CN116020356A - Method and system for dehydrogenating low-carbon alkane by countercurrent moving bed - Google Patents
Method and system for dehydrogenating low-carbon alkane by countercurrent moving bed Download PDFInfo
- Publication number
- CN116020356A CN116020356A CN202111239994.9A CN202111239994A CN116020356A CN 116020356 A CN116020356 A CN 116020356A CN 202111239994 A CN202111239994 A CN 202111239994A CN 116020356 A CN116020356 A CN 116020356A
- Authority
- CN
- China
- Prior art keywords
- reactor
- catalyst
- dehydrogenation
- dehydrogenation reaction
- reaction zone
- 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.)
- Granted
Links
- 238000000034 method Methods 0.000 title claims abstract description 59
- 229910052799 carbon Inorganic materials 0.000 title claims description 41
- 238000004939 coking Methods 0.000 claims abstract description 111
- 239000003054 catalyst Substances 0.000 claims abstract description 107
- 238000006356 dehydrogenation reaction Methods 0.000 claims abstract description 105
- 239000003112 inhibitor Substances 0.000 claims abstract description 97
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 45
- 150000001335 aliphatic alkanes Chemical class 0.000 claims abstract description 41
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 33
- 239000011593 sulfur Substances 0.000 claims abstract description 33
- 238000010438 heat treatment Methods 0.000 claims abstract description 29
- 229910052751 metal Inorganic materials 0.000 claims abstract description 29
- 239000002184 metal Substances 0.000 claims abstract description 29
- 238000011144 upstream manufacturing Methods 0.000 claims abstract description 26
- 238000004064 recycling Methods 0.000 claims abstract description 7
- 150000001875 compounds Chemical class 0.000 claims abstract description 6
- 230000001172 regenerating effect Effects 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims description 58
- 238000011069 regeneration method Methods 0.000 claims description 24
- 230000008929 regeneration Effects 0.000 claims description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 10
- WQOXQRCZOLPYPM-UHFFFAOYSA-N dimethyl disulfide Chemical group CSSC WQOXQRCZOLPYPM-UHFFFAOYSA-N 0.000 claims description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 9
- 239000001257 hydrogen Substances 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 9
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 9
- 239000007789 gas Substances 0.000 claims description 8
- 238000004891 communication Methods 0.000 claims description 7
- 239000012530 fluid Substances 0.000 claims description 7
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 5
- 239000000460 chlorine Substances 0.000 claims description 5
- 229910052801 chlorine Inorganic materials 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 229910052736 halogen Inorganic materials 0.000 claims description 4
- 150000002367 halogens Chemical class 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 229910052697 platinum Inorganic materials 0.000 claims description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 3
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 2
- 238000010304 firing Methods 0.000 claims description 2
- 229910052733 gallium Inorganic materials 0.000 claims description 2
- 229910052732 germanium Inorganic materials 0.000 claims description 2
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 2
- 229910052738 indium Inorganic materials 0.000 claims description 2
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 2
- 229910052716 thallium Inorganic materials 0.000 claims description 2
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 10
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 16
- 239000002994 raw material Substances 0.000 description 10
- 239000001294 propane Substances 0.000 description 8
- 239000007795 chemical reaction product Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 239000000571 coke Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 6
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 6
- 239000000376 reactant Substances 0.000 description 6
- 238000002347 injection Methods 0.000 description 5
- 239000007924 injection Substances 0.000 description 5
- 239000012188 paraffin wax Substances 0.000 description 4
- 238000002161 passivation Methods 0.000 description 4
- 239000003638 chemical reducing agent Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- -1 carbon alkane Chemical class 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- 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
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention relates to the field of petrochemical industry, in particular to a method and a system for dehydrogenating light alkane by a countercurrent moving bed, wherein the method comprises the following steps: introducing a lower alkane from an inlet of the dehydrogenation reaction zone into countercurrent contact with the dehydrogenation catalyst; the dehydrogenation reaction zone comprises at least 2 reactors which are sequentially connected in series, so that a gas phase stream can sequentially pass through each reactor; obtaining a spent catalyst from the most upstream reactor; sequentially regenerating and reducing the spent catalyst to obtain a regenerated catalyst; recycling the regenerated catalyst back to the most downstream reactor; and introducing a coking inhibitor into each reactor, wherein the coking inhibitor is a sulfur-containing compound. The method provided by the invention can sufficiently passivate the inner wall of the reactor, the inner member and the inner wall of the heating furnace tube, inhibit the metal catalytic coking tendency and ensure the stable operation of the device.
