CN113171801A - Catalyst for preparing olefin by low-carbon alkane dehydrogenation and preparation method and application thereof - Google Patents

Catalyst for preparing olefin by low-carbon alkane dehydrogenation and preparation method and application thereof Download PDF

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CN113171801A
CN113171801A CN202011376367.5A CN202011376367A CN113171801A CN 113171801 A CN113171801 A CN 113171801A CN 202011376367 A CN202011376367 A CN 202011376367A CN 113171801 A CN113171801 A CN 113171801A
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catalyst
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alumina
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谷育英
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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
    • B01J37/08—Heat treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/06—Halogens; Compounds thereof
    • B01J27/135—Halogens; Compounds thereof with titanium, zirconium, hafnium, germanium, tin or lead
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • 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
    • B01J37/0203—Impregnation the impregnation liquid containing organic compounds
    • 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
    • B01J37/12—Oxidising
    • B01J37/14—Oxidising with gases containing free oxygen
    • 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
    • B01J37/16—Reducing
    • B01J37/18—Reducing with gases containing free hydrogen
    • 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
    • B01J37/22—Halogenating
    • B01J37/24—Chlorinating
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
    • C07C5/327—Formation of non-aromatic carbon-to-carbon double bonds only
    • C07C5/333—Catalytic processes
    • C07C5/3335—Catalytic processes with metals
    • C07C5/3337—Catalytic processes with metals of the platinum group
    • 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

Abstract

The invention belongs to the field of preparation of dehydrogenation catalysts, and particularly relates to a catalyst for preparing olefin by dehydrogenation of low-carbon alkane, and a preparation method and application thereof. The catalyst comprises an alumina carrier and four catalytic components, wherein the first component is Pt metal and accounts for 0.01-2.00 wt% of the total mass of the catalyst; the second component is alkali metal and/or alkaline earth metal element, which accounts for 0.05-5.00 wt% of the total mass of the catalyst; the third component is IVA group elements which account for 0.01 to 1.00wt percent of the total mass of the catalyst, and the molar ratio of Pt to IVA group elements is 1.0 to 1.5: 1; the fourth component is Cl element which accounts for 0.05-2.00 wt% of the total mass of the catalyst; the rest is an alumina carrier. The catalyst has the characteristics of good metal dispersibility and dispersion stability, is applied to the reaction of preparing olefin by dehydrogenating low-carbon alkane, and has the advantages of high activity, good selectivity, low carbon deposition rate, high regeneration rate and the like.

Description

Catalyst for preparing olefin by low-carbon alkane dehydrogenation and preparation method and application thereof
Technical Field
The invention belongs to the field of preparation of dehydrogenation catalysts, and particularly relates to a catalyst for preparing olefin by dehydrogenation of low-carbon alkane with stably dispersed active components on alumina, and a preparation method and application thereof.
Background
The low-carbon olefins such as ethylene, propylene, butylene and the like are important organic chemical raw materials, and the sources of the low-carbon olefins include oil refining products and byproducts and a process for specially producing olefins, for example, crude oil is distilled and subjected to oil refining processes to obtain product oil, low-carbon olefins are produced as byproducts, naphtha is subjected to steam cracking to obtain ethylene, propylene and butylene are produced as byproducts, olefins are produced from coal or methanol, and olefins are produced by catalytic dehydrogenation. With the increase of the demand of low-carbon olefin, the catalytic dehydrogenation technology has obvious advantages due to short device flow and low investment cost and operation cost.
