CN109320392B - Reaction and regeneration process of fixed fluidized bed for preparing propylene by propane dehydrogenation - Google Patents

Reaction and regeneration process of fixed fluidized bed for preparing propylene by propane dehydrogenation Download PDF

Info

Publication number
CN109320392B
CN109320392B CN201811356906.1A CN201811356906A CN109320392B CN 109320392 B CN109320392 B CN 109320392B CN 201811356906 A CN201811356906 A CN 201811356906A CN 109320392 B CN109320392 B CN 109320392B
Authority
CN
China
Prior art keywords
regeneration
catalyst
reaction
reactor
mixed gas
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201811356906.1A
Other languages
Chinese (zh)
Other versions
CN109320392A (en
Inventor
韩伟
潘相米
王科
吴砚会
程牧曦
李博
艾珍
郑敏
谭亚南
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Southwest Research and Desigin Institute of Chemical Industry
Original Assignee
Southwest Research and Desigin Institute of Chemical Industry
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Southwest Research and Desigin Institute of Chemical Industry filed Critical Southwest Research and Desigin Institute of Chemical Industry
Priority to CN201811356906.1A priority Critical patent/CN109320392B/en
Publication of CN109320392A publication Critical patent/CN109320392A/en
Application granted granted Critical
Publication of CN109320392B publication Critical patent/CN109320392B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • 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
    • 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
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/56—Platinum group metals
    • B01J23/62—Platinum group metals with gallium, indium, thallium, germanium, tin or lead
    • B01J23/622—Platinum group metals with gallium, indium, thallium, germanium, tin or lead with germanium, tin or lead
    • B01J23/626—Platinum group metals with gallium, indium, thallium, germanium, tin or lead with germanium, tin or lead with tin
    • 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
    • B01J23/90—Regeneration or reactivation
    • B01J23/96—Regeneration or reactivation of catalysts comprising metals, oxides or hydroxides of the noble metals
    • 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
    • B01J38/00—Regeneration or reactivation of catalysts, in general
    • B01J38/02—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
    • B01J38/00—Regeneration or reactivation of catalysts, in general
    • B01J38/04—Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst
    • 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
    • B01J38/00—Regeneration or reactivation of catalysts, in general
    • B01J38/04—Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst
    • B01J38/10—Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst using elemental 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
    • B01J38/00—Regeneration or reactivation of catalysts, in general
    • B01J38/04—Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst
    • B01J38/12—Treating with free oxygen-containing gas
    • B01J38/14—Treating with free oxygen-containing gas with control of oxygen content in oxidation gas
    • 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
    • B01J38/00—Regeneration or reactivation of catalysts, in general
    • B01J38/04—Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst
    • B01J38/42—Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst using halogen-containing material
    • B01J38/44—Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst using halogen-containing material and adding simultaneously or subsequently free oxygen; using oxyhalogen compound
    • 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
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals
    • C07C2523/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36
    • C07C2523/56—Platinum group metals
    • C07C2523/62—Platinum group metals with gallium, indium, thallium, germanium, tin or lead
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/584—Recycling of catalysts

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)

Abstract

The invention provides a fixed fluidized bed reaction and regeneration process for preparing propylene by propane dehydrogenation, and belongs to the technical field of preparing propylene by propane dehydrogenation. The process adopts a plurality of fixed fluidized bed reactors, dehydrogenation catalyst beds are arranged in the reactors, when the reactor is in normal operation, one part of the reactors is in catalytic dehydrogenation reaction, the other part of the reactors is in catalyst regeneration, the reactors are switched by alternately carrying out catalytic dehydrogenation-catalyst regeneration operation, so that the whole reaction is stably carried out, and the dehydrogenation catalyst is periodically supplemented into the required reactor by calculating the abrasion loss of the dehydrogenation catalyst in each reactor. The reaction and regeneration process of the fixed fluidized bed provided by the invention not only has the characteristics of high conversion rate and high selectivity of the traditional fluidized bed, but also realizes the continuity of the whole reaction process through a plurality of sets of reactors, and simultaneously, the catalyst is only circulated in each reactor, so that the abrasion rate is greatly reduced. The invention has simple whole process flow and good industrialization prospect.

