CN107486196B - Fixed bed dehydrogenation process of low-carbon alkane - Google Patents

Fixed bed dehydrogenation process of low-carbon alkane Download PDF

Info

Publication number
CN107486196B
CN107486196B CN201610412996.6A CN201610412996A CN107486196B CN 107486196 B CN107486196 B CN 107486196B CN 201610412996 A CN201610412996 A CN 201610412996A CN 107486196 B CN107486196 B CN 107486196B
Authority
CN
China
Prior art keywords
dehydrogenation
low
catalyst
regeneration
space velocity
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
CN201610412996.6A
Other languages
Chinese (zh)
Other versions
CN107486196A (en
Inventor
李长明
周金波
李博
王艳飞
李秋颖
程中克
苟文甲
董炳利
唐迎春
马艳捷
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.)
Petrochina Co Ltd
Original Assignee
Petrochina Co Ltd
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 Petrochina Co Ltd filed Critical Petrochina Co Ltd
Priority to CN201610412996.6A priority Critical patent/CN107486196B/en
Publication of CN107486196A publication Critical patent/CN107486196A/en
Application granted granted Critical
Publication of CN107486196B publication Critical patent/CN107486196B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/24—Chromium, molybdenum or tungsten
    • B01J23/26—Chromium
    • 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
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/85—Chromium, molybdenum or tungsten
    • B01J23/86—Chromium
    • B01J23/862—Iron and chromium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/85—Chromium, molybdenum or tungsten
    • B01J23/86—Chromium
    • B01J23/864—Cobalt and chromium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/85—Chromium, molybdenum or tungsten
    • B01J23/86—Chromium
    • B01J23/866—Nickel and chromium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/85—Chromium, molybdenum or tungsten
    • B01J23/86—Chromium
    • B01J23/868—Chromium copper and chromium
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
    • C07C5/327—Formation of non-aromatic carbon-to-carbon double bonds only
    • C07C5/333—Catalytic processes
    • 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
    • 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
    • C07C2523/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • C07C2523/24—Chromium, molybdenum or tungsten
    • C07C2523/26—Chromium
    • 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
    • C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
    • C07C2523/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36
    • C07C2523/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • C07C2523/85—Chromium, molybdenum or tungsten
    • C07C2523/86—Chromium
    • 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

Landscapes

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

Abstract

The invention discloses a low-carbon alkane dehydrogenation process. The catalyst is prepared by dissolving a precursor of high-valence chromium in a reducing agent solution, soaking the precursor in an alumina-based carrier, washing, filtering and drying. The catalyst is combined with a fixed bed process, so that the whole dehydrogenation process flow is simple, the equipment investment is low, the catalyst is cheap, the stability is high, the conversion rate of low-carbon alkane is high, and the selectivity is good.