The mature catalyst and the matched process comprise Oleflex process and CB of UOP company&The catalyst adopts Pt-Sn/Al as catalyst in Catofin process of Lummus company and STAR process of Krupp-Uhde company2O3、CrOX/Al2O3、Pt-Sn/ZnAl2O3. The olefin preparation by catalytic dehydrogenation of the low-carbon alkane is an exothermic reaction, so that high conversion rate is more favorably obtained by high temperature and low alkane partial pressure. However, it is limited by thermodynamic equilibrium, cracking and deep dehydrogenation easily occur to cause carbon deposition, the catalyst is rapidly deactivated, regeneration treatment is required, and after the catalyst is subjected to multiple regenerations, activity is lost due to structural changes of active species and irreversible deactivation is performed. Obviously, how to reduce the carbon deposition of the catalyst is a key problem of the catalytic reaction, and simultaneously, the maintenance of the catalytic performance after frequent regeneration is another key technology of the catalyst. Therefore, the high activity, high selectivity, high stability and low carbon deposition rate are key techniques for developing the catalyst for preparing olefin by catalytic dehydrogenation of low-carbon alkaneAnd (4) performing the operation.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention provides a catalyst for preparing olefin by dehydrogenating light alkane, and a preparation method and application thereof. The catalyst has the characteristics of good metal dispersibility and dispersion stability, is applied to the reaction of preparing olefin by dehydrogenating low-carbon alkane, and has the advantages of high activity, good selectivity, low carbon deposition rate, high regeneration rate and the like.
A catalyst for preparing olefin by dehydrogenating light alkane comprises an alumina carrier and four catalytic components, wherein the first component is Pt metal and accounts for 0.01-2.00 wt% of the total mass of the catalyst; the second component is alkali metal and/or alkaline earth metal element, which accounts for 0.05-5.00 wt% of the total mass of the catalyst; the third component is IVA group elements which account for 0.01 to 1.00wt percent of the total mass of the catalyst, and the molar ratio of Pt to IVA group elements is 1.0 to 1.5: 1; the fourth component is Cl element which accounts for 0.05-2.00 wt% of the total mass of the catalyst; the rest is an alumina carrier.
Illustratively, the first component comprises 0.01 wt%, 0.02 wt%, 0.05 wt%, 0.1 wt%, 0.3 wt%, 0.5 wt%, 0.8 wt%, 1 wt%, 1.2 wt%, 1.5 wt%, 1.8 wt%, 2.00 wt% of the total mass of the catalyst; the second component accounts for 0.05 wt%, 0.1 wt%, 0.2 wt%, 0.5 wt%, 0.8 wt%, 1 wt%, 1.2 wt%, 1.5 wt%, 1.8 wt%, 2 wt%, 2.5 wt%, 2.8 wt%, 3 wt%, 3.2 wt%, 3.5 wt%, 3.8 wt%, 4 wt%, 4.2 wt%, 4.5 wt%, 4.8 wt%, 5 wt% of the total mass of the catalyst; the third component accounts for 0.01 wt%, 0.02 wt%, 0.05 wt%, 0.1 wt%, 0.2 wt%, 0.5 wt%, 0.8 wt%, 1 wt% of the total mass of the catalyst, and the molar ratio of Pt to the IVA group element is 1:1, 1.2:1, 1.3:1, 1.4:1, 1.5: 1; the fourth component accounts for 0.05 wt%, 0.1 wt%, 0.2 wt%, 0.5 wt%, 0.8 wt%, 1 wt%, 1.2 wt%, 1.5 wt%, 1.8 wt%, 2 wt% of the total mass of the catalyst.
According to the invention, the alumina carrier is a small ball with the diameter of 1.3-2.0mm and the specific surface area of 50-300m2Per g, pore volume of 0.55-0.85ml/g, most probable pore diameter of 20-50 nm; the pore volume of pores with diameter of 2-20nm is 5-20% of total pore volume, and the pore volume of pores with diameter of 20-50nm is10-40% of (a), the pore volume of pores having a diameter of more than 50nm but not more than 500nm representing 50-80% of the total pore volume; the apparent bulk density is 0.515-0.695 g/ml.
The diameter of the alumina spheres is preferably 1.6-1.8mm, and the specific surface area is preferably 70-150m2A pore volume of preferably 0.65 to 0.75ml/g, the pore volume of pores having a most probable pore diameter of 30 to 40nm, a pore volume of pores having a diameter of 2 to 20nm of 10 to 20% of the total pore volume, a pore volume of pores having a diameter of 20 to 50nm of 20 to 30% of the total pore volume, and a pore volume of pores having a diameter of more than 50nm but not more than 500nm of 55 to 70% of the total pore volume; the apparent bulk density is 0.53-0.65 g/ml.
According to the invention, the alkali metal and/or alkaline earth metal element, preferably the element K, accounts for 0.40-2.00 wt% of the total mass of the catalyst.