Description

Reaction and regeneration process of fixed fluidized bed for preparing propylene by propane dehydrogenation
Technical Field
The invention belongs to the technical field of propylene preparation by propane dehydrogenation, and particularly relates to a reaction and regeneration process of a fixed fluidized bed for preparing propylene by propane dehydrogenation.
Background
Propylene is one of important basic organic chemical raw materials, is mainly used for producing polypropylene, propylene oxide, acrylonitrile, acrylic acid and the like, and has an important position in modern petroleum and chemical industries. At present, 70 percent of propylene in the world comes from a byproduct produced by ethylene production through steam cracking, and 28 percent of propylene comes from a byproduct produced by gasoline and diesel oil production through catalytic cracking (FCC) in an oil refinery. However, with the increasing demand of propylene, the traditional propylene production capacity can not meet the increase rate of the demand far away, so that a new technology for increasing the yield of the propylene on an industrial scale with high efficiency and reasonability is sought, the technology becomes one of the new technologies of chemical enterprises, and the technology is more and more emphasized due to simple process, single product, low carbon and environmental protection.
The dehydrogenation catalyst systems which have been commercialized at present are mainly Cr2O3/Al2O3System and Pt/Al2O3In this system, the industrial Pt-based propane dehydrogenation processes include Oleflex process from UOP, STAR process from wood, and linde-basff PDH process. The Oleflex moving bed process has the advantages that the reactor is operated continuously, the reaction does not need to be stopped for the regeneration of the catalyst, but the investment cost of the device of the process is high, the catalyst circulates between 4-5 reactors and the regenerator, so that the abrasion rate of the catalyst is high, the reaction fluctuation is large, the propane conversion rate and the propylene selectivity are restricted by the reaction conditions, and the propylene yield is always low; both the STAR process and the Linde-Pasteur PDH process adopt a tubular fixed bed dehydrogenation reactor, preferablyThe method has the advantages of less catalyst consumption, in-reactor regeneration, complex reactor design, frequent switching and higher requirement on valves.
In addition to the three commercial dehydrogenation processes described above, many patents also disclose some of the more novel dehydrogenation processes. However, the prior published patents adopt a circulating fluidized bed reaction system for improving the reactor process, i.e. reaction and regeneration are not in the same reactor, and the particle size of the catalyst is basically between 20 and 200 microns. Although various optimizations have been made to the fluidized bed reactor to increase the reaction performance, the fluidization circulation of the fine particle catalyst between the different reactors, especially in the stripping phase, is still unavoidable, leading to a greater attrition of the catalyst. Aiming at the Pt dehydrogenation catalyst, the price is high, and higher requirements are provided for the abrasion of the catalyst, and the circulating fluidized dehydrogenation process is difficult to meet the requirements of low abrasion.
In a word, for the Pt-based catalyst, the mass and heat transfer in the fixed dehydrogenation process are not uniform, and the carbon deposition amount is high, so that no industrial device for the Pt-based dehydrogenation system exists at present; the catalysts in the moving bed and the circulating fluidized bed need to be circulated in the whole reaction system, the abrasion rate is high, and the control stability is not good, which is always the biggest problem of the catalyst of the system in the industrial production process.
Disclosure of Invention
The invention aims to provide a reaction and regeneration process of a fixed fluidized bed for preparing propylene by propane dehydrogenation. By adopting the fixed fluidized bed process provided by the invention, the catalyst does not need to be subjected to sedimentation collection and lifting processes, the abrasion is obviously reduced, the control stability is increased, the economy of the whole device is favorably improved, and the process has good industrialization prospect.
The purpose of the invention is realized by the following technical scheme:
a reaction and regeneration process of a fixed fluidized bed for preparing propylene by propane dehydrogenation adopts a plurality of fixed fluidized bed reactors, dehydrogenation catalyst beds are arranged in the reactors, when the reactor is in normal operation, one part of the reactors is in catalytic dehydrogenation reaction, the other part of the reactors is in catalyst regeneration, the plurality of reactors are switched between catalytic dehydrogenation and catalyst regeneration in turn, so that the whole reaction is stably carried out, and the dehydrogenation catalyst is replenished into the required reactor at regular time by calculating the abrasion loss of the dehydrogenation catalyst in each reactor.
Furthermore, the process adopts three fixed fluidized bed reactors, dehydrogenation catalyst beds are arranged in the reactors, when the process is in normal operation, two reactors carry out catalytic dehydrogenation reaction, one reactor carries out catalyst regeneration, and the three reactors carry out catalytic dehydrogenation-catalyst regeneration switching in turn, so that the whole reaction is stably carried out, and the dehydrogenation catalyst is replenished into a required reactor at regular time by calculating the abrasion loss of the dehydrogenation catalyst in each reactor.
Further, the preheated raw material gas mixture is continuously contacted with a dehydrogenation catalyst in the fixed fluidized bed reactor and subjected to catalytic dehydrogenation reaction under the reaction condition to produce the target product propylene, and the catalyst is continuously deactivated by carbon deposition.
Further, the catalyst is a Pt catalyst with the particle size of 50-150 meshes, the catalyst is in a stable fluidized state in the reactor during normal reaction, and the pulverized small-particle catalyst with the particle size of less than 150 meshes is taken out by reaction gas and enters a cyclone separation system.
Further, gas generated in the reaction process or gas generated in the regeneration process is collected together uniformly and then subjected to dust removal through a cyclone separation system, dust is collected, the consumption of the catalyst is calculated according to the dust, and the catalyst is added into the reactor once a week.