Description

Fixed bed dehydrogenation process of low-carbon alkane
Technical Field
The invention relates to a low-carbon alkane dehydrogenation process method, in particular to a process method for preparing butylene by butane dehydrogenation and preparing propylene by propane dehydrogenation.
Background
In recent years, with the rapid development of the global petrochemical industry, the demand for low-carbon olefins is increasing. The catalytic dehydrogenation technology of the low-carbon alkane is an effective way for increasing the yield of C3-C4 olefin.
The catalytic dehydrogenation reaction of the low-carbon alkane is limited by thermodynamic equilibrium and needs to be carried out under the harsh conditions of high temperature and low pressure. The excessive temperature causes the alkane cracking reaction and deep dehydrogenation to be intensified and the selectivity to be reduced; meanwhile, the carbon deposition on the surface of the catalyst is accelerated, so that the catalyst is quickly deactivated. Therefore, the catalyst needs to be periodically regenerated, and in order to enable continuous and smooth operation of industrial plants, the Oleflex process of UOP corporation uses a Pt-based catalyst (US3584060, 3878131, 4438288) and a moving bed reactor, and continuously regenerates the deactivated catalyst. The main problems of the technology are high cost of the noble metal catalyst and large investment of the moving bed reactor.
The Catofin process of Lummus corporation adopts fixed bed process, the catalyst is chromium oxide/aluminium oxide catalyst, but it needs to be carried out under negative pressure to have higher conversion rate of low carbon alkane.
US4167532, 4902849, 4926005 discloses a process for the dehydrogenation of isobutane to isobutene using a noble metal Pt-based catalyst supported on a zinc aluminate spinel carrier and a tubular fixed bed. The use of the tubular fixed bed can ensure that the temperature distribution of the bed layer is relatively uniform, the regeneration period of the catalyst is prolonged to a certain extent, but the manufacturing cost of the tubular reactor is still higher.
CN1213662A discloses a dehydrogenation process technology of isobutane, wherein a dehydrogenation reaction is carried out in a fluidized bed reactor, the used catalyst is a chromium microsphere catalyst, the catalyst of the process can be continuously regenerated, and the production can be continuously carried out, but the manufacture, use and recovery of the chromium catalyst for the fluidized bed have strict environmental protection requirements.
The invention aims to provide a low-carbon alkane fixed bed dehydrogenation process which is simple in process flow, low in equipment investment, low in catalyst cost, strong in stability, high in low-carbon alkane conversion rate and good in selectivity.
Disclosure of Invention
Aiming at the problems, the invention provides a low-carbon alkane dehydrogenation process method which adopts a fixed bed process and is filled with a Cr-series catalyst. The catalyst mainly adjusts the dispersion state of Cr species on the carrier through in-situ reaction, so that the activity, selectivity and stability of the catalyst are correspondingly improved.
The invention provides a low-carbon alkane dehydrogenation process which is characterized in that a low-carbon alkane raw material enters a fixed bed reactor filled with a chromium dehydrogenation catalyst for dehydrogenation reaction, and the preparation method of the chromium dehydrogenation catalyst is that a high-valence chromium precursor is dissolved in a reducing agent solution capable of reducing the high-valence chromium precursor into low-valence chromium, and then the low-valence chromium precursor is soaked in an alumina-based carrier, washed, filtered and dried to obtain the low-carbon alkane dehydrogenation catalyst.
In the preparation method of the chromium-based dehydrogenation catalyst, the conventional operations in the field can be adopted for impregnation, washing, filtering, drying and the like. The dipping temperature can be 30-200 ℃, preferably 60-150 ℃, and the dipping time can be 0.5-20 h, preferably 0.5-6 h.
In the preparation method of the chromium dehydrogenation catalyst, the high-valence chromium precursor is CrO3、(NH4)2Cr2O7、Na2Cr2O7、K2Cr2O7、(NH4)2CrO4、Na2CrO4And K2CrO4One or more of them.
In the preparation method of the chromium-based dehydrogenation catalyst, the reducing agent solution is an aqueous solution containing glycol, glycerol, glucose, oxalic acid or ascorbic acid.
In the preparation method of the chromium-based dehydrogenation catalyst, when the reducing agent solution is an aqueous solution containing a glucose, oxalic acid or ascorbic acid component, the mass concentration of the glucose, oxalic acid or ascorbic acid component is preferably 1 wt.% to 60 wt.%, and more preferably 3 wt.% to 30 wt.%.
In the preparation method of the chromium-based dehydrogenation catalyst, the alumina-based carrier is preferably an alumina carrier or an alumina carrier containing a refractory inorganic oxide; the refractory inorganic oxide is preferably one or more of silicon oxide, zirconium oxide and titanium oxide; the refractory inorganic oxide is preferably present in the alumina-based support in an amount of 5 wt.% or less.
In the preparation method of the chromium-based dehydrogenation catalyst, the mol ratio of the reducing agent to the high-valence chromium precursor is preferably 0.5-10: 1, more preferably 1 to 5: 1.
In the preparation method of the chromium dehydrogenation catalyst, the alumina-based carrier is impregnated and dried, and then the functional auxiliary agent can be impregnated, and then the chromium dehydrogenation catalyst is obtained after drying and roasting.
In the preparation method of the chromium-based dehydrogenation catalyst, the auxiliary agent is preferably one or more of nitrate or acetate of Na, K, Ca, Sr, La, Sn, Cu, Ni, Co, Fe and Zn.
The preferred preparation method of the chromium-based dehydrogenation catalyst comprises the following steps: dissolving a high-valence chromium precursor in a reducing agent solution capable of reducing the high-valence chromium precursor into low-valence chromium, soaking the low-valence chromium precursor into an alumina-based carrier at the soaking temperature of 30-200 ℃ for 0.5-20 h, washing, filtering, drying, soaking a functional auxiliary agent, drying and roasting to obtain the chromium dehydrogenation catalyst.
In the preparation method of the chromium-based dehydrogenation catalyst, the drying and roasting are carried out in an air atmosphere, and the drying is preferably carried out at 60-100 ℃ for 1-8 h; the roasting is preferably carried out at 650-750 ℃ for 2-10 h.