Description
Technical Field
The invention relates to the field of petrochemical industry, in particular to a method and a system for dehydrogenating low-carbon alkane by a countercurrent moving bed.
Background
The moving bed reaction-regeneration process is one of the common processing processes in the fields of petroleum refining and petrochemical industry, and is mainly used in the fields of preparing high-octane gasoline components or preparing olefin by catalyzing and reforming naphtha, preparing arene, preparing low-carbon alkane by dehydrogenation, and the like.
CN102746085a discloses a process for the preparation of propylene from paraffins by mixing a fresh propane feed with a propane-rich material separated from the reaction product, and introducing it into a paraffin dehydrogenation reactor, which may be a moving bed reactor packed with a dehydrogenation catalyst or other reactor configuration for paraffin dehydrogenation, to convert it to propylene at a temperature of 575-675 ℃. However, this method fails to address the problem of metal-catalyzed coking that occurs when hydrocarbons come into contact with metal walls at high temperatures.
CN111170820A, CN110452085a discloses a process for producing propylene by moving bed propane dehydrogenation in which the reaction feed is countercurrently contacted with the regenerated catalyst, wherein the combined reaction feed flow of propane is the same as the serial number sequence of the reactors, the regenerated catalyst is countercurrently contacted with the reaction feed by first entering the last reactor in the opposite direction to the feed. Similarly, this process also fails to address the problem of metal-catalyzed coking that occurs when hydrocarbons come into contact with metal walls at high temperatures.
CN110234432a discloses a method for managing sulfur on a catalyst during light paraffin dehydrogenation by injecting demineralized water at any one of the reactor inlets of a paraffin dehydrogenation reaction system and transferring coked deactivated spent catalyst from the last reactor outlet first to a sulfur stripper, removing at least 50% of the sulfur on the spent catalyst and then to a regenerator for coke burning regeneration, reducing the formation of sulfate on the catalyst during the regeneration coke burning. According to the method, the sulfur-containing passivating agent is injected into the reaction feed to reduce the occurrence probability of metal catalytic coking, and desulfurization is carried out at the outlet of the last reactor to reduce the generation of sulfate in the regeneration process, but the sulfur-containing passivating agent is only injected into the reaction feed, so that the passivation effect is ensured, and the injection amount is higher.
In the actual operation of a moving bed low-carbon alkane dehydrogenation industrial device, the inner wall of a subsequent reactor, the inner member and the inner wall of a heating furnace tube are not thoroughly passivated because sulfur is only injected into reaction raw materials, and the moving bed low-carbon alkane dehydrogenation device is frequently stopped due to metal catalytic coking, so that the stable operation of the device is influenced.
Disclosure of Invention
The invention aims to solve the problems of insufficient passivation of the inner wall of a reactor and the inner wall of a heating furnace tube and easy occurrence of metal catalytic coking in the existing moving bed low-carbon alkane dehydrogenation technology.
The inventors have found in research that in the prior art process flow shown in fig. 1, the countercurrent moving bed low carbon alkane dehydrogenation process injects coking inhibitors only at the inlet of the reaction feed heat exchanger.