According to the invention, the group IVA element is preferably Sn element, and accounts for 0.05-1.00 wt% of the total mass of the catalyst, and the molar ratio of Pt to the group IVA element is 1.05-1.45: 1.
According to the invention, the first component has a radial dispersity of 90 to 110; the radial dispersion of the second component is 100-.
The first component and the second component are loaded on the alumina carrier by a co-impregnation method. Specifically, a Pt precursor, a soluble alkali metal salt and/or an alkaline earth metal salt and water are mixed to prepare an impregnation liquid, and alumina is impregnated into the impregnation liquid; the volume ratio of the impregnating solution to the alumina is 0.8-1.4:1, preferably 0.9-1.2: 1.
In order to promote the alkali metal and/or alkaline earth metal elements to be uniformly dispersed in the catalyst and have dispersion stability, a cosolvent can be added in the preparation process of the impregnating solution for co-impregnating the first component and the second component, wherein the cosolvent is selected from one or more of citric acid, ethylenediamine tetraacetic acid, tetramethylammonium hydroxide, ammonia water and hydrochloric acid, and the addition amount of the cosolvent is 0-10% of the total mass of the impregnating solution. The co-solvent may be added before, during, or after the Pt precursor, soluble alkali metal salt and/or alkaline earth metal salt and water are mixed. The impregnation solution is required to be clear and free of precipitates or insolubles.
In order to further promote the Pt, the alkali metal and/or the alkaline earth metal elements to be evenly distributedDispersing in catalyst and having dispersion stability, aging the impregnated material at 40-100 deg.C for 2-10 hr to make the loss on ignition of the aged material at 700 deg.C be 10-25%. The aging treatment can be dynamic aging treatment or static aging treatment; the dynamic ageing treatment can be carried out by using a rotary evaporator and a double-cone rotary evaporator. In the aging treatment process, the evaporation of water on the surface of the catalyst can be accelerated by a heat medium (hot air, hot nitrogen and the like), and the airspeed of the heat medium passing through the catalyst per unit volume is 0-2.0h-1。
The third component may be introduced during the preparation of the support, either before or after the introduction of the first or second component, or simultaneously with the introduction of the first or second component. Specifically, the third component can be added in the gelling process of the alumina to form an alumina carrier containing the third component; the third component can also be added by means of co-mixing, dipping and the like before the first component and the second component are loaded to form the alumina carrier containing the third component; the third component can also be added in the preparation process of the first and second components co-impregnation liquid to form the first, second and third components co-impregnation liquid; the third component may be supported by a second impregnation after the first and second components are supported. The third component may be added in whole or in part in any of the processes described above.
The fourth component may be introduced during the preparation of the support, either before or after the introduction of the first or second component, or simultaneously with the introduction of the first or second component. Specifically, the fourth component can be added in the gelling process of the alumina to form an alumina carrier containing the fourth component; the fourth component can also be added in the preparation process of the first and second components co-impregnation liquid to form the co-impregnation liquid containing the first, second and fourth components; the fourth component may also be added during thermal activation by adding a compound in air that decomposes to produce the fourth component at the thermal activation temperature. The fourth component may be added in whole or in part in any of the processes described above.
Drying the catalyst precursor containing the first, second, third and/or fourth components at the temperature of 100 ℃ and 300 ℃ for 0.5-12h, wherein the loss on ignition of the dried material at the temperature of 700 ℃ is 0.03-5%; dry matterThe dried material is thermally activated for 0.5 to 24 hours at the temperature of 400 ℃ and 700 ℃ in the air, and the space velocity is 500-2000 hours-1(ii) a The catalyst is obtained by thermal reduction for 0.5-72h at 400-700 ℃ in a hydrogen-containing atmosphere.
Illustratively, the preparation method of the catalyst comprises the following steps:
(1) mixing group IVA metal salt, alkali metal salt and/or alkaline earth metal salt, Pt precursor and water to prepare impregnation liquid;
(2) dipping alumina into the dipping solution in the step (1);
(3) carrying out aging treatment, drying treatment and activating treatment on the material impregnated in the step (2) to obtain an oxidation state product;
(4) and (4) carrying out thermal reduction treatment on the oxidation state product obtained in the step (3) to prepare the catalyst for preparing olefin by dehydrogenating low-carbon alkane.