Cr in the chromium-based dehydrogenation catalyst of the invention2O3The content of the functional additive is 3-20 wt%, and the content of the functional additive is 0.5-6 wt%. The low-carbon alkane raw material enters a fixed bed reactor filled with the catalyst to carry out dehydrogenation reaction, and a plurality of fixed bed reactors are switched according to process conditions.
The number of the fixed bed reactors is at least more than 3, at least one reactor carries out dehydrogenation reaction, at least one reactor carries out regeneration reaction and 1 or more spare reactors.
Besides the catalyst, the fixed bed of the invention is also filled with an inert carrier, the filling amount of the inert carrier is 30-300 wt% of the catalyst, and the inert carrier is quartz sand, ceramic balls and inert alumina balls.
The fixed bed dehydrogenation reaction temperature is 550-650 ℃.
The fixed bed dehydrogenation reaction pressure is 0.05-0.3 MPa.
The low-carbon alkane has a mass space velocity of 0.1-10 h-1。
The on-line time of the fixed bed reactor is 0.1-1.0 h, and then switching is carried out to enter a regeneration mode.
The regeneration temperature of the fixed bed is 630-720 ℃.
The regeneration pressure of the fixed bed is 0.05-0.3 MPa.
The regeneration gas of the fixed bed is air, and the volume space velocity is 100-5000 h-1。
The on-line time of the fixed bed regenerator is 0.2-2.0 h.
The process method is used for catalytic dehydrogenation of alkane components of C3-C6.
Reaction of high-valence chromium with reducing agent to generate Cr2O3By controlling the limiting function of the pore and the reaction condition, Cr2O3The directly generated sub-nanometer clusters are attached to the hole wall, and the cluster size is uniform and can be regulated and controlled in the process. Compared with the methods such as an immersion method, a precipitation method and the like, the method of the in-situ reaction can obtain Cr with different dispersity2O3A base catalyst. The surface of the highly dispersed Cr contains more Cr-OH corresponding to more B acid centers, so that in the dehydrogenation reaction of low-carbon alkane, the deep cracking reaction is easy to induce the rapid carbon deposition of the catalyst to inactivate, the selectivity of the catalyst is poor, and the inactivation speed is high; at low dispersion, the Cr atoms agglomerate into large particles of Cr2O3Because the dehydrogenation reaction of the low-carbon alkane is a surface catalytic reaction, Cr atoms in the particles are completely wrapped to cause atom utilizationThe efficiency becomes low and at the same time, large-grained Cr2O3Easy to induce cracking and other side reactions, and relatively low catalytic activity and selectivity. According to the invention, the dispersion state of Cr species on the carrier is effectively regulated and controlled, and the activity, selectivity and stability of the catalyst are correspondingly improved. The catalyst is combined with a fixed bed process, so that the whole dehydrogenation process flow is simple, the equipment investment is low, the catalyst is cheap, the stability is high, the conversion rate of low-carbon alkane is high, and the selectivity is good.
The method has the advantages that the low-carbon alkane dehydrogenation catalyst has controllable Cr clusters, the catalyst with moderate Cr dispersion degree is obtained by an in-situ reduction method, the acid content of B on the surface of the catalyst is reduced, the utilization efficiency of active atom Cr is improved, and the dehydrogenation activity, selectivity and carbon deposition resistance of the catalyst are improved. The low-carbon alkane dehydrogenation process has simple flow and low equipment investment.
Drawings
FIG. 1 is a schematic process flow diagram of the present invention.
In the figure, 1-3-preheater, 4-6-valve, 7-fixed bed reactor, 8-12-valve, 13-fixed bed reactor, 14, 15-valve.
Detailed Description
The present invention is described in further detail below by way of examples, which should not be construed as limiting the invention thereto.
Description of the Process
The raw materials enter a fixed bed reactor 7 filled with catalyst and inert carriers through a valve 4 after being preheated by a preheater 1, products after dehydrogenation reaction enter a product conveying pipe network through a valve 8, and after reaction for a period of time, the reactor is switched: closing the valve 4 and the valve 8, opening the valve 10 and the valve 14, and starting the fixed bed reactor 13 to perform dehydrogenation reaction; and opening the valve 5, the valve 6 and the valve 9, carrying out regeneration reaction on the fixed bed reactor 7, closing the valve 5 after regeneration is finished, closing the valve 6 and the valve 9 after nitrogen purging, and enabling the reactor 7 to enter a standby state. The starting of the standby reactor can be reasonably controlled according to the reaction and regeneration process conditions.
Example 1
223g(NH4)2Cr2O7Dissolving in 800ml of ethylene glycol, and soaking in an equal volume to 1000g of porous gamma-Al2O3In the powder. The powder was placed in an oven at 120 ℃ for 4h, washed with deionized water, filtered and dried at 80 ℃ for 2 h. 37g KNO3Dissolving in 800ml deionized water, soaking in the treated powder in the same volume, drying at 80 deg.C for 4 hr, calcining at 680 deg.C for 5 hr, molding and sieving to obtain catalyst A.
Dehydrogenation of butane:
the reaction process conditions are that the reaction temperature is 590 ℃, the pressure is 0.11MPa, and the butane mass space velocity is 1.0h-1The filling amount of the inert carrier is 100 wt% of the filling amount of the catalyst A, and the reaction time is 0.7 h; the regeneration gas is air, the regeneration temperature is 660 ℃, the regeneration pressure is 0.10MPa, and the volume space velocity is 1000h-1The regeneration time is 0.6h, and the nitrogen gas stripping space velocity is 1000h-1And the air stripping time is 0.1 h.
Dehydrogenation of propane:
the reaction process conditions comprise that the reaction temperature is 600 ℃, the pressure is 0.11MPa, and the mass space velocity of propane is 1.0h-1The filling amount of the inert carrier is 100 wt% of the filling amount of the catalyst A, and the reaction time is 0.7 h; the regeneration gas is air, the regeneration temperature is 660 ℃, the regeneration pressure is 0.10MPa, and the volume space velocity is 1000h-1The regeneration time is 0.6h, and the nitrogen gas stripping space velocity is 1000h-1And the air stripping time is 0.1 h.
Comparative example 1
708g Cr(NO3)3·9H2O、37g KNO3Dissolving in 400ml deionized water, soaking in 1000g porous gamma-Al in equal volume2O3Drying the powder at 80 ℃ for 4h, roasting at 680 ℃ for 5h, and molding and screening to obtain a catalyst, which is recorded as catalyst B.
Dehydrogenation of butane:
