the mass content of zirconia in the carrier is 1%) with Zr modification, phi 2.9-3 mm and length of 4-6 mm.
(2) 52.65g of chromium nitrate, 2g of nitric acid, was weighed and dissolved in 50g of deionized water to obtain an impregnating solution I. In addition, 26.3g of chromium nitrate, 1.71g of sodium carbonate was weighed and dissolved in 50g of deionized water to obtain an impregnating solution II.
(3) And (3) immersing the impregnating solution I in the step (2) into 100g of the cylindrical carrier after roasting in the step (1), roasting for 4 hours in a 100 ℃ oven, and then transferring into a 600 ℃ muffle furnace for roasting for 1 hour to obtain the catalyst intermediate.
(4) And (3) impregnating the catalyst intermediate in the step (3) by using the impregnating solution II in the step (2), putting the impregnated sample into a baking oven at 150 ℃ for 4 hours, and then transferring the impregnated sample into a muffle furnace at 600 ℃ for baking for 8 hours to obtain a catalyst sample 8.
The TPR test results from catalyst sample 8 are shown in FIG. 2, and no significant peak appears in the range of 380 to 580 ℃.
Evaluation of catalyst sample 8 performance: the catalyst evaluation device and the evaluation conditions were the same as in example 1 by the regeneration method, and the catalyst evaluation results are shown in table 1.
Comparative example 2
Extrusion molding of a carrier and preparation of a catalyst:
(1) Weighing 300g of pseudo-boehmite according to the weight ratio of the pseudo-boehmite to nitric acid, sesbania powder and deionized water of 300:9:9:220, weighing corresponding raw materials, adding the raw materials into a kneader, and kneading for 30min at a rotational speed of 300 rpm to obtain dough. The materials are put into a sleeve of a single screw extruder, and a strip cylinder with the diameter phi of 3mm is extruded under the pressure of 10 MPa. Placing the extruded material at room temperature for 24 hours, then drying the extruded material in a drying oven at 100 ℃ for 6 hours, and then transferring the extruded material into a muffle furnace at 650 ℃ for roasting for 4 hours to obtain the cylindrical carrier with the diameter of 2.9-3 mm and the length of 4-6 mm.
(2) 35.1g of chromium nitrate, 10.5g of zirconium nitrate and 2g of nitric acid are weighed and dissolved in 50g of deionized water to obtain an impregnating solution I. In addition, 17.55g of chromium nitrate, 2.15g of potassium nitrate was weighed and dissolved in 50g of deionized water to obtain an immersion liquid II.
(3) And (3) immersing the impregnating solution I in the step (2) into 100g of the cylindrical carrier after roasting in the step (1), roasting for 2 hours in a 100 ℃ oven, and then transferring into a 550 ℃ muffle furnace for roasting for 2 hours to obtain the catalyst intermediate.
(4) And (3) impregnating the catalyst intermediate in the step (3) by using the impregnating solution II in the step (2), putting the impregnated sample into a 100 ℃ oven for treatment for 4 hours, and then transferring the impregnated sample into a 750 ℃ muffle furnace for roasting for 6 hours to obtain a catalyst sample 9. The TPR diagram is shown in FIG. 4.
The TPR test results from catalyst sample 9 are shown in FIG. 3, and no significant peak appears in the range of 380 to 580 ℃.
Evaluation of the catalyst sample 9 performance: the catalyst evaluation device and the evaluation conditions were the same as in example 1 by the regeneration method, and the catalyst evaluation results are shown in table 1.
TABLE 1
The above describes in detail the specific embodiments of the present invention, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.

Claims (14)