Further, the catalyst regeneration comprises the steps of:
a. after the catalyst is deactivated, firstly introducing inert gas to sweep the deactivated catalyst, then sequentially introducing oxygen-containing regeneration gas and chlorine-containing regeneration gas to carry out carbon burning and Pt redispersion treatment on the catalyst, and finally introducing air to carry out treatment;
in the above step, the oxygen-containing regeneration gas removes carbon deposits on the catalyst through a carbon burning reaction. In the carbon burning process, the active center metal platinum is gathered together, so chlorine-containing regeneration gas is needed to be introduced to realize the oxidation and redispersion of the active metal, and finally, air is introduced to remove the redundant organic chlorine compounds.
b. After the carbon burning and the Pt are redispersed, firstly introducing inert gas to sweep the catalyst, then introducing reducing gas to reduce the catalyst so as to restore the activity of the catalyst, then raising the temperature to the temperature required by the reaction again, and introducing propane and hydrogen to continue the reaction.
Further, the raw material mixed gas is propane and hydrogen, and the molar ratio of the hydrogen to the propane is 0-0.3.
Further, the conditions of the catalytic dehydrogenation reaction are as follows: the reaction temperature is 550-650 ℃, the reaction pressure is 0-500 Kpa, and the gas space velocity of the raw material gas is 600-4000 h-1(ii) a Preferably: the reaction temperature is 580-630 ℃, the reaction pressure is 30-300 KPa, and the gas space velocity of the raw material gas is 1000-3000 h-1。
Further, the inactivation of the catalyst by carbon deposition means that the activity of the catalyst is reduced by 1-20% relative to the initial activity after the normal reaction is carried out for 2-48 h.
Further, the catalyst regeneration process is carried out at the temperature of 450-650 ℃ and under the pressure of 0-200 Kpa, the oxygen-containing regeneration gas is a mixture of oxygen and inert gas, wherein the content of the oxygen is 5-10%, and the chlorine-containing regeneration gas is inert gas and O2Or H2O, mixtures of organic chlorides, in which O2Or H2The O content is 0.05-3%, the organic chlorine content is 10-1000 ppm, and the catalyst regeneration time is 1-12 h. Further, the catalyst regeneration process is carried out at the temperature of 500-550 ℃ and under the pressure of 30-100 Kpa, the content of organic chlorine is preferably 50-500 ppm, and the catalyst regeneration time is 1-4 hours.
Further, the reduction temperature is 400-600 ℃, preferably 500-550 ℃, and the space velocity of the reduction gas is 500-5000 h-1Preferably 1000 to 3000 hours-1。
The inert gas according to the present invention is a conventionally known inert gas, preferably N2Or Ar, the reducing gas preferably being H2。
The catalyst for catalytic dehydrogenation is a Pt catalyst, and the reaction and regeneration process of the fixed fluidized bed for preparing propylene by propane dehydrogenation, which is provided by the invention, is designed for preparing propylene by propane dehydrogenation catalyzed by the Pt catalyst, so that the regeneration of the Pt catalyst can be realized, and the continuous operation of the whole dehydrogenation catalytic reaction is ensured. The components and the production method of the Pt-based catalyst are not particularly limited, and the Pt-based catalyst having a particle size of 50 to 150 mesh is preferable.
Compared with the prior art, the invention has the following beneficial effects:
the invention provides a novel process for preparing propylene by propane dehydrogenation, namely a fixed fluidized bed dehydrogenation process, which has the characteristics of high conversion rate and high selectivity of a traditional fluidized bed, realizes the regeneration of a dehydrogenation catalyst while catalyzing dehydrogenation reaction, ensures the continuous operation of the whole reaction, circulates only in the reactor, can greatly reduce the abrasion rate, and has simple integral process flow and good industrialization prospect.
Drawings
FIG. 1 is a schematic diagram of a fixed fluidized bed reaction and regeneration process for producing propylene by propane dehydrogenation when the number of reactors is three.
Reference numerals: the reactor comprises a 1-1# reactor, a 2-2# reactor, a 3-3# reactor, 4-raw material mixed gas, 5-regeneration mixed gas, 6-catalyst feeding system, 7-cyclone separator, 8-regeneration cyclone separator, 1a-1# reactor product gas, 2a-2# reactor product gas, 3a-3# reactor product gas, 1b-1# reactor regeneration gas, 2b-2# reactor regeneration gas and 3b-3# reactor regeneration gas.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Process for the preparation of a catalyst
FIG. 1 is a schematic diagram of a fixed fluidized bed reaction and regeneration process for producing propylene by propane dehydrogenation when the number of reactors is three. Taking three reactors as an example, other reactors are similar to the process.
Dehydrogenation catalyst beds are arranged in the three reactors. The raw material mixed gas 4 (hydrogen and propane) after external heat exchange and heating firstly enters the No. 1 reactor 1 for dehydrogenation reaction in the initial material flow (50% of the normal flow); after the reaction period is over half, the flow of the raw material mixed gas 4 is increased to 100%, and 50% of the raw material mixed gas 4 is divided to enter the No. 2 reactor 2 for dehydrogenation reaction; after reacting for one period, stopping feeding the raw material mixed gas 4 into the No. 1 reactor 1, and introducing the regenerated mixed gas 5 into the No. 1 reactor 1 for regeneration treatment; the 50% raw material gas mixture 4 enters the 3# reactor 3 for reaction. Reaction time to 1.5 cycles, 1# reactor 1 regeneration was complete. At the moment, the feeding of the No. 2 reactor 2 is stopped, the regeneration mixed gas 5 is introduced into the No. 2 reactor 2 for regeneration treatment, and 50% of the raw material mixed gas 4 enters the No. 1 reactor 1 again for reaction. Reaction time 2 cycles, 2# reactor 2 regeneration was complete. At this time, the feeding of the 3# reactor 3 is stopped, the regeneration mixed gas 5 is introduced into the 3# reactor 3 for regeneration treatment, and 50% of the raw material mixed gas 4 enters the 2# reactor 2 again for reaction. The three reactors are sequentially switched from catalytic dehydrogenation reaction to catalyst regeneration according to the flow, so that the stability of the system is kept, and the catalyst is added into the required reactor from the catalyst feeding system 6 at regular time by calculating the abrasion loss of the catalyst in each reactor.