the reaction process conditions are that the reaction temperature is 590 ℃, the pressure is 0.11MPa, and the butane mass space velocity is 1.0h-1The filling amount of the inert carrier is 100 wt% of the filling amount of the catalyst A, and the reaction time is 0.7 h; the regeneration gas is air, the regeneration temperature is 660 ℃, the regeneration pressure is 0.10MPa, and the volume isThe space velocity is 1000h-1The regeneration time is 0.6h, and the nitrogen gas stripping space velocity is 1000h-1And the air stripping time is 0.1 h.
Dehydrogenation of propane:
the reaction process conditions comprise that the reaction temperature is 600 ℃, the pressure is 0.11MPa, and the mass space velocity of propane is 1.0h-1The filling amount of the inert carrier is 100 wt% of the filling amount of the catalyst A, and the reaction time is 0.7 h; the regeneration gas is air, the regeneration temperature is 660 ℃, the regeneration pressure is 0.10MPa, and the volume space velocity is 1000h-1The regeneration time is 0.6h, and the nitrogen gas stripping space velocity is 1000h-1And the air stripping time is 0.1 h.
Example 2
177g CrO3、248g(NH4)2C2O4Dissolving in 800ml deionized water, soaking in 1000g porous gamma-Al in equal volume2O3In the powder. The powder was placed in an oven at 60 ℃ for 6h, washed with deionized water, filtered and dried at 100 ℃ for 2 h. 78gCu (NO)3)2·3H2O、112g Fe(NO3)3·9H2Dissolving O in 700ml deionized water, soaking the powder in the same volume, drying at 120 deg.C for 3 hr, calcining at 700 deg.C for 6 hr, and sieving to obtain catalyst C.
Dehydrogenation of butane:
the reaction process conditions are that the reaction temperature is 585 ℃, the pressure is 0.11MPa, and the butane mass space velocity is 2.5h-1The filling amount of the inert carrier is 200 wt% of the filling amount of the catalyst C, and the reaction time is 0.5 h; the regeneration gas is air, the regeneration temperature is 670 ℃, the regeneration pressure is 0.10MPa, and the volume space velocity is 1000h-1The regeneration time is 0.9h, and the nitrogen gas stripping space velocity is 3000h-1And the air stripping time is 0.1 h.
Dehydrogenation of propane:
the reaction process conditions comprise 595 ℃ of reaction temperature, 0.11MPa of pressure and 5.5h of propane mass space velocity-1The filling amount of the inert carrier is 200 wt% of the filling amount of the catalyst C, and the reaction time is 0.5 h; the regeneration gas is air, the regeneration temperature is 670 ℃, the regeneration pressure is 0.10MPa, and the volume space velocity is 1000h-1The regeneration time is 0.9hAir lift space velocity of nitrogen gas is 3000h-1And the air stripping time is 0.1 h.
Comparative example 2
708g Cr(NO3)3·9H2O、78g Cu(NO3)2·3H2O、112g Fe(NO3)3·9H2Dissolving O in 350ml deionized water, soaking in 1000g of porous gamma-Al in equal volume2O3Drying the powder at 80 ℃ for 4h, roasting the powder at 700 ℃ for 6h, and forming and screening the powder to obtain a catalyst which is recorded as a catalyst D.
Dehydrogenation of butane:
the reaction process conditions are that the reaction temperature is 585 ℃, the pressure is 0.11MPa, and the butane mass space velocity is 2.5h-1The filling amount of the inert carrier is 200 wt% of the filling amount of the catalyst C, and the reaction time is 0.5 h; the regeneration gas is air, the regeneration temperature is 670 ℃, the regeneration pressure is 0.10MPa, and the volume space velocity is 1000h-1The regeneration time is 0.9h, and the nitrogen gas stripping space velocity is 3000h-1And the air stripping time is 0.1 h.
Dehydrogenation of propane:
the reaction process conditions comprise 595 ℃ of reaction temperature, 0.11MPa of pressure and 5.5h of propane mass space velocity-1The filling amount of the inert carrier is 200 wt% of the filling amount of the catalyst C, and the reaction time is 0.5 h; the regeneration gas is air, the regeneration temperature is 670 ℃, the regeneration pressure is 0.10MPa, and the volume space velocity is 1000h-1The regeneration time is 0.9h, and the nitrogen gas stripping space velocity is 3000h-1And the air stripping time is 0.1 h.
Example 3
130g K2Cr2O7Dissolving in 800ml of glycerol, and soaking in 1000g of porous gamma-Al in equal volume2O3In the powder. The powder was placed in an oven at 140 ℃ for 1h, washed with deionized water, filtered and dried at 80 ℃ for 4 h. 33g NaNO3、82g Ni(NO3)2·6H2Dissolving O in 800ml deionized water, soaking in the treated powder in the same volume, drying at 60 deg.C for 6 hr, calcining at 720 deg.C for 4 hr, molding and sieving to obtain catalyst, named as catalyst E.
Dehydrogenation of butane:
the reaction process conditions comprise that the reaction temperature is 610 ℃, the pressure is 0.2MPa, and the butane mass space velocity is 0.5h-1The filling amount of the inert carrier is 50 wt% of the filling amount of the catalyst D, and the reaction time is 0.2 h; the regeneration gas is air, the regeneration temperature is 650 ℃, the regeneration pressure is 0.10MPa, and the volume space velocity is 3000h-1The regeneration time is 0.5h, and the nitrogen gas stripping space velocity is 3000h-1And the air stripping time is 0.1 h.
Dehydrogenation of propane:
the reaction process conditions comprise that the reaction temperature is 620 ℃, the pressure is 0.2MPa, and the mass space velocity of propane is 1.5h-1The filling amount of the inert carrier is 50 wt% of the filling amount of the catalyst D, and the reaction time is 0.6 h; the regeneration gas is air, the regeneration temperature is 650 ℃, the regeneration pressure is 0.10MPa, and the volume space velocity is 3000h-1The regeneration time is 0.5h, and the nitrogen gas stripping space velocity is 3000h-1And the air stripping time is 0.1 h.
Comparative example 3
354g Cr(NO3)3·9H2O、33g NaNO3、82g Ni(NO3)2·6H2Dissolving O in 600ml deionized water, soaking in 1000g of porous gamma-Al in equal volume2O3Drying the powder at 80 deg.C for 4 hr, calcining at 720 deg.C for 4 hr, and sieving to obtain catalyst F.
Dehydrogenation of butane:
the reaction process conditions comprise that the reaction temperature is 610 ℃, the pressure is 0.2MPa, and the butane mass space velocity is 0.5h-1The filling amount of the inert carrier is 50 wt% of the filling amount of the catalyst D, and the reaction time is 0.2 h; the regeneration gas is air, the regeneration temperature is 650 ℃, the regeneration pressure is 0.10MPa, and the volume space velocity is 3000h-1The regeneration time is 0.5h, and the nitrogen gas stripping space velocity is 3000h-1And the air stripping time is 0.1 h.
Dehydrogenation of propane:
the reaction process conditions comprise that the reaction temperature is 620 ℃, the pressure is 0.2MPa, and the mass space velocity of propane is 1.5h-1The filling amount of the inert carrier is 50 wt% of the filling amount of the catalyst D, and the reaction time is 0.6 h; the regeneration gas is air, the regeneration temperature is 650 ℃, the regeneration pressure is 0.10MPa, and the volume space velocity is 3000h-1The regeneration time is 0.5h, and the nitrogen gas stripping space velocity is 3000h-1And the air stripping time is 0.1 h.