1. A propane dehydrogenation catalyst comprising: taking alumina containing IVB group elements as a carrier, cr or oxide thereof as an active component, and IA group and/or IIA group elements or oxide thereof as an auxiliary component; wherein, the catalyst passes TPR test, and alloy peaks of IVB group element and active component Cr element appear in the range of 380-580 ℃;
the catalyst is obtained by loading part of active component Cr on an alumina carrier containing IVB element, roasting, loading the rest part of active component Cr and auxiliary agent component, and roasting, wherein the IVB element is introduced into the carrier by adopting a mixing method.
2. The catalyst according to claim 1, characterized in that it comprises, in parts by weight:
a) 10-30 parts of Cr element or oxide thereof;
b) 0.1 to 5 parts of auxiliary components, namely at least one element or oxide thereof selected from elements of group IA and/or group IIA;
c) 60-90 parts of carrier;
the carrier contains 0.1-5 parts of an element selected from group IVB or an oxide thereof.
3. The catalyst according to claim 1 or 2, wherein the group IVB element is selected from any one or both of Ti and Zr;
and/or group IA elements selected from any one or more of Li, na, K, cs;
and/or the group IIA element is selected from any one or two of Mg and Ca.
4. Catalyst according to claim 1 or 2, characterized in that the group IA element is selected from Na and/or K;
5. the catalyst according to claim 1, wherein the content of the auxiliary component in the catalyst is 0.1 to 3.0 parts;
and/or the carrier contains 0.5-3.0 parts of an element selected from group IVB or an oxide thereof.
6. The catalyst according to claim 1, wherein the content of the auxiliary component in the catalyst is 0.1 to 2.0 parts.
7. A process for preparing a propane dehydrogenation catalyst as defined in any one of claims 1-6 comprising:
(1) Preparing an alumina carrier containing IVB group elements, wherein the IVB group elements are introduced into the carrier by adopting a mixing method;
(2) Preparing a first Cr-containing compound and an acidic substance into an impregnating solution I, and preparing a second Cr-containing compound and an auxiliary agent-containing compound into an impregnating solution II;
(3) Impregnating the carrier in the step (1) by using the impregnating solution I, and obtaining a catalyst intermediate through first drying and first roasting;
(4) And (3) impregnating the catalyst intermediate in the step (3) with the impregnating solution II, and obtaining the propane dehydrogenation catalyst through second drying and second roasting.
8. The method of claim 7, wherein the step (1) of preparing the carrier comprises: preparing an alumina precursor and a compound containing IVB elements into a molded body, and drying and roasting to obtain an alumina carrier containing IVB elements; the drying and roasting are carried out in an oxygen-containing atmosphere, and the drying conditions are as follows: the drying temperature is 80-180 ℃ and the drying time is 2-24 h; the roasting conditions are as follows: the roasting temperature is 500-900 ℃ and the roasting time is 2-12 h.
9. The method of claim 7, wherein in step (2), the first Cr-containing compound and the second Cr-containing compound are each independently selected from soluble compounds;
and/or in the step (2), the compound containing the group IA element is selected from at least one of nitrate, chloride or sulfate, and the compound containing the group IIA element is selected from at least one of nitrate and chloride.
10. The method according to claim 9, wherein the soluble compound is at least one selected from the group consisting of nitrate, sulfate and chromate.
11. The process according to claim 7, wherein in the step (2), the acidic substance is at least one selected from the group consisting of nitric acid, formic acid, acetic acid, adipic acid, oxalic acid and maleic acid; in the impregnating solution I, the mass concentration of acidic substances is 1.5-10%, and the mass concentration of Cr is 7-30%;
and/or, in the impregnating solution II, the mass concentration of the auxiliary agent in terms of elements is 0.4-3.5%, and the mass concentration of Cr is 5-20%;
and/or the mass ratio of the amount of Cr introduced into the catalyst through the impregnating solution I to the amount of Cr introduced into the catalyst through the impregnating solution II is 1-3: 1.
12. the method of claim 7, wherein the first drying and the first firing in step (3) are performed under an oxygen-containing atmosphere, and the first drying conditions are as follows: the drying temperature is 80-160 ℃, the drying time is 2-24 h, and the first roasting condition is as follows: the roasting temperature is 550-800 ℃ and the roasting time is 1-10 h;
and/or, the second drying and the second roasting in the step (4) are performed under an oxygen-containing atmosphere, and the second drying conditions are as follows: the drying temperature is 80-150 ℃, the drying time is 1-16 h, and the second roasting condition is as follows: the roasting temperature is 600-800 ℃ and the roasting time is 2-15 h.
13. Use of the propane dehydrogenation catalyst according to any of claims 1-6 in the dehydrogenation of propane to propylene.
14. The use according to claim 13, wherein the reaction conditions for the dehydrogenation of propane are as follows: the reaction temperature is 550-620 ℃, the reaction pressure is 0.05-0.1 MPa, and the volume space velocity of propane is 0.4-1.0 h -1 。
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110560043A (en) * 2018-06-05 2019-12-13 中国石油化工股份有限公司 Method for producing propylene by propane dehydrogenation
CN110560041A (en) * 2018-06-05 2019-12-13 中国石油化工股份有限公司 catalyst for producing propylene by propane dehydrogenation

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110560043A (en) * 2018-06-05 2019-12-13 中国石油化工股份有限公司 Method for producing propylene by propane dehydrogenation
CN110560041A (en) * 2018-06-05 2019-12-13 中国石油化工股份有限公司 catalyst for producing propylene by propane dehydrogenation

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