Three streams of product gas (1a,2a,3a) of the three reactors are collected uniformly and then enter a cyclone separator 7 for dust removal treatment, catalyst powder is collected, and the clean material after dust removal enters a next-stage separation system. The regenerated gases (1b, 2b,3b) are collected together through three streams respectively and then are dedusted by a regeneration cyclone separator 8, catalyst powder is collected, and the dedusted regenerated gases enter a next-stage treatment and discharge system.
Examples 1 to 6 the above-mentioned process was used for the fixed fluidized bed reaction of propane dehydrogenation to propylene and the regeneration of the dehydrogenation catalyst.
Example 1
Catalyst preparation
1) Mixing weighed pseudo-boehmite with distilled water, gradually dropwise adding dilute nitric acid for acidification under the heating condition of 70 ℃, and controlling the pH value to be between 3.0 and 4.0 to form alumina sol; followed byThen adding polyvinyl alcohol, stirring for 1h, finally cooling to 30 ℃ and spraying in a spray drying agent to prepare Al2O3Spherical microspheroidal particles. Calcining the microsphere particles at 600 ℃ for 2h, and sieving to obtain particles of 50-100 meshes for later use.
2) 100g of the particle carrier and distilled water required for equal volume impregnation are weighed respectively. And then weighing a certain amount of chloroplatinic acid, stannous chloride, lithium nitrate and gallium nitrate, respectively dissolving in distilled water, uniformly mixing, finally soaking the carrier in the mixed solution in an equal volume, soaking overnight, drying, and calcining at 550 ℃ for 4 hours to obtain the finally required fresh catalyst. The catalyst comprises the following components: pt (0.29%), Sn (0.4%), Li (0.6%), Ga (0.3%) and Al for the rest2O3。
The catalyst is applied to the fixed fluidized bed reaction for preparing propylene by propane dehydrogenation and the activity evaluation of the regenerated catalyst:
the fresh catalyst is subjected to pure hydrogen reduction treatment for 1h at the temperature of 550 ℃, and the volume space velocity is 2000h-1Then heating to the reaction temperature for reaction, and adopting the above-mentioned technological process to make propane dehydrogenation produce propylene, and make fixed fluidized bed reaction and regeneration.
Propane dehydrogenation activity conditions: reaction temperature 605 ℃, catalyst loading 100g, H in feed gas2:C3H80.25 percent and the volume space velocity of 1500h-1The reaction pressure is 0.1MPa, and the regeneration is carried out after the reaction is carried out for 18 h.
Regeneration conditions are as follows: the regeneration temperature is 550 ℃, the regeneration pressure is 50Kpa, nitrogen is firstly introduced to purge the catalyst, and then the composition N is introduced2、O2(10%) oxygen-containing regeneration gas was subjected to carbon burning. After burning for 2h, introducing C2H5-CH3Cl2(200ppm)、H2N of O (0.08%)2Treating the catalyst with gas at 550 deg.C for 1H, then changing to air for 1H, purging with nitrogen, and introducing H2After treatment at 550 ℃ for 1h, regeneration was complete.
The activity test of the regenerated catalyst was carried out according to the fresh catalyst, and the activity test of the regenerated catalyst is shown in Table 1.
Example 2
Catalyst and process for preparing samePreparation: the preparation was carried out as in example 1, except that the modifying compounds were chloroplatinic acid, stannous chloride, sodium nitrate and zinc nitrate; the catalyst comprises the following components: pt (0.35%), Sn (0.8%), Na (1.0%), Zn (0.25%), and Al for the rest2O3。
The catalyst is applied to the fixed fluidized bed reaction for preparing propylene by propane dehydrogenation and the activity evaluation of the regenerated catalyst:
pure hydrogen reduction treatment is carried out on a fresh catalyst for 1h at the temperature of 550 ℃, and the volume space velocity is 1500h-1And then raising the temperature to the reaction temperature for reaction. The above process is adopted to carry out the reaction and regeneration of the fixed fluidized bed for preparing the propylene by propane dehydrogenation.
Propane dehydrogenation activity conditions: reaction temperature 605 ℃, catalyst loading 100g, H in feed gas2:C3H80.20, volume space velocity 1000h-1And the reaction pressure is 70KPa, and the reaction time is 12 h.
Regeneration conditions are as follows: the regeneration temperature is 550 ℃, the regeneration pressure is 30KPa, nitrogen is firstly introduced to purge the catalyst, and then the composition N is introduced2、O2(8%) oxygen-containing regeneration gas was subjected to carbon burning. After burning for 2h, introducing CCl4(300ppm)、O2(3%) N2Treating with gas at 550 deg.C for 1H, then changing to air for 1H, purging with nitrogen, and introducing H2After treatment at 550 ℃ for 1h, regeneration was complete.
The activity test of the regenerated catalyst was carried out according to the fresh catalyst, and the activity test thereof is shown in Table 1.
Example 3
Preparing a catalyst: the preparation method is carried out according to example 1, except that the modified compounds are chloroplatinic acid, stannous chloride and lithium nitrate; the catalyst comprises the following components: pt (0.26%), Sn (0.25%), Li (0.9%), and Al for the rest2O3。
The catalyst is applied to the fixed fluidized bed reaction for preparing propylene by propane dehydrogenation and the activity evaluation of the regenerated catalyst:
pure hydrogen reduction treatment is carried out on a fresh catalyst for 1h at the temperature of 500 ℃, and the volume space velocity is 3000h-1And then raising the temperature to the reaction temperature for reaction. Adopting the above processCarrying out reaction and regeneration of the fixed fluidized bed for preparing propylene by propane dehydrogenation.
Propane dehydrogenation activity conditions: reaction temperature 605 ℃, catalyst loading 100g, H in feed gas2:C3H80.35, volume space velocity of 2000h-1The reaction pressure is 0.2MPa, and the regeneration is carried out after the reaction is carried out for 24 hours.
Regeneration conditions are as follows: the regeneration temperature is 500 ℃, the regeneration pressure is 50KPa, nitrogen is firstly introduced to purge the catalyst, and then the composition N is introduced2、O2(6%) oxygen-containing regeneration gas was subjected to carbon burning. After carbon burning for 3h, the mixture is introduced with HCl (500ppm) and O2(2%) N2Treating with gas at 500 deg.C for 1 hr, then changing to air for 1 hr, purging with nitrogen, and introducing H2After 1h of treatment at 500 ℃, the regeneration is completed.