Example 4
230g Na2CrO439g of glucose was dissolved in 800ml of deionized water and the solution was immersed in 1000g of porous gamma-Al in equal volume2O3In the powder. The powder was placed in an oven at 85 ℃ for 4h, washed with deionized water, filtered and dried at 95 ℃ for 3 h. 37gKNO3、32g La(NO3)3·6H2O、114g Fe(NO3)2·9H2Dissolving O in 700ml deionized water, soaking in the treated powder in the same volume, drying at 70 deg.C for 5 hr, calcining at 690 deg.C for 6 hr, molding and sieving to obtain catalyst G.
Comparative example 4
566g Cr(NO3)3·9H2O、37g KNO3、32g La(NO3)3·6H2O、114gFe(NO3)2·9H2Dissolving O in 480ml deionized water, soaking in 1000g of porous gamma-Al in equal volume2O3Drying the powder at 80 ℃ for 4H, roasting the powder at 690 ℃ for 6H, and forming and screening the dried powder to obtain a catalyst which is recorded as a catalyst H.
Dehydrogenation of butane:
the reaction process conditions are that the reaction temperature is 600 ℃, the pressure is 0.10MPa, and the mass space velocity of the low-carbon alkane is 2.0h-1The filling amount of the inert carrier is 300 wt% of the filling amount of the catalyst E, and the reaction time is 0.5 h; the regeneration gas is air, the regeneration temperature is 680 ℃, the regeneration pressure is 0.09MPa, and the volume space velocity is 2000h-1The regeneration time is 0.5h, and the nitrogen gas stripping space velocity is 2000h-1And the air stripping time is 0.1 h.
Dehydrogenation of propane:
the reaction process conditions comprise that the reaction temperature is 610 ℃, the pressure is 0.10MPa, and the mass space velocity of the low-carbon alkane is 2.0h-1The filling amount of the inert carrier is 300 wt% of the filling amount of the catalyst E, and the reaction time is 0.5 h; the regeneration gas is air, the regeneration temperature is 680 ℃, the regeneration pressure is 0.09MPa, and the volume space velocity is 2000h-1The regeneration time is 0.5h, and the nitrogen gas stripping space velocity is 2000h-1And the air stripping time is 0.1 h.
Comparative example 4
566g Cr(NO3)3·9H2O、37g KNO3、32g La(NO3)3·6H2O、114gFe(NO3)2·9H2Dissolving O in 480ml deionized water, soaking in 1000g of porous gamma-Al in equal volume2O3Drying the powder at 80 ℃ for 4H, roasting the powder at 690 ℃ for 6H, and forming and screening the dried powder to obtain a catalyst which is recorded as a catalyst H.
Dehydrogenation of butane:
the reaction process conditions are that the reaction temperature is 600 ℃, the pressure is 0.10MPa, and the mass space velocity of the low-carbon alkane is 2.0h-1The filling amount of the inert carrier is 300 wt% of the filling amount of the catalyst E, and the reaction time is 0.5 h; the regeneration gas is air, the regeneration temperature is 680 ℃, the regeneration pressure is 0.09MPa, and the volume space velocity is 2000h-1The regeneration time is 0.5h, and the nitrogen gas stripping space velocity is 2000h-1And the air stripping time is 0.1 h.
Dehydrogenation of propane:
the reaction process conditions comprise that the reaction temperature is 610 ℃, the pressure is 0.10MPa, and the mass space velocity of the low-carbon alkane is 2.0h-1The filling amount of the inert carrier is 300 wt% of the filling amount of the catalyst E, and the reaction time is 0.5 h; the regeneration gas is air, the regeneration temperature is 680 ℃, the regeneration pressure is 0.09MPa, and the volume space velocity is 2000h-1The regeneration time is 0.5h, and the nitrogen gas stripping space velocity is 2000h-1And the air stripping time is 0.1 h.
Example 5
377g K2CrO4282g ascorbic acid in 800ml deionized water, and soaking in 1000g porous gamma-Al in equal volume2O3In the powder. The powder was placed in an oven at 60 ℃ for 1h, washed with deionized water, filtered and dried at 80 ℃ for 4 h. 28gKNO3、65g Cu(NO3)2·3H2Dissolving O in 800ml deionized water, soaking in the treated powder in the same volume, drying at 60 deg.C for 6 hr, calcining at 720 deg.C for 4 hr, molding and sieving to obtain catalyst I.
Dehydrogenation of butane:
the reaction process conditions are that the reaction temperature is 600 ℃, the pressure is 0.10MPa, and the mass space velocity of the low-carbon alkane is 2.0h-1The filling amount of the inert carrier is 200 wt% of the filling amount of the catalyst E, and the reaction time is 0.5 h; the regeneration gas is air, the regeneration temperature is 680 ℃, the regeneration pressure is 0.2MPa, and the volume space velocity is 2000h-1The regeneration time is 0.6h, and the nitrogen gas stripping space velocity is 2000h-1And the air stripping time is 0.1 h.
Dehydrogenation of propane:
the reaction process conditions comprise that the reaction temperature is 610 ℃, the pressure is 0.10MPa, and the mass space velocity of the low-carbon alkane is 2.0h-1The filling amount of the inert carrier is 200 wt% of the filling amount of the catalyst E, and the reaction time is 0.5 h; the regeneration gas is air, the regeneration temperature is 680 ℃, the regeneration pressure is 0.2MPa, and the volume space velocity is 3000h-1The regeneration time is 0.5h, and the nitrogen gas stripping space velocity is 2000h-1And the air stripping time is 0.1 h.
Comparative example 5
779g Cr(NO3)3·9H2O、28g KNO3、65g Cu(NO3)2·3H2Dissolving O in 300ml deionized water, soaking in 1000g of porous gamma-Al in equal volume2O3Drying the powder at 80 deg.C for 4 hr, calcining at 720 deg.C for 4 hr, and sieving to obtain catalyst J. Dehydrogenation of butane:
the reaction process conditions are that the reaction temperature is 600 ℃, the pressure is 0.10MPa, and the mass space velocity of the low-carbon alkane is 2.0h-1The filling amount of the inert carrier is 200 wt% of the filling amount of the catalyst E, and the reaction time is 0.5 h; the regeneration gas is air, the regeneration temperature is 680 ℃, the regeneration pressure is 0.2MPa, and the volume space velocity is 2000h-1The regeneration time is 0.6h, and the nitrogen gas stripping space velocity is 2000h-1And the air stripping time is 0.1 h.
Dehydrogenation of propane:
the reaction process conditions comprise that the reaction temperature is 610 ℃, the pressure is 0.10MPa, and the mass space velocity of the low-carbon alkane is 2.0h-1The filling amount of the inert carrier is 200 wt% of the filling amount of the catalyst E, and the reaction time is 0.5 h; the regeneration gas is air, the regeneration temperature is 680 ℃, the regeneration pressure is 0.2MPa, and the volume space velocity is 3000h-1Then, againThe production time is 0.5h, and the nitrogen gas stripping space velocity is 2000h-1And the air stripping time is 0.1 h.