Specifically, in fig. 1, the solid line indicates the flow direction of the reactant stream in the moving bed light alkane dehydrogenation reaction device, and the broken line indicates the flow direction of the catalyst in the moving bed light alkane dehydrogenation reaction device;
the low-carbon alkane is mixed with the coking inhibitor introduced through the coking inhibitor pipeline 101 through the raw material pipeline 100, enters the reaction feed heat exchanger 150, exchanges heat with the reaction product from the pipeline 111, then enters the feed heating furnace 151 through the pipeline 103 after being mixed with the hydrogen-rich gas from the gas pipeline 102, enters the first reactor 152 through the pipeline 104 after being heated, enters the second reactor inlet heating furnace 153 through the pipeline 105 after being heated, enters the second reactor 154 through the pipeline 106, enters the third reactor inlet heating furnace 155 through the pipeline 107 after being heated, enters the third reactor 156 through the pipeline 108 after being heated, enters the fourth reactor inlet heating furnace 157 through the pipeline 109 after being heated, enters the fourth reactor 158 through the pipeline 110 after being heated, enters the reaction feed heat exchanger 150 through the pipeline 111, exchanges heat with the reaction raw material, and then goes to the downstream reaction product compression cooling separation device through the pipeline 112;
the catalyst to be regenerated is obtained from the first reactor 152, lifted by a catalyst line 186, enters a regenerator 159 of a catalyst regeneration zone, is regenerated to obtain an oxidized regenerated catalyst, lifted by a catalyst line 181, enters a reducer 160, is reduced to obtain a regenerated catalyst, enters a fourth reactor 158 by a lower catalyst line 182, lifted by a catalyst line 183, enters a third reactor 156, lifted by a catalyst line 184, enters a second reactor 154, lifted by a catalyst line 185, enters the first reactor 152, and is obtained from the first reactor 152, thereby performing a reaction-regeneration cycle of the catalyst.
In the moving bed light alkane dehydrogenation reaction system shown in fig. 1, which typically comprises four reactors, the temperature drop in the first reactor is highest, whether it be a countercurrent moving bed or a conventional concurrent moving bed. In order to achieve the same inlet temperature as the first reactor, the heat load provided by the second reactor inlet furnace to the reaction materials is highest in four reactor inlet furnaces, the heating intensity is the highest, and the metal catalytic coking tendency in the heating furnace tubes is the highest; because the flow rate of the materials in the heating furnace tube is high, the coke generated by metal catalysis is easy to carry into the second reactor, and the coke is continuously grown and grown in the second reactor, so that the inner components of the second reactor are damaged by extrusion, the pressure drop from the inlet to the outlet of the second reactor is increased, and the device cannot normally operate and is stopped.
Moreover, the inventor also found that the temperature drop from the inlet to the outlet of the fourth reactor is the lowest in the four reactors, the weighted average bed temperature is the highest, the metal catalytic coking tendency on the inner wall or the inner member of the reactor is also high, the inner member of the fourth reactor is easy to be crushed and damaged, and the pressure drop from the inlet to the outlet of the fourth reactor is increased, so that the device cannot operate normally and is stopped.
The inventor further found in the study that in the process of circulating and conveying the catalyst of the countercurrent low-carbon alkane dehydrogenation device, the regenerated fresh catalyst has the lowest sulfur content, and after entering the fourth reactor, the adsorption effect on hydrogen sulfide in the reaction material is strongest, so that the concentration of the hydrogen sulfide in the reaction material in the fourth reactor is rapidly reduced, and the passivation effect on metal internals is further weakened.
Accordingly, the inventors believe that metal-catalyzed coking occurs more readily inside the fourth reactor of a countercurrent moving bed low-carbon alkane dehydrogenation process than in a conventional forward moving bed process, in the manner and in the amount of injection of coking inhibitors into the low-carbon alkane dehydrogenation feed.
In view of the above, the inventors provide a scheme of the present invention, and the method provided by the present invention is capable of effectively reducing the total injection amount of the coking inhibitor and improving the overall activity of the catalyst in the reactor on the premise of ensuring sufficient passivation of the inner wall of each reactor, the inner member and the inner wall of the heating furnace tube, by injecting the coking inhibitor into not only the reaction feed line but also the inlet line of the intermediate heating furnace of each reactor, and distributing the injection ratio of the coking inhibitor according to the adsorption tendency of the catalyst in each reactor to sulfur in the countercurrent moving bed low-carbon alkane dehydrogenation process.