The activity test of the regenerated catalyst was carried out according to the fresh catalyst, and the activity test thereof is shown in Table 1.
Example 4
Preparing a catalyst: the preparation method was carried out as in example 1, except that the modified compounds were chloroplatinic acid, stannous chloride, potassium nitrate, lanthanum nitrate; the catalyst comprises the following components: pt (0.35%), Sn (0.35%), K (0.4%), La (0.25%), and Al for the rest2O3。
The catalyst is applied to the fixed fluidized bed reaction for preparing propylene by propane dehydrogenation and the activity evaluation of the regenerated catalyst:
the fresh catalyst is subjected to pure hydrogen reduction treatment for 1h at the temperature of 550 ℃, and the volume space velocity is 2000h-1And then raising the temperature to the reaction temperature for reaction. The above process is adopted to carry out the reaction and regeneration of the fixed fluidized bed for preparing the propylene by propane dehydrogenation.
Propane dehydrogenation activity conditions: reaction temperature 605 ℃, catalyst loading 100g, H in feed gas2:C3H80.15 and volume space velocity of 3000h-1And reacting for 12 hours at the reaction pressure of 50KPa for regeneration.
Regeneration conditions are as follows: the regeneration temperature is 550 ℃, the regeneration pressure is 30KPa, nitrogen is firstly introduced to purge the catalyst, and then the composition N is introduced2、O2(5%) oxygen-containing regeneration gas was subjected to carbon burning. After burning carbon for 2h, introducing CH2Cl2(50ppm)、H2N of O (0.05%)2Treating with gas at 550 deg.C for 1H, then changing to air for 1H, purging with nitrogen, and introducing H2After treatment at 550 ℃ for 1h, regeneration was complete.
The activity test of the regenerated catalyst was carried out according to the fresh catalyst, and the activity test thereof is shown in Table 1.
Example 5
Preparing a catalyst: the preparation was carried out as in example 1, except that the modified compounds were chloroplatinic acid, stannous chloride, calcium nitrate, cesium nitrate; the catalyst comprises the following components: pt (0.30%), Sn (0.55%), Ca (0.4%), Cs (0.2%), and Al for the rest2O3。
The catalyst is applied to the fixed fluidized bed reaction for preparing propylene by propane dehydrogenation and the activity evaluation of the regenerated catalyst:
pure hydrogen reduction treatment is carried out on fresh catalyst for 1h at 530 ℃, and the volume space velocity is 2500h-1And then raising the temperature to the reaction temperature for reaction. The above process is adopted to carry out the reaction and regeneration of the fixed fluidized bed for preparing the propylene by propane dehydrogenation.
Propane dehydrogenation activity conditions: reaction temperature 605 ℃, catalyst loading 100g, H in feed gas2:C3H80.20, volume space velocity of 2000h-1And reacting for 8 hours at the reaction pressure of 30KPa for regeneration.
Regeneration conditions are as follows: the regeneration temperature is 530 ℃, the regeneration pressure is 100KPa, nitrogen is firstly introduced to purge the catalyst, and then the composition N is introduced2、O2(6%) oxygen-containing regeneration gas was subjected to carbon burning. After burning carbon for 1h, introducing CH2Cl2(100ppm)、O2(1%) N2Treating with gas at 530 deg.C for 1H, then changing to air for 1H, purging with nitrogen, and introducing H2The regeneration was completed by treatment at 530 ℃ for 1 h.
The activity test of the regenerated catalyst was carried out according to the fresh catalyst, and the activity test thereof is shown in Table 1.
Example 6
Preparing a catalyst: the preparation was carried out as in example 1, except that the modifying compounds were chloroplatinic acid, stannous chloride, calcium nitrateCesium nitrate; the catalyst comprises the following components: pt (0.30%), Sn (0.55%), Ca (0.4%), Cs (0.2%), and Al for the rest2O3。
The catalyst is applied to the fixed fluidized bed reaction for preparing propylene by propane dehydrogenation and the activity evaluation of the regenerated catalyst:
pure hydrogen reduction treatment is carried out on a fresh catalyst for 1h at the temperature of 550 ℃, and the volume space velocity is 1800h-1And then raising the temperature to the reaction temperature for reaction. The above process is adopted to carry out the reaction and regeneration of the fixed fluidized bed for preparing the propylene by propane dehydrogenation.
Propane dehydrogenation activity conditions: reaction temperature 605 ℃, catalyst loading 100g, H in feed gas2:C3H80.25, volume space velocity 1000h-1And reacting for 16 hours at the reaction pressure of 50KPa for regeneration.
Regeneration conditions are as follows: the regeneration temperature is 550 ℃, the regeneration pressure is 50KPa, nitrogen is firstly introduced to purge the catalyst, and then the composition N is introduced2、O2(8%) oxygen-containing regeneration gas was subjected to carbon burning. After burning carbon for 4h, introducing CH2Cl2(200ppm)、O2(2%) N2Treating with gas at 550 deg.C for 1H, then changing to air for 1H, purging with nitrogen, and introducing H2After treatment at 550 ℃ for 1h, regeneration was complete.
The activity test of the regenerated catalyst was carried out according to the fresh catalyst, and the activity test thereof is shown in Table 1.
Comparative example 1
The reaction of propane dehydrogenation to propylene and the regeneration of the catalyst were carried out on a fixed bed reactor using the catalyst sample prepared in example 2, the reaction conditions and the regeneration conditions were the same as those in example 2, and the activity test of the regenerated catalyst is shown in table 1.
Comparative example 2
The reaction of propane dehydrogenation to propylene and the regeneration of the catalyst were carried out on the catalyst sample prepared in example 5 in a circulating fluidized bed reactor under the same reaction conditions and regeneration conditions as those in example 5, and the activity test of the regenerated catalyst is shown in table 1.
The results of the catalyst activity test after 20 regenerations of examples and comparative examples are shown in table 1 below.
TABLE 1 regenerated catalyst Activity test results
Figure GDA0002543636410000101
Figure GDA0002543636410000111
As can be seen from the data in Table 1, the propylene yield of the same catalyst was significantly reduced after testing using either the fluidized bed or the fixed reaction system, indicating that: the fixed fluidized bed reactor and the P with the particle size of 50-150 meshes are adoptedtThe catalyst is matched, and the propane dehydrogenation effect is optimal.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.