Example 6
323g(NH4)2CrO4Dissolving in 800ml of ethylene glycol, and soaking in an equal volume to 1000g of porous gamma-Al2O3In the powder. The powder was placed in an oven at 150 ℃ for 0.5h, washed with deionized water, filtered and dried at 80 ℃ for 2 h. 28g KNO3、65gCu(NO3)2·3H2Dissolving O in 800ml deionized water, soaking the powder in the same volume, drying at 80 deg.C for 4 hr, calcining at 680 deg.C for 8 hr, and sieving to obtain catalyst K.
Dehydrogenation of butane:
the reaction process conditions are that the reaction temperature is 600 ℃, the pressure is 0.10MPa, and the mass space velocity of the low-carbon alkane is 2.0h-1The filling amount of the inert carrier is 200 wt% of the filling amount of the catalyst E, and the reaction time is 0.5 h; the regeneration gas is air, the regeneration temperature is 690 ℃, the regeneration pressure is 0.2MPa, and the volume space velocity is 500h-1The regeneration time is 1.5h, and the nitrogen gas stripping space velocity is 2000h-1And the air stripping time is 0.1 h.
Dehydrogenation of propane:
the reaction process conditions comprise that the reaction temperature is 610 ℃, the pressure is 0.10MPa, and the mass space velocity of the low-carbon alkane is 2.0h-1The filling amount of the inert carrier is 200 wt% of the filling amount of the catalyst E, and the reaction time is 0.5 h; the regeneration gas is air, the regeneration temperature is 680 ℃, the regeneration pressure is 0.2MPa, and the volume space velocity is 3000h-1The regeneration time is 0.5h, and the nitrogen gas stripping space velocity is 2000h-1And the air stripping time is 0.1 h.
Comparative example 6
323g(NH4)2CrO4、28g KNO3、65g Cu(NO3)2·3H2Dissolving O in 760ml deionized water, soaking in the treated powder in equal volume, drying at 80 deg.C for 4 hr, calcining at 680 deg.C for 8 hr, molding, and sieving to obtain catalyst L.
Dehydrogenation of butane:
reaction process conditions, reaction temperature600 ℃, the pressure of 0.10MPa and the mass space velocity of the low-carbon alkane of 2.0h-1The filling amount of the inert carrier is 200 wt% of the filling amount of the catalyst E, and the reaction time is 0.5 h; the regeneration gas is air, the regeneration temperature is 690 ℃, the regeneration pressure is 0.2MPa, and the volume space velocity is 500h-1The regeneration time is 1.5h, and the nitrogen gas stripping space velocity is 2000h-1And the air stripping time is 0.1 h.
Dehydrogenation of propane:
the reaction process conditions comprise that the reaction temperature is 610 ℃, the pressure is 0.10MPa, and the mass space velocity of the low-carbon alkane is 2.0h-1The filling amount of the inert carrier is 200 wt% of the filling amount of the catalyst E, and the reaction time is 0.5 h; the regeneration gas is air, the regeneration temperature is 680 ℃, the regeneration pressure is 0.2MPa, and the volume space velocity is 3000h-1The regeneration time is 0.5h, and the nitrogen gas stripping space velocity is 2000h-1And the air stripping time is 0.1 h.
Example 7
166g(NH4)2Cr2O7、163g Na2CrO492g of glucose is dissolved in 800ml of deionized water, and the solution is dipped into 1000g of porous gamma-Al in equal volume2O3In the powder. The powder was placed in an oven at 95 ℃ for 2h, washed with deionized water, filtered and dried at 60 ℃ for 10 h. 16g Ca (NO)3)2·4H2O、11gSr(NO3)2、233g Co(NO3)2·6H2Dissolving O in 700ml deionized water, soaking the powder in the same volume, drying at 80 deg.C for 4 hr, calcining at 750 deg.C for 10 hr, and sieving to obtain catalyst M.
Dehydrogenation of butane:
the reaction process conditions are that the reaction temperature is 600 ℃, the pressure is 0.10MPa, and the mass space velocity of the low-carbon alkane is 2.0h-1The filling amount of the inert carrier is 200 wt% of the filling amount of the catalyst E, and the reaction time is 0.5 h; the regeneration gas is air, the regeneration temperature is 690 ℃, the regeneration pressure is 0.2MPa, and the volume space velocity is 500h-1The regeneration time is 1.5h, and the nitrogen gas stripping space velocity is 2000h-1And the air stripping time is 0.1 h.
Dehydrogenation of propane:
the reaction process conditions comprise that the reaction temperature is 610 ℃, the pressure is 0.10MPa, and the mass space velocity of the low-carbon alkane is 2.0h-1The filling amount of the inert carrier is 200 wt% of the filling amount of the catalyst E, and the reaction time is 0.5 h; the regeneration gas is air, the regeneration temperature is 700 ℃, the regeneration pressure is 0.2MPa, and the volume space velocity is 3000h-1The regeneration time is 0.5h, and the nitrogen gas stripping space velocity is 2000h-1And the air stripping time is 0.1 h.
Comparative example 7
930g Cr(NO3)3·9H2O、16g Ca(NO3)2·4H2O、11g Sr(NO3)2、233gCo(NO3)2·6H2Dissolving O in 380ml deionized water, and soaking in 1000g of porous gamma-Al in equal volume2O3Drying the powder at 80 ℃ for 4h, roasting the powder at 750 ℃ for 10h, and forming and screening the powder to obtain a catalyst which is recorded as a catalyst N.
Dehydrogenation of butane:
the reaction process conditions are that the reaction temperature is 600 ℃, the pressure is 0.10MPa, and the mass space velocity of the low-carbon alkane is 2.0h-1The filling amount of the inert carrier is 200 wt% of the filling amount of the catalyst E, and the reaction time is 0.5 h; the regeneration gas is air, the regeneration temperature is 690 ℃, the regeneration pressure is 0.2MPa, and the volume space velocity is 500h-1The regeneration time is 1.5h, and the nitrogen gas stripping space velocity is 2000h-1And the air stripping time is 0.1 h.
Dehydrogenation of propane:
the reaction process conditions comprise that the reaction temperature is 610 ℃, the pressure is 0.10MPa, and the mass space velocity of the low-carbon alkane is 2.0h-1The filling amount of the inert carrier is 200 wt% of the filling amount of the catalyst E, and the reaction time is 0.5 h; the regeneration gas is air, the regeneration temperature is 700 ℃, the regeneration pressure is 0.2MPa, and the volume space velocity is 3000h-1The regeneration time is 0.5h, and the nitrogen gas stripping space velocity is 2000h-1And the air stripping time is 0.1 h.
TABLE 1 fixed bed dehydrogenation results for different examples
Figure BDA0001015988900000121
As can be seen from table 1, the catalyst synthesized using the in-situ reduction (example) using the fixed bed process is superior in conversion, selectivity and stability to the directly impregnated catalyst (comparative example). After the process is optimized, the activity of the catalyst is further improved.
The present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof, and it is therefore intended that all such changes and modifications as fall within the true spirit and scope of the invention be considered as within the following claims.