Preferably, in step (1), the metal salt in the group IVA metal salt, alkali metal salt and/or alkaline earth metal salt may be, for example, one or more of a metal nitrate, a metal sulfate, a metal chloride, and the like, and may be, for example, a metal chloride;
preferably, in step (1), the group IVA metal is selected from tin (Sn); the group IVA metal salt is selected from the group consisting of stannic chloride, stannic nitrate, stannous chloride, stannic sulfate.
Preferably, in step (1), the alkali metal salt is selected from soluble hydroxide, chloride or nitrate, and may be potassium hydroxide, potassium chloride;
preferably, in the step (1), the Pt precursor is selected from one or more of chloroplatinic acid hexahydrate, potassium tetrachloroplatinate, potassium hexachloroplatinate and sodium chloroplatinate.
Preferably, in the step (3), the aging treatment may be, for example, an aging treatment at 40 to 100 ℃ for 2 to 10 hours;
preferably, in the step (3), the drying treatment may be, for example, drying treatment at 100-300 ℃ for 0.5-12 h;
preferably, in the step (3), the water vapor activation treatment may be, for example, water vapor activation treatment at 400-700 ℃ for 0.5-24 h.
Wherein, in the step (4), the thermal reduction treatment is carried out in a hydrogen atmosphere, and the thermal reduction treatment is carried out for 4-30h at 400-700 ℃;
wherein, the volume content of hydrogen in the hydrogen atmosphere is 10-100 vol%, and the volume content of nitrogen is 0-90 vol%.
The invention also provides the application of the catalyst for preparing olefin by dehydrogenating the low-carbon alkane, and the catalyst is used for the reaction for preparing olefin by dehydrogenating the low-carbon alkane.
According to the invention, the lower alkanes comprise alkanes having 2 to 4 carbon atoms, such as ethane, propane, n-butane, isobutane.
According to the invention, the olefin is the main product after the alkane dehydrogenation reaction, and comprises ethylene, propylene, butylene and isobutene.
According to the invention, the reaction temperature is 450-650 ℃, the reaction pressure is 100-1500kPa, and the liquid hourly space velocity is 0.5-40h-1Hydrogen to hydrocarbon ratio of 0.5 to 2; in the reaction process, a sulfur-containing compound needs to be injected, and the mass content of sulfur in the raw material is controlled to be 50-200 ppm. The sulfur-containing compound may be hydrogen sulfide, dimethyl disulfide.
The invention has the beneficial effects that:
alkali metal and alkaline earth metal elements can improve the carbon deposition resistance of the catalyst, but in the preparation process of the catalyst, due to the introduction of multiple components, the competitive adsorption among the components is easy to cause uneven dispersion of the components and poor dispersion stability, so that the synergistic effect of the elements cannot be well exerted.
According to the invention, macroporous alumina is used as a carrier, Pt, alkali metal and/or alkaline earth metal are loaded in a co-impregnation mode, the molar ratio of the Pt and the alkali metal and/or the alkaline earth metal is controlled, and then a multi-component is uniformly dispersed on the alumina in a low-temperature aging mode to generate a synergistic effect, so that the problem of nonuniform metal content from the edge to the center along the diameter of the carrier caused by competitive adsorption can be solved, and the radial dispersion degree and the dispersion stability are improved.
When the catalyst with high dispersion and dispersion stability is applied to dehydrogenation reaction, the catalyst shows good high activity, good selectivity and carbon deposition resistance, and the regenerated metal component can still keep a high dispersion state and has small performance loss and the like.
Detailed Description
The present invention will be described in further detail with reference to specific examples. It is to be understood that the following examples are only illustrative and explanatory of the present invention and should not be construed as limiting the scope of the present invention. All the technologies realized based on the above-mentioned contents of the present invention are covered in the protection scope of the present invention.
The experimental methods used in the following examples are all conventional methods unless otherwise specified; reagents, materials and the like used in the following examples are commercially available unless otherwise specified.