Claims (3)

1. A reaction and regeneration process of a fixed fluidized bed for preparing propylene by propane dehydrogenation is characterized in that three fixed fluidized bed reactors are adopted, dehydrogenation catalyst beds are arranged in the three reactors, raw material mixed gas 4 of hydrogen and propane is subjected to external heat exchange and heating, and initial material flow of the raw material mixed gas, namely 50% of normal flow, firstly enters a No. 1 reactor 1 to perform dehydrogenation reaction; after the reaction period is over half, the flow of the raw material mixed gas 4 is increased to 100%, and 50% of the raw material mixed gas 4 is divided to enter the No. 2 reactor 2 for dehydrogenation reaction;
after reacting for one period, stopping feeding the raw material mixed gas 4 into the No. 1 reactor 1, and introducing the regenerated mixed gas 5 into the No. 1 reactor 1 for regeneration treatment; 50 percent of raw material mixed gas 4 enters a No. 3 reactor 3 for reaction;
when the reaction time is 1.5 periods, the regeneration of the 1# reactor 1 is completed; at the moment, the feeding of the No. 2 reactor 2 is stopped, the regeneration mixed gas 5 is introduced into the No. 2 reactor 2 for regeneration treatment, and 50% of the raw material mixed gas 4 enters the No. 1 reactor 1 again for reaction;
when the reaction is carried out for 2 periods, the regeneration of the 2# reactor 2 is completed, at the moment, the feeding of the 3# reactor 3 is stopped, the regenerated mixed gas 5 is introduced into the 3# reactor 3 for regeneration treatment, and 50% of the raw material mixed gas 4 reenters the 2# reactor 2 for reaction;
the three reactors are sequentially switched from catalytic dehydrogenation reaction to catalyst regeneration according to the flow, so that the stability of the system is kept, and the catalyst is added into the required reactor from the catalyst feeding system 6 at regular time by calculating the abrasion loss of the catalyst in each reactor;
three streams of product gas 1a,2a and 3a of the three reactors are collected uniformly and then enter a cyclone separator 7 for dust removal treatment, catalyst powder is collected, and the clean material after dust removal enters a next-stage separation system; the regenerated gases 1b,2b and 3b are collected together through three streams of material flows respectively and then are dedusted by a regeneration cyclone separator 8, catalyst powder is collected, and the dedusted regenerated gases enter a next-stage treatment and discharge system;
preparing a catalyst:
1) mixing weighed pseudo-boehmite with distilled water, gradually dropwise adding dilute nitric acid for acidification under the heating condition of 70 ℃, and controlling the pH value to be between 3.0 and 4.0 to form alumina sol; then adding polyvinyl alcohol, stirring for 1h, finally cooling to 30 ℃ and spraying in a spray drying agent to prepare Al2O3Calcining the microsphere particles at 600 ℃ for 2 hours, and sieving the microsphere particles to obtain particles of 50-100 meshes for later use;
2) weighing 100g of the particle carrier and distilled water required by isovolumetric impregnation of the particle carrier, then weighing a certain amount of chloroplatinic acid, stannous chloride, lithium nitrate and gallium nitrate, respectively dissolving in the distilled water and uniformly mixing, finally impregnating the carrier in the mixed solution in an isovolumetric manner overnight, drying, calcining at 550 ℃ for 4 hours, and obtaining the finally required fresh catalyst, wherein the catalyst comprises the following components: pt0.29%, Sn0.4%, Li0.6%, Ga0.3%, and the balance Al2O3；
The fresh catalyst is subjected to pure hydrogen reduction treatment for 1h at the temperature of 550 ℃, and the volume space velocity is 2000h-1Then raising the temperature to the reaction temperature for reaction, and carrying out propane dehydrogenation by adopting the processReacting and regenerating the fixed fluidized bed for preparing the propylene;
propane dehydrogenation activity conditions: reaction temperature 605 ℃, catalyst loading 100g, H in feed gas2:C3H80.25 percent and the volume space velocity of 1500h-1Reacting for 18 hours under the reaction pressure of 0.1MPa for regeneration;
regeneration conditions are as follows: the regeneration temperature is 550 ℃, the regeneration pressure is 50Kpa, nitrogen is firstly introduced to purge the catalyst, and then the composition N is introduced2、O2Burning 10% oxygen-containing regeneration gas; after burning for 2h, introducing C2H5-CH3Cl2200ppm、H2O0.08% of N2Treating the catalyst with gas at 550 deg.C for 1H, then changing to air for 1H, purging with nitrogen, and introducing H2After treatment at 550 ℃ for 1h, regeneration was complete.
2. A reaction and regeneration process of a fixed fluidized bed for preparing propylene by propane dehydrogenation is characterized in that three fixed fluidized bed reactors are adopted, dehydrogenation catalyst beds are arranged in the three reactors, raw material mixed gas 4 of hydrogen and propane is subjected to external heat exchange and heating, and initial material flow of the raw material mixed gas, namely 50% of normal flow, firstly enters a No. 1 reactor 1 to perform dehydrogenation reaction; after the reaction period is over half, the flow of the raw material mixed gas 4 is increased to 100%, and 50% of the raw material mixed gas 4 is divided to enter the No. 2 reactor 2 for dehydrogenation reaction;
after reacting for one period, stopping feeding the raw material mixed gas 4 into the No. 1 reactor 1, and introducing the regenerated mixed gas 5 into the No. 1 reactor 1 for regeneration treatment; 50 percent of raw material mixed gas 4 enters a No. 3 reactor 3 for reaction;
when the reaction time is 1.5 periods, the regeneration of the 1# reactor 1 is completed; at the moment, the feeding of the No. 2 reactor 2 is stopped, the regeneration mixed gas 5 is introduced into the No. 2 reactor 2 for regeneration treatment, and 50% of the raw material mixed gas 4 enters the No. 1 reactor 1 again for reaction;
when the reaction is carried out for 2 periods, the regeneration of the 2# reactor 2 is completed, at the moment, the feeding of the 3# reactor 3 is stopped, the regenerated mixed gas 5 is introduced into the 3# reactor 3 for regeneration treatment, and 50% of the raw material mixed gas 4 reenters the 2# reactor 2 for reaction;
the three reactors are sequentially switched from catalytic dehydrogenation reaction to catalyst regeneration according to the flow, so that the stability of the system is kept, and the catalyst is added into the required reactor from the catalyst feeding system 6 at regular time by calculating the abrasion loss of the catalyst in each reactor;
three streams of product gas 1a,2a and 3a of the three reactors are collected uniformly and then enter a cyclone separator 7 for dust removal treatment, catalyst powder is collected, and the clean material after dust removal enters a next-stage separation system; the regenerated gases 1b,2b and 3b are collected together through three streams of material flows respectively and then are dedusted by a regeneration cyclone separator 8, catalyst powder is collected, and the dedusted regenerated gases enter a next-stage treatment and discharge system;