Claims (18)

1. A low-carbon alkane dehydrogenation process is characterized in that a low-carbon alkane raw material enters a fixed bed reactor filled with a chromium dehydrogenation catalyst for dehydrogenation reaction, and the preparation method of the chromium dehydrogenation catalyst is that a high-valence chromium precursor is dissolved in a reducing agent solution capable of reducing the high-valence chromium precursor into low-valence chromium, and then the low-valence chromium precursor is dipped into an alumina-based carrier, washed, filtered and dried to obtain the low-carbon alkane dehydrogenation catalyst; the chromium in the high-valence chromium precursor is + 6-valence, and the low-valence chromium is + 3-valence; the reducing agent solution is selected from an aqueous solution containing glycol, glycerol, glucose, oxalic acid or ascorbic acid, and the molar ratio of the reducing agent to the high-valence chromium precursor is 0.5-10: 1.
2. The light alkane dehydrogenation process of claim 1, wherein the high valence chromium precursor is selected from the group consisting of CrO3、(NH4)2Cr2O7、Na2Cr2O7、K2Cr2O7、(NH4)2CrO4、Na2CrO4And K2CrO4One or more of them.
3. The process of claim 1, wherein the mass concentration of the glucose, oxalic acid or ascorbic acid component is 1 wt.% to 60 wt.% when the reducing agent solution is an aqueous solution containing the glucose, oxalic acid or ascorbic acid component.
4. The process of claim 1, wherein the mass concentration of the glucose, oxalic acid or ascorbic acid component is 3 wt.% to 30 wt.% when the reducing agent solution is an aqueous solution containing the glucose, oxalic acid or ascorbic acid component.
5. The process for dehydrogenating light alkanes of claim 1, wherein the impregnation temperature is 30-200 ℃.
6. The process for dehydrogenating light alkanes of claim 1, wherein the impregnation temperature is 60-150 ℃.
7. The dehydrogenation process of low-carbon alkane, according to claim 1, wherein the impregnation time is 0.5-20 h.
8. The process for dehydrogenating light alkanes of claim 1, wherein the time for the impregnation is 0.5-6 hours.
9. The dehydrogenation process of claim 1, wherein the molar ratio of the reducing agent to the high valence chromium precursor is 1-5: 1.
10. The process of claim 1, wherein the alumina-based support is an alumina support or an alumina support containing a refractory inorganic oxide.
11. The dehydrogenation process of lower alkanes according to claim 1, wherein the chromium-based dehydrogenation catalyst is prepared by impregnating an alumina-based carrier and drying, then impregnating a functional auxiliary, drying, and calcining.
12. The process of claim 11, wherein the functional promoter is selected from the group consisting of nitrates and acetates of one or more of Na, K, Ca, Sr, La, Sn, Cu, Ni, Co, Fe, and Zn.
13. The process of claim 11, wherein the chromium-based dehydrogenation catalyst comprises Cr2O3The content of the functional additive is 3-20 wt%, and the content of the functional additive is 0.5-6 wt%.
14. The dehydrogenation process of low-carbon alkane according to claim 1, wherein the fixed bed dehydrogenation reaction temperature is 550-650 ℃.
15. The dehydrogenation process of low-carbon alkane as claimed in claim 1, wherein the fixed bed dehydrogenation reaction pressure is 0.05-0.3 MPa.
16. The dehydrogenation process of light alkanes of claim 1, wherein the mass space velocity of the light alkanes is 0.1-10 h-1。
17. The dehydrogenation process of low-carbon alkane as claimed in claim 1, wherein the on-line time of the fixed bed reactor is 0.1-1.0 h, and then the fixed bed reactor is switched to enter a regeneration mode.
18. The process for dehydrogenating lower alkanes of claim 17, wherein in the fixed bed regeneration mode: the regeneration temperature is 630-720 ℃, and the regeneration pressure is 0.05-0.3 MPa.
CN201610412996.6A 2016-06-13 2016-06-13 Fixed bed dehydrogenation process of low-carbon alkane Active CN107486196B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201610412996.6A CN107486196B (en) 2016-06-13 2016-06-13 Fixed bed dehydrogenation process of low-carbon alkane