To achieve the above object, a first aspect of the present invention provides a countercurrent moving bed low-carbon alkane dehydrogenation method, which is implemented in a moving bed low-carbon alkane dehydrogenation reaction device, comprising:
introducing light alkane from an inlet of a dehydrogenation reaction zone of the moving bed light alkane dehydrogenation reaction device in the presence of hydrogen to make countercurrent contact with a dehydrogenation catalyst, and obtaining a first material flow from an outlet of the dehydrogenation reaction zone; the dehydrogenation reaction zone comprises at least 2 reactors which are sequentially connected in series, so that a gas phase stream in the moving bed low-carbon alkane dehydrogenation reaction device can sequentially pass through each reactor; and
obtaining spent catalyst from the reactor upstream most of the dehydrogenation reaction zone;
introducing the spent catalyst into a catalyst regeneration zone of the moving bed low-carbon alkane dehydrogenation reaction device to sequentially perform regeneration and reduction so as to obtain a regenerated catalyst;
recycling the regenerated catalyst back to the most downstream reactor of the dehydrogenation reaction zone; and
introducing a coking inhibitor into each reactor of the dehydrogenation reaction zone, wherein the coking inhibitor is a sulfur-containing compound; the ratio of the mass rate R1 of the introduced low-carbon alkane to the mass rate R2 of the introduced coking inhibitor calculated as sulfur element is R1: r2=100: 0.001-0.05.
In a second aspect, the present invention provides a countercurrent moving bed system for dehydrogenating light alkanes, the system comprising:
a dehydrogenation reaction zone for countercurrent contacting of the lower alkane with a dehydrogenation catalyst therein, the dehydrogenation reaction zone comprising at least 2 reactors connected in series in sequence;
a catalyst regeneration zone in fluid communication with the most upstream and downstream reactors of the dehydrogenation reaction zone, respectively, for sequentially regenerating and reducing spent catalyst from the most upstream reactor therein to obtain regenerated catalyst and recycling the regenerated catalyst back to the most downstream reactor.
The method provided by the invention can sufficiently passivate the inner wall of the reactor, the inner member and the inner wall of the heating furnace tube, inhibit the metal catalytic coking tendency and prevent shutdown caused by the metal catalytic coking; and the total amount of injected coking inhibitor is lower than that of the conventional method which is only injected at the inlet of a reaction feed heat exchanger, so that sulfur on the spent catalyst before entering a regeneration zone is easy to remove, and the activity influence is small.
The method provided by the invention has the advantages of simple process flow and low investment, and can be used for the transformation of the existing device and the new device.
Drawings
FIG. 1 is a schematic process flow diagram of a conventional countercurrent moving bed low-carbon alkane dehydrogenation process with only the injection of coking inhibitors at the inlet of the reaction feed heat exchanger;
FIG. 2 is a schematic process flow diagram of a preferred embodiment of the process of the present invention with coke inhibitors injected in the heating furnace lines at the inlet of the reaction feed heat exchanger and the inlet of the second and fourth reactors;
FIG. 3 is a schematic process flow diagram of a preferred embodiment of the process of the present invention with coke inhibitors injected in the furnace lines at the inlet of the reaction feed heat exchanger and the inlet of the second, third and fourth reactors.
Description of the reference numerals
100. Raw material pipeline 101 coking inhibitor pipeline
102. Gas line 103 line
104. Line 105 line
106. Pipeline 107 pipeline
108. Line 109 line
110. Line 111 line
112. Pipeline 150 reaction feed heat exchanger
151. First reactor of feed heating furnace 152
153. Second reactor inlet furnace 154 second reactor
155. Third reactor Inlet furnace 156 third reactor
157. Fourth reactor Inlet furnace 158 fourth reactor
159. Regenerator 160 restorer
181. Catalyst line 182 catalyst line
183. Catalyst line 184 catalyst line
185. Catalyst line 186 catalyst line
201. Coking inhibitor line 202 coking inhibitor line
301. Coking inhibitor line 302 coking inhibitor line
303. Coking inhibitor pipeline
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
In the present invention, the pressures are gauge pressures unless otherwise specified.