preparing a catalyst:
1) mixing weighed pseudo-boehmite with distilled water, gradually dropwise adding dilute nitric acid for acidification under the heating condition of 70 ℃, and controlling the pH value to be between 3.0 and 4.0 to form alumina sol; then adding polyvinyl alcohol, stirring for 1h, finally cooling to 30 ℃ and spraying in a spray drying agent to prepare Al2O3Calcining the microsphere particles at 600 ℃ for 2 hours, and sieving the microsphere particles to obtain particles of 50-100 meshes for later use;
2) weighing 100g of the particle carrier and distilled water required by equal-volume impregnation of the particle carrier, then weighing a certain amount of chloroplatinic acid, stannous chloride and lithium nitrate, respectively dissolving in the distilled water, uniformly mixing, finally impregnating the carrier in equal volume in a mixed solution, impregnating overnight, drying, and calcining at 550 ℃ for 4 hours to obtain a finally required fresh catalyst, wherein the catalyst comprises the following components: pt0.26%, Sn0.25%, Li0.9%, and Al for the rest2O3(ii) a Pure hydrogen reduction treatment is carried out on a fresh catalyst for 1h at the temperature of 500 ℃, and the volume space velocity is 3000h-1Then heating to the reaction temperature for reaction, and carrying out reaction and regeneration of the fixed fluidized bed for preparing propylene by propane dehydrogenation by adopting the technical process;
propane dehydrogenation activity conditions: reaction temperature 605 ℃, catalyst loading 100g, H in feed gas2:C3H80.35, volume space velocity of 2000h-1Reaction pressure 0.2MPa, reacting for 24 hours for regeneration;
regeneration conditions are as follows: the regeneration temperature is 500 ℃, the regeneration pressure is 50KPa, nitrogen is firstly introduced to purge the catalyst, and then the composition N is introduced2、O2Burning carbon with 6% oxygen-containing regeneration gas for 3h, introducing HCl500ppm and O22% of N2Treating with gas at 500 deg.C for 1 hr, then changing to air for 1 hr, purging with nitrogen, and introducing H2After 1h of treatment at 500 ℃, the regeneration is completed.
3. A reaction and regeneration process of a fixed fluidized bed for preparing propylene by propane dehydrogenation is characterized in that three fixed fluidized bed reactors are adopted, dehydrogenation catalyst beds are arranged in the three reactors, raw material mixed gas 4 of hydrogen and propane is subjected to external heat exchange and heating, and initial material flow of the raw material mixed gas, namely 50% of normal flow, firstly enters a No. 1 reactor 1 to perform dehydrogenation reaction; after the reaction period is over half, the flow of the raw material mixed gas 4 is increased to 100%, and 50% of the raw material mixed gas 4 is divided to enter the No. 2 reactor 2 for dehydrogenation reaction;
after reacting for one period, stopping feeding the raw material mixed gas 4 into the No. 1 reactor 1, and introducing the regenerated mixed gas 5 into the No. 1 reactor 1 for regeneration treatment; 50 percent of raw material mixed gas 4 enters a No. 3 reactor 3 for reaction;
when the reaction time is 1.5 periods, the regeneration of the 1# reactor 1 is completed; at the moment, the feeding of the No. 2 reactor 2 is stopped, the regeneration mixed gas 5 is introduced into the No. 2 reactor 2 for regeneration treatment, and 50% of the raw material mixed gas 4 enters the No. 1 reactor 1 again for reaction;
when the reaction is carried out for 2 periods, the regeneration of the 2# reactor 2 is completed, at the moment, the feeding of the 3# reactor 3 is stopped, the regenerated mixed gas 5 is introduced into the 3# reactor 3 for regeneration treatment, and 50% of the raw material mixed gas 4 reenters the 2# reactor 2 for reaction;
the three reactors are sequentially switched from catalytic dehydrogenation reaction to catalyst regeneration according to the flow, so that the stability of the system is kept, and the catalyst is added into the required reactor from the catalyst feeding system 6 at regular time by calculating the abrasion loss of the catalyst in each reactor;
three streams of product gas 1a,2a and 3a of the three reactors are collected uniformly and then enter a cyclone separator 7 for dust removal treatment, catalyst powder is collected, and the clean material after dust removal enters a next-stage separation system; the regenerated gases 1b,2b and 3b are collected together through three streams of material flows respectively and then are dedusted by a regeneration cyclone separator 8, catalyst powder is collected, and the dedusted regenerated gases enter a next-stage treatment and discharge system;
preparing a catalyst:
1) mixing weighed pseudo-boehmite with distilled water, gradually dropwise adding dilute nitric acid for acidification under the heating condition of 70 ℃, and controlling the pH value to be between 3.0 and 4.0 to form alumina sol; then adding polyvinyl alcohol, stirring for 1h, finally cooling to 30 ℃ and spraying in a spray drying agent to prepare Al2O3Calcining the microsphere particles at 600 ℃ for 2 hours, and sieving the microsphere particles to obtain particles of 50-100 meshes for later use;
2) weighing 100g of the particle carrier and distilled water required by equal-volume impregnation of the particle carrier, then weighing a certain amount of chloroplatinic acid, stannous chloride, potassium nitrate and lanthanum nitrate, respectively dissolving in the distilled water and uniformly mixing, finally impregnating the carrier in equal volume in a mixed solution, impregnating overnight and drying, and calcining at 550 ℃ for 4 hours to obtain a finally required fresh catalyst, wherein the catalyst comprises the following components: pt0.35%, Sn0.35%, K0.4%, La0.25%, and Al in balance2O3；
The fresh catalyst is subjected to pure hydrogen reduction treatment for 1h at the temperature of 550 ℃, and the volume space velocity is 2000h-1Then heating to the reaction temperature for reaction, and carrying out reaction and regeneration of the fixed fluidized bed for preparing propylene by propane dehydrogenation by adopting the technical process;
propane dehydrogenation activity conditions: reaction temperature 605 ℃, catalyst loading 100g, H in feed gas2:C3H80.15 and volume space velocity of 3000h-1Reacting for 12 hours at the reaction pressure of 50KPa for regeneration;
regeneration conditions are as follows: the regeneration temperature is 550 ℃, the regeneration pressure is 30KPa, nitrogen is firstly introduced to purge the catalyst, and then the composition N is introduced2、O2Burning carbon with 5% oxygen-containing regeneration gas for 2h, introducing CH2Cl250ppm、H2O0.05% of N2Treating with gas at 550 deg.C for 1H, then changing to air for 1H, purging with nitrogen, and introducing H2After treatment at 550 ℃ for 1h, regeneration was complete.
CN201811356906.1A 2018-11-15 2018-11-15 Reaction and regeneration process of fixed fluidized bed for preparing propylene by propane dehydrogenation Active CN109320392B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201811356906.1A CN109320392B (en) 2018-11-15 2018-11-15 Reaction and regeneration process of fixed fluidized bed for preparing propylene by propane dehydrogenation