Calculating the radial dispersion degree of metal: using SEM scanning of the metal content of the catalyst profile from edge to center, the metal radial dispersion was calculated for one metal as follows:
the radial dispersion degree is the average metal content in the range of 0.2mm inward of the edge of the pellet/the average metal content in the range of 0.2mm inward of the center of the pellet is 100;
the loss on ignition test was carried out by weighing M after baking 5g of the sample in a muffle furnace at 700 ℃ for 4h and calculating the loss on ignition: loss on ignition is (5-M)/5 x 100.
The performance of the catalyst was evaluated using a 20ml fixed bed tubular reactor, the reactant was propane, the reaction temperature was 650 ℃, the reaction pressure was 130kPa, and the propane mass space velocity was 9h-1The hydrogen-hydrocarbon ratio is 0.7, and dimethyl disulfide is injected in the reaction process to ensure that the mass content of sulfur in reactants reaches 100 ppm; testing the selectivity and the conversion rate of the catalyst at 4h and 20h of reaction; and (3) regenerating the catalyst after reacting for 20h, continuously testing the regenerated catalyst according to the reaction conditions, and testing the selectivity and the conversion rate of the catalyst after 5 times of reaction regeneration.
Conversion ═ (inlet propane mass-outlet propane mass)/inlet propane mass 100;
selectivity is the mass of propylene produced/(mass of inlet propane-mass of outlet propane) × 100.
Example 1
The alumina pellets containing 0.17 wt% of Sn were prepared by oil drop method, the carrier diameter was 1.8mm, the specific surface area was 90m2A pore volume of 0.65ml/g, a mode pore diameter of 38nm, an apparent bulk density of 0.54g/ml, a pore volume of pores having a diameter of 2 to 20nm of 10% of the total pore volume, a pore volume of pores having a diameter of 20 to 50nm of 28% of the total pore volume, and a pore volume of pores having a diameter of more than 50nm but not more than 500nm of 62% of the total pore volume.
Respectively adding 19g of potassium chloride, 9g of hydrochloric acid and 9.1g of chloroplatinic acid hexahydrate into 1700g of water, stirring until the potassium chloride, the hydrochloric acid and the chloroplatinic acid are completely dissolved to prepare a co-impregnation liquid, putting 1000g of the alumina carrier into the impregnation liquid for impregnation for 0.5h, aging the impregnated alumina at 80 ℃ for 8h, wherein the loss on ignition of the aged impregnated alumina is 15%; drying the impregnated alumina at 280 ℃ for 2h, wherein the loss on ignition of the dried impregnated alumina is 1.7%; thermally activating at 550 ℃ under 1800L/h of air for 4h, and injecting hydrochloric acid solution at the flow rate of 28.5ml/h in the activation process by air to obtain an oxidation state catalyst; the reduction was carried out at 570 ℃ for 8 hours in a nitrogen atmosphere containing 30% hydrogen to obtain a reduced catalyst 1. In the catalyst 1, the content of Pt is 0.34 wt%, the content of Sn is 0.17 wt%, the content of K is 0.85 wt%, and the content of Cl is 1.1 wt%; the Pt/Sn molar ratio is 1.2; the Pt radial dispersion was 105 and the K radial dispersion was 135.
Comparative example 1
Adding 22.4g of potassium chloride and 12g of chloroplatinic acid hexahydrate into 1700g of water respectively, stirring until the potassium chloride and the chloroplatinic acid are completely dissolved to prepare a co-impregnation liquid, and putting 1000g of the alumina carrier in the embodiment 1 into the impregnation liquid for impregnation for 0.5 h; drying the impregnated alumina at 280 ℃ for 2h, wherein the loss on ignition of the dried impregnated alumina is 1.7%; thermally activating at 550 ℃ under 1800L/h of air for 4h, and injecting hydrochloric acid solution at the flow rate of 28.5ml/h in the activation process by air to obtain an oxidation state catalyst; the reduction was carried out at 570 ℃ for 8 hours in a nitrogen atmosphere containing 30% hydrogen to obtain a reduced catalyst 2. In the catalyst 2, the content of Pt is 0.45 wt%, the content of Sn is 0.17 wt%, the content of K is 1 wt%, and the content of Cl is 1.1 wt%; the Pt/Sn molar ratio is 1.6; the Pt radial dispersion was 105 and the K radial dispersion was 180.