As previously described, a first aspect of the present invention provides a countercurrent moving bed process for the dehydrogenation of light alkanes, the process being carried out in a moving bed light alkane dehydrogenation reaction unit comprising:
introducing light alkane from an inlet of a dehydrogenation reaction zone of the moving bed light alkane dehydrogenation reaction device in the presence of hydrogen to make countercurrent contact with a dehydrogenation catalyst, and obtaining a first material flow from an outlet of the dehydrogenation reaction zone; the dehydrogenation reaction zone comprises at least 2 reactors which are sequentially connected in series, so that a gas phase stream in the moving bed low-carbon alkane dehydrogenation reaction device can sequentially pass through each reactor; and
obtaining spent catalyst from the reactor upstream most of the dehydrogenation reaction zone;
introducing the spent catalyst into a catalyst regeneration zone of the moving bed low-carbon alkane dehydrogenation reaction device to sequentially perform regeneration and reduction so as to obtain a regenerated catalyst;
recycling the regenerated catalyst back to the most downstream reactor of the dehydrogenation reaction zone; and
introducing a coking inhibitor into each reactor of the dehydrogenation reaction zone, wherein the coking inhibitor is a sulfur-containing compound; the ratio of the mass rate R1 of the introduced low-carbon alkane to the mass rate R2 of the introduced coking inhibitor calculated as sulfur element is R1: r2=100: 0.001-0.05.
Preferably, the ratio between the mass rate R1 of introduction of the lower alkane and the mass rate R2 of introduction of the coking inhibitor in elemental sulfur is R1: r2=100: 0.005-0.04, more preferably R1: r2=100: 0.008-0.02.
In the dehydrogenation reaction zone, the upstream and downstream directions of the reactors connected in series are the same as the direction of the reactant flow, the feeding side is upstream, and the discharging side is downstream; the serial number of each reactor is also the same as the direction of the reactant flow, i.e. the reactant feed first enters the first reactor at the most upstream, then enters the second reactor and the third reactor in turn until entering the reactor at the most downstream, and the lower alkane dehydrogenation reaction product flow flows out of the reactors.
In the invention, the regenerated catalyst circularly flows through a circulating conveying system in the direction opposite to the direction of the reactant flow, namely, enters the most downstream reactor firstly, then enters the next-to-last reactor and the third-to-last reactor in sequence until entering the first reactor at the most upstream, and becomes a spent catalyst to flow out of the first reactor, and then enters the catalyst regeneration zone for regeneration and reduction in sequence, so as to obtain the regenerated catalyst in a reduced state.
In the present invention, the coking inhibitor is heated to gasify prior to being introduced into each reactor of the dehydrogenation zone.
In the present invention, the mass rate R1 of the lower alkane represents the sum of the mass of the lower alkane-rich material fed with fresh feed of the lower alkane and the reaction product fed into the dehydrogenation reaction zone in unit time after subsequent separation, and the mass rate R1 of the lower alkane may be, for example, kg/h.
In the present invention, the mass rate R2 of the coking inhibitor in elemental sulfur represents the sum of the masses of the coking inhibitor in elemental sulfur in each reactor fed into the dehydrogenation reaction zone per unit time, and the mass rate R2 of the coking inhibitor in elemental sulfur may be in kg/h, for example.
Preferably, the location of introduction of the coking inhibitor is selected from at least one of the inlet of each reactor of the dehydrogenation reaction zone, the line upstream of the inlet of each reactor.
Preferably, the location of introduction of the coking inhibitor is selected from at least one of a reaction feed heat exchanger, an intermediate heating furnace, a pipeline of the dehydrogenation reaction zone upstream of the inlet of the respective reactor.