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201811356906.1A CN109320392B (en) 2018-11-15 2018-11-15 Reaction and regeneration process of fixed fluidized bed for preparing propylene by propane dehydrogenation

Publications (2)

Publication Number Publication Date
CN109320392A CN109320392A (en) 2019-02-12
CN109320392B true CN109320392B (en) 2020-09-01

Family

ID=65257691

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201811356906.1A Active CN109320392B (en) 2018-11-15 2018-11-15 Reaction and regeneration process of fixed fluidized bed for preparing propylene by propane dehydrogenation

Country Status (1)

Country Link
CN (1) CN109320392B (en)

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109796294A (en) * 2019-02-22 2019-05-24 西南化工研究设计院有限公司 Using the preparing propylene by dehydrogenating propane reaction system and methods and applications of platinum group catalyst
WO2021151813A1 (en) * 2020-01-30 2021-08-05 Haldor Topsøe A/S Process for dehydrogenation of a hydrocarbon feed stock in a fixed bed reactor
CN111790382A (en) * 2020-08-13 2020-10-20 福州大学 Active regeneration method for Pt-based catalyst for preparing propylene by propane dehydrogenation
CN112250573B (en) * 2020-10-20 2021-08-17 西南化工研究设计院有限公司 Method for preparing methyl acetate by dimethyl ether carbonylation
CN114570364A (en) * 2022-03-28 2022-06-03 福州大学 Pretreatment method of Pt-based catalyst for preparing propylene by propane dehydrogenation
CN115350652B (en) * 2022-08-04 2023-06-20 西南化工研究设计院有限公司 Fluidized bed propane dehydrogenation device using dehydrogenation catalyst and process thereof
CN115155613B (en) * 2022-08-04 2023-12-05 西南化工研究设计院有限公司 Preparation method and application of novel environment-friendly propane dehydrogenation catalyst
CN117160369B (en) * 2023-11-01 2024-04-09 中海石油气电集团有限责任公司 Method and device for catalytic conversion of normal-para-hydrogen by continuous and efficient operation of catalyst

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10060099A1 (en) * 2000-12-04 2002-06-06 Basf Ag Regeneration of a dehydrogenation catalyst
CA2645563A1 (en) * 2006-03-29 2007-10-11 Basf Se Method for producing propene from propane
CN103265394B (en) * 2013-05-27 2015-06-03 神华集团有限责任公司 Methanation reaction system and regeneration technology of methanation catalyst
CN104941640A (en) * 2015-05-29 2015-09-30 南开大学 Catalyst for production of propylene through catalytic dehydrogenation of propane, and preparation method thereof
CN106674010B (en) * 2015-11-10 2020-01-07 上海浦景化工技术股份有限公司 Process for preparing methyl methacrylate by aldol condensation method
CN108187671B (en) * 2018-01-04 2020-05-12 西南化工研究设计院有限公司 Regeneration method of aluminum oxide loaded platinum-tin dehydrogenation catalyst

Also Published As

Publication number Publication date
CN109320392A (en) 2019-02-12

Similar Documents

Publication Publication Date Title
CN109320392B (en) Reaction and regeneration process of fixed fluidized bed for preparing propylene by propane dehydrogenation
CN107848910B (en) Improved oxidative dehydrogenation catalyst
CN1040422C (en) Method for preparation of light alkene by dehydrogenation from relative paraffin
CN107486195B (en) Preparation method of low-carbon alkane dehydrogenation catalyst
US10406517B2 (en) Double peroxide treatment of oxidative dehydrogenation catalyst
CN101687182B (en) Process for reactivation of metathesis catalysts and process for production of olefins comprising the reactivation
CN105727930A (en) Catalyst for propylene production using propane dehydrogenation and preparation method and application of catalyst
CN104203401A (en) Process for making ethylene and acetic acid
EP3528945A1 (en) Process for producing oxidative dehydrogenation catalysts using hydrothermal treatment and peroxide treatment
CN108409523A (en) The method for carrying out dehydrogenating low-carbon alkane using metal oxide
CN112552140B (en) Method for catalyzing propane dehydrogenation by using transition metal oxide-silicon oxide molecular sieve catalyst
CN110721705B (en) Platinum-based catalyst and method for preparing propylene by propane dehydrogenation in fixed bed
CN111686709B (en) Propane dehydrogenation propylene supported catalyst with specific pore structure and preparation method thereof
CN113058586A (en) Catalyst for preparing olefin by oxidizing low-carbon alkane with carbon dioxide and preparation method thereof
EP1251961B1 (en) Hydrocarbon dehydrogenation catalyst and process
CN110193365A (en) A kind of method that technique for atomic layer deposition prepares platinum based catalyst and its application in dehydrogenating propane reaction
WO2019176247A1 (en) Method for producing indane
CN107488093B (en) Dehydrogenation process of low-carbon alkane
CN114433220B (en) Preparation method of benzene and synthesis gas alkylation catalyst
CN110075855B (en) Dehydrogenation catalyst and preparation method and application thereof
CN107486196B (en) Fixed bed dehydrogenation process of low-carbon alkane
CN113385172B (en) Catalyst for preparing ethylene by ethane hydrogen dehydrogenation and preparation and application thereof
CN114433217B (en) Benzene and synthesis gas alkylation catalyst and preparation method and application thereof
CN113117741B (en) Preparation method and application of aluminum-zinc phosphate molecular sieve catalyst
CN109317142B (en) Catalyst for preparing propylene by propane dehydrogenation and preparation method and application thereof

Legal Events

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