Example 2
By means of rollersThe alumina pellets are prepared by a ball method, the diameter of the carrier is 1.6mm, and the specific surface area is 125m2A pore volume of 0.70ml/g, a mode pore diameter of 35nm, an apparent bulk density of 0.63g/ml, a pore volume of pores having a diameter of 2 to 20nm of 12% of the total pore volume, a pore volume of pores having a diameter of 20 to 50nm of 24% of the total pore volume, and a pore volume of pores having a diameter of more than 50nm but not more than 500nm of 64% of the total pore volume.
Respectively adding 10.5 g of stannous chloride dihydrate, 28g of potassium hydroxide, 88g of citric acid and 16.5g of potassium hexachloroplatinate into 3300g of water, stirring until the stannous chloride dihydrate, the potassium hydroxide, the citric acid and the potassium hexachloroplatinate are completely dissolved to prepare impregnation liquid, putting 2200g of the alumina into the impregnation liquid, impregnating for 1h, introducing air into the impregnated alumina at 90 ℃ at the flow rate of 6.5L/h, aging the impregnated alumina for 4h, wherein the loss on ignition of the aged impregnated alumina is 20%; drying the impregnated alumina at 130 ℃ for 4h, wherein the loss on ignition of the dried impregnated alumina is 3.5%; thermally activating at 560 ℃ for 4h under 3000L/h of air, and introducing chlorine gas in the activation process in terms of air, wherein the chlorine gas flow is 50ml/h, so as to obtain an oxidation state catalyst; reducing for 6h at 600 ℃ in hydrogen atmosphere to obtain the reduced catalyst 3. In the catalyst 3, the content of Pt is 0.45 wt%, the content of Sn is 0.25 wt%, the content of K is 1 wt%, and the content of Cl is 1.6 wt%; the Pt/Sn molar ratio is 1.1; the Pt radial dispersion was 105 and the K radial dispersion was 120.
Example 3
The alumina pellets containing 0.16 wt% of Sn were prepared by oil drop method, the carrier diameter was 1.6mm, the specific surface area was 120m2A pore volume of 0.68ml/g, a mode pore diameter of 26nm, an apparent bulk density of 0.67g/ml, a pore volume of pores having a diameter of 2 to 20nm of 7% of the total pore volume, a pore volume of pores having a diameter of 20 to 50nm of 35% of the total pore volume, and a pore volume of pores having a diameter of more than 50nm but not more than 500nm of 58% of the total pore volume.
Respectively adding 2.3g of potassium chloride, 1.2g of hydrochloric acid and 8g of chloroplatinic acid hexahydrate into 180g of water, stirring until the materials are completely dissolved to prepare co-impregnation liquid, putting 100g of the alumina carrier into the impregnation liquid, impregnating in a rotary evaporator for 0.5h, introducing air with the flow rate of 30ml/h at 100 ℃ to age the impregnated alumina for 4h, wherein the loss on ignition of the aged impregnated alumina is 5%; drying the impregnated alumina at 240 ℃ for 2h, wherein the loss on ignition of the dried impregnated alumina is 1.1%; thermally activating for 6 hours at 580 ℃ under 100L/h of air to obtain an oxidation state catalyst; reducing for 4h at 550 ℃ in a hydrogen atmosphere to obtain a reduced catalyst 4. In the catalyst 4, the content of Pt is 0.3 wt%, the content of Sn is 0.16 wt%, the content of K is 1.0 wt%, and the content of Cl is 1.05 wt%; the Pt/Sn molar ratio is 1.14; the Pt radial dispersion was 110 and the K radial dispersion was 125.