Preferably, the regenerating operation includes sequentially performing scorching, oxychlorination, and calcination.
In the present invention, the operation of regeneration is performed in a regenerator of the catalyst regeneration zone, the regenerator comprising a burn zone, an oxychlorination zone, and a calcination zone.
Preferably, the sulfur-containing compound is a disulfide, the alkyl group in the disulfide being selected from C 1 -C 3 At least one of the alkyl groups of (a).
Preferably, the disulfide is dimethyl disulfide.
Preferably, the dehydrogenation reaction zone contains 3-5 reactors connected in series in sequence.
Preferably, the reaction conditions in each of the reactors each independently comprise: the reaction temperature is 500-670 deg.c and the reaction pressure is 0.01-1.0MPa.
More preferably, the reaction conditions in each of the reactors each independently comprise: the reaction temperature is 550-650 ℃, and the reaction pressure is 0.02-0.2Mpa.
Further preferably, the reaction conditions in each of the reactors each independently include: the reaction temperature is 600-650 ℃, and the reaction pressure is 0.03-0.1Mpa.
Preferably, the reaction conditions in the most upstream reactor include: the volume ratio of the hydrogen to the low-carbon alkane is 0.5-6:1, the space velocity of the feeding volume is 0.3 to 5h -1 Preferably 0.5-2h -1 。
Preferably, the dehydrogenation catalyst comprises a carrier and an active component supported on the carrier, wherein the carrier is alumina, the active component comprises platinum element, a second metal component element, a group IA metal component element and halogen, and the second metal component element is at least one of tin, germanium, lead, indium, gallium and thallium; and the content of the platinum element is 0.1 to 2.0 mass%, the content of the second metal component element is 0.1 to 2.0 mass%, the content of the group IA metal component element is 0.5 to 5.0 mass%, and the content of the halogen is 0.3 to 10.0 mass%, based on the total weight of the carrier.
Preferably, the alumina is θ -alumina.
Preferably, the alumina is spherical.
Preferably, the alumina has an average diameter of 1.5-2.0mm.
Preferably, the operation of burning comprises: the spent catalyst is contacted with nitrogen having an oxygen content of 0.5 to 5.0% by volume at 480 to 600 ℃.
Preferably, the oxychlorination operation comprises: and contacting the burnt spent catalyst with nitrogen or air at the temperature of 500-520 ℃, wherein the nitrogen contains chlorine and oxygen, and the air contains chlorine.
Preferably, the firing operation includes: and roasting the spent catalyst which is subjected to the scorching and the oxychlorination in sequence in air at the temperature of 520-565 ℃.
Preferably, the operation of reducing comprises: the regenerated spent catalyst is contacted with hydrogen at a temperature of 350-550 ℃.
In the present invention, the operation of reduction is performed in a reducer of the catalyst regeneration zone.
Preferably, the lower alkane is C 3 -C 5 At least one of the paraffins of (a).