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201610412996.6A CN107486196B (en) 2016-06-13 2016-06-13 Fixed bed dehydrogenation process of low-carbon alkane

Publications (2)

Publication Number Publication Date
CN107486196A CN107486196A (en) 2017-12-19
CN107486196B true CN107486196B (en) 2020-04-10

Family

ID=60643109

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201610412996.6A Active CN107486196B (en) 2016-06-13 2016-06-13 Fixed bed dehydrogenation process of low-carbon alkane

Country Status (1)

Country Link
CN (1) CN107486196B (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112007589B (en) * 2020-10-22 2021-01-26 山东神驰石化有限公司 Propane catalytic dehydrogenation reactor

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103225131A (en) * 2013-05-06 2013-07-31 渤海大学 Al2O3, Cr2O3 composite nanofiber or nanosheet prepared from chromium-bearing aluminium sludge and preparation method thereof
CN103265078A (en) * 2013-04-12 2013-08-28 湖北振华化学股份有限公司 Method for preparing color hydrated chromium oxide by using atmospheric pressure reduction process
CN103769079A (en) * 2012-10-24 2014-05-07 中国石油化工股份有限公司 Low carbon alkane dehydrogenation catalyst and its preparation method and application
CN104209123A (en) * 2014-08-11 2014-12-17 中国海洋石油总公司 Light alkane dehydrogenation catalyst containing silver and boron and preparation method thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103769079A (en) * 2012-10-24 2014-05-07 中国石油化工股份有限公司 Low carbon alkane dehydrogenation catalyst and its preparation method and application
CN103265078A (en) * 2013-04-12 2013-08-28 湖北振华化学股份有限公司 Method for preparing color hydrated chromium oxide by using atmospheric pressure reduction process
CN103225131A (en) * 2013-05-06 2013-07-31 渤海大学 Al2O3, Cr2O3 composite nanofiber or nanosheet prepared from chromium-bearing aluminium sludge and preparation method thereof
CN104209123A (en) * 2014-08-11 2014-12-17 中国海洋石油总公司 Light alkane dehydrogenation catalyst containing silver and boron and preparation method thereof

Also Published As

Publication number Publication date
CN107486196A (en) 2017-12-19

Similar Documents

Publication Publication Date Title
CN107486195B (en) Preparation method of low-carbon alkane dehydrogenation catalyst
CN109320392B (en) Reaction and regeneration process of fixed fluidized bed for preparing propylene by propane dehydrogenation
CN107486197B (en) Preparation method of low-carbon alkane dehydrogenation microspherical catalyst
CN103769156B (en) A kind of dehydrogenation and its preparation method and application
CN103769079A (en) Low carbon alkane dehydrogenation catalyst and its preparation method and application
NO178611B (en) Catalyst useful for the conversion of synthesis gas to hydrocarbons as well as process for the conversion of synthesis gas to hydrocarbons
JP2010537807A (en) Olefin oxide catalyst carrier
CN108409523A (en) The method for carrying out dehydrogenating low-carbon alkane using metal oxide
CN116457091A (en) Dehydrogenation catalyst for preparing olefin from alkane gas and preparation method thereof
CN110869122A (en) Platinum-gallium based alkane dehydrogenation catalysts containing oxidation promoters
CN107486196B (en) Fixed bed dehydrogenation process of low-carbon alkane
CN107488096B (en) Dehydrogenation process of low-carbon alkane circulating fluidized bed
TW201703856A (en) Catalyst and hydrocarbon conversion process utilizing the catalyst
CN110898844B (en) Preparation method of multi-metal composite oxygen carrier
CN111686709B (en) Propane dehydrogenation propylene supported catalyst with specific pore structure and preparation method thereof
CN106928007B (en) Hydrogenation alkyne-removing method for methanol-to-olefin product
JP6426711B2 (en) Method for producing unsaturated hydrocarbon
CN107519914B (en) Molecular sieve catalyst for carbonylation reaction and preparation method and application thereof
JP6446033B2 (en) Process for producing unsaturated hydrocarbons
CN107488093B (en) Dehydrogenation process of low-carbon alkane
CN115634678A (en) Ethane dehydrogenation catalyst and method for simultaneously preparing ethylene and hydrogen by ethane dehydrogenation
WO2021107541A1 (en) Dehydrogenation catalyst for preparing olefine from alkanes gas and method for preparing same
CN106563440A (en) Crystal-grain-distribution-controlled light alkane dehydrogenation catalyst and preparation method thereof
CN109608301B (en) Method for preparing butylene and butadiene through catalytic dehydrogenation of butane
CN114632545B (en) Ultra-stable acetylene selective hydrogenation catalyst 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