Comparative example 2
Adding 1.2g of hydrochloric acid and 8g of chloroplatinic acid hexahydrate into 180g of water respectively, stirring until the hydrochloric acid and the chloroplatinic acid are completely dissolved, putting 100g of the alumina carrier in example 3 into an impregnation liquid, and impregnating for 4 hours at 25 ℃ in a rotary evaporator; drying the impregnated alumina at 120 ℃ for 12h, and roasting at 500 ℃ for 4 h; adding 3.2g of potassium nitrate into 180g of water, stirring until the potassium nitrate is completely dissolved, putting the alumina subjected to primary soaking roasting into a soaking solution, and soaking for 4 hours at 25 ℃ in a rotary evaporator; drying the impregnated alumina at 120 ℃ for 12h, and roasting at 600 ℃ for 4 h; reducing for 4h at 550 ℃ in a hydrogen atmosphere to obtain the reduced catalyst 5. In the catalyst 5, the content of Pt is 0.3 wt%, the content of Sn is 0.16 wt%, the content of K is 1.0 wt%, and the content of Cl is 1.05 wt%; the Pt/Sn molar ratio is 1.14; pt is radially distributed in a surface layer of which the thickness is 0.42mm from the edge to the inside of the spherical carrier, the radial dispersion degree of the Pt is infinite because the Pt is only distributed in the surface layer, and K is radially distributed in the surface layer of which the thickness is 0.45mm from the edge to the inside of the spherical carrier, and the radial dispersion degree of the K is infinite because the K is only distributed in the surface layer.
Example 4
The alumina pellets are prepared by an oil drop method, the diameter of the carrier is 1.7mm, and the specific surface area is 65m2A pore volume of 0.60ml/g, a mode pore diameter of 25nm, an apparent bulk density of 0.6g/ml, a pore volume of pores having a diameter of 2 to 20nm constituting 10% of the total pore volume, a pore volume of pores having a diameter of 20 to 50nm constituting 40% of the total pore volume, and a pore volume of pores having a diameter of more than 50nm but not more than 500nm constituting 50% of the total pore volume.
Adding 11.5g of stannous chloride dihydrate into 8500g of water, stirring until the stannous chloride dihydrate is completely dissolved to prepare a steeping fluid, putting 5000g of the alumina into the steeping fluid for steeping for 2 hours, drying at 120 ℃ for 4 hours, and roasting at 550 ℃ for 4 hours;
adding 46g of potassium hydroxide, 50g of ethylenediamine and 35g of potassium hexachloroplatinate into 8500g of water respectively, stirring until the potassium hydroxide, the ethylenediamine and the potassium hexachloroplatinate are completely dissolved to prepare impregnation liquid, putting the alumina subjected to primary impregnation roasting into the impregnation liquid for impregnation for 2 hours, aging the impregnated alumina in a rotary evaporator for 10 hours at 65 ℃, wherein the loss on ignition of the aged impregnated alumina is 16%; drying the impregnated alumina at 110 ℃ for 12h, wherein the loss on ignition of the dried impregnated alumina is 3.5%; thermally activating for 6h in the air at 580 ℃, introducing chlorine gas in the activation process, wherein the chlorine gas flow is 100ml/h, and obtaining an oxidation state catalyst; reducing for 18h at 580 ℃ in hydrogen atmosphere to obtain the reduced catalyst 6. In the catalyst 6, the content of Pt was 0.28 wt%, the content of Sn was 0.12 wt%, the content of K was 0.75 wt%, and the content of Cl was 1.2 wt%; the Pt/Sn molar ratio is 1.42; the Pt radial dispersion is 102 and the K radial dispersion is 122.
The performance of the reduced catalysts 1-6 was evaluated and the results are shown in the following table:
Figure BDA0002808297890000101
as can be seen from the above table, catalyst 1, catalyst 3, and catalyst 4 have good conversion rate and selectivity, and lower carbon deposition rate; after 20 hours of operation and 5 times of regeneration, the conversion rate and the selectivity are not obviously reduced; in the first use process of the catalyst 2, the catalyst shows good conversion rate and selectivity after reacting for 4 hours, but after the reaction is carried out for 20 hours, the conversion rate and the selectivity are both reduced, after 5 times of regeneration, the catalyst can recover the performance of the catalyst in the first use, but after 20 hours of reaction, the conversion rate and the selectivity are obviously reduced, and the carbon deposition rate is higher. The catalyst 5 has good conversion rate and selectivity in the first use process, but after 5 times of regeneration, the conversion rate, the selectivity and the carbon deposition rate cannot be recovered to the numerical values of the first reaction.
The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (10)

1. A catalyst for preparing olefin by dehydrogenating light alkane comprises an alumina carrier and four catalytic components, wherein the first component is Pt metal and accounts for 0.01-2.00 wt% of the total mass of the catalyst; the second component is alkali metal and/or alkaline earth metal element, which accounts for 0.05-5.00 wt% of the total mass of the catalyst; the third component is IVA group elements which account for 0.01 to 1.00wt percent of the total mass of the catalyst, and the molar ratio of Pt to IVA group elements is 1.0 to 1.5: 1; the fourth component is Cl element which accounts for 0.05-2.00 wt% of the total mass of the catalyst; the rest is an alumina carrier.
2. The catalyst as claimed in claim 1, wherein the alumina carrier is a pellet with a diameter of 1.3-2.0mm and a specific surface area of 50-300m2Per g, pore volume of 0.55-0.85ml/g, most probable pore diameter of 20-50 nm; the pore volume of pores with diameter of 2-20nm is 5-20% of total pore volume, the pore volume of pores with diameter of 20-50nm is 10-40% of total pore volume, and the pore volume of pores with diameter of more than 50nm but not more than 500nm is 50-80% of total pore volume; the apparent bulk density is 0.515-0.695 g/ml.
3. Catalyst according to claim 2, wherein the alumina spheres have a diameter preferably ranging from 1.6 to 1.8mm and a specific surface area preferably ranging from 70 to 150m2A pore volume of preferably 0.65 to 0.75ml/g, the pore volume of pores having a most probable pore diameter of 30 to 40nm, a pore volume of pores having a diameter of 2 to 20nm of 10 to 20% of the total pore volume, a pore volume of pores having a diameter of 20 to 50nm of 20 to 30% of the total pore volume, and a pore volume of pores having a diameter of more than 50nm but not more than 500nm of 55 to 70% of the total pore volume; the apparent bulk density is 0.53-0.65 g/ml.
4. A catalyst according to any one of claims 1 to 3, wherein the alkali and/or alkaline earth element, preferably the element K, represents 0.40 to 2.00 wt% of the total mass of the catalyst.
5. The catalyst according to any one of claims 1 to 4, wherein the group IVA element, preferably Sn, is present in an amount of 0.05 to 1.00 wt% based on the total mass of the catalyst, and the molar ratio of Pt to group IVA element is 1.05 to 1.45: 1.
6. The catalyst of any of claims 1-5, wherein the first component radial dispersity is in the range of from 90 to 110; the radial dispersion of the second component is 100-.
7. A catalyst as claimed in any one of claims 1 to 6, wherein the first component and the second component are supported on an alumina support by co-impregnation. Specifically, a Pt precursor, a soluble alkali metal salt and/or an alkaline earth metal salt and water are mixed to prepare an impregnation liquid, and alumina is impregnated into the impregnation liquid; the volume ratio of the impregnation liquid to the alumina is 0.8-1.4: 1;
a cosolvent can be added in the preparation process of the impregnating solution for co-impregnating the first component and the second component, the cosolvent is selected from one or more of citric acid, ethylenediamine tetraacetic acid, tetramethylammonium hydroxide, ammonia water and hydrochloric acid, and the addition amount of the cosolvent is 0-10% of the total mass of the impregnating solution.
8. A catalyst as claimed in any one of claims 1 to 7 wherein the impregnated mass is aged at 40 to 100 ℃ for 2 to 10 hours to a loss on ignition at 700 ℃ of the aged mass of 10 to 25%.
9. Use of the catalyst for preparing olefin by dehydrogenating light alkane according to any one of claims 1 to 8, wherein the catalyst is used for preparing olefin by dehydrogenating light alkane.
10. The use of claim 9, wherein the lower alkane comprises ethane, propane, n-butane, isobutane;
the olefin comprises ethylene, propylene, butylene and isobutene;
the temperature of the reaction is 450-650 ℃, and the pressure of the reactionThe force is 100-1500kPa, and the liquid hourly space velocity is 0.5-40h-1Hydrogen to hydrocarbon ratio of 0.5 to 2; in the reaction process, a sulfur-containing compound needs to be injected, and the mass content of sulfur in the raw material is controlled to be 50-200 ppm.
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