The following provides a process flow of a preferred embodiment of the countercurrent moving bed process for the dehydrogenation of light alkanes according to the present invention in connection with FIG. 2:
the solid line in the figure shows the flow direction of the reactant stream in the moving bed light alkane dehydrogenation reaction device, and the dotted line shows the flow direction of the catalyst in the moving bed light alkane dehydrogenation reaction device;
the low-carbon alkane is mixed with the coking inhibitor introduced through the coking inhibitor pipeline 101 through the raw material pipeline 100, enters the reaction feed heat exchanger 150, exchanges heat with the reaction product from the pipeline 111, then enters the feed heating furnace 151 through the pipeline 103 after being mixed with the hydrogen-rich gas from the gas pipeline 102, enters the first reactor 152 through the pipeline 104 after being heated, enters the second reactor inlet heating furnace 153 through the pipeline 105 after being heated, enters the second reactor 154 through the pipeline 106, enters the third reactor inlet heating furnace 155 through the pipeline 107 after being heated, enters the third reactor 156 through the pipeline 108 after being heated, enters the fourth reactor inlet heating furnace 157 through the pipeline 109 after being heated, enters the fourth reactor 158 through the pipeline 110 after being heated, enters the reaction feed heat exchanger 150 through the pipeline 111, exchanges heat with the reaction raw material, and then goes to the downstream reaction product compression cooling separation device through the pipeline 112;
the catalyst to be regenerated is obtained from the first reactor 152, lifted by a catalyst pipeline 186, enters a regenerator 159 of a catalyst regeneration zone, is regenerated to obtain an oxidized regenerated catalyst, lifted by a catalyst pipeline 181, enters a reducer 160, is reduced to obtain a regenerated catalyst, enters a fourth reactor 158 by a lower catalyst pipeline 182, lifted by a catalyst pipeline 183, enters a third reactor 156, lifted by a catalyst pipeline 184, enters a second reactor 154, lifted by a catalyst pipeline 185, enters the first reactor 152, and is obtained from the first reactor 152 to perform a reaction-regeneration cycle of the catalyst;
introducing a coking inhibitor into line 105 through coking inhibitor line 201 to passivate the interior walls of the furnace tubes of second reactor inlet furnace 153 and the interior walls and internals of second reactor 154; coking inhibitors are introduced into line 109 through coking inhibitor line 202 to passivate the interior walls of the furnace tubes of fourth reactor inlet furnace 157 and the interior walls and internals of fourth reactor 158.
The following provides a process flow of a preferred embodiment of the countercurrent moving bed process for the dehydrogenation of light alkanes according to the present invention in connection with FIG. 3:
unlike fig. 2, the coking inhibitor line 201 and the coking inhibitor line 202 are replaced with a coking inhibitor line 301, a coking inhibitor line 302, and a coking inhibitor line 303, specifically, a coking inhibitor is introduced into the line 105 through the coking inhibitor line 301 to passivate the inner walls of the furnace tubes of the second reactor inlet furnace 153 and the inner walls and internals of the second reactor 154; introducing a coking inhibitor into line 107 through coking inhibitor line 302 to passivate the inner walls of the furnace tubes of the third reactor inlet furnace 155 and the inner walls and internals of the third reactor 156; a coking inhibitor is introduced into line 109 through coking inhibitor line 303 to passivate the interior walls of the furnace tubes of fourth reactor inlet furnace 157 and the interior walls and internals of fourth reactor 158.
As previously described, a second aspect of the present invention provides a countercurrent moving bed system for the dehydrogenation of light alkanes, the system comprising:
a dehydrogenation reaction zone for countercurrent contacting of the lower alkane with a dehydrogenation catalyst therein, the dehydrogenation reaction zone comprising at least 2 reactors connected in series in sequence;
a catalyst regeneration zone in fluid communication with the most upstream and downstream reactors of the dehydrogenation reaction zone, respectively, for sequentially regenerating and reducing spent catalyst from the most upstream reactor therein to obtain regenerated catalyst and recycling the regenerated catalyst back to the most downstream reactor.
Preferably, the dehydrogenation reaction zone contains 3 to 5 reactors connected in series in sequence.
Preferably, the system further comprises:
a reaction feed heat exchanger in fluid communication with the most upstream reactor of the dehydrogenation reaction zone for heat exchange therebetween of the lower alkane and the coking inhibitor and introduction into the most upstream reactor;
an intermediate heating furnace in fluid communication with each of said reactors at each end for heating therein the product stream and coking inhibitors from said reactor upstream and introducing into said reactor downstream adjacent thereto.
The invention will be described in detail below by way of examples.
In the following examples, all of the raw materials used were commercial products unless otherwise specified.
Example 1
This example employs the process flow shown in fig. 2 for countercurrent moving bed low-carbon alkane dehydrogenation.
Spherical low-carbon alkane dehydrogenation catalysts are filled in the first reactor to the fourth reactor of the moving bed low-carbon alkane dehydrogenation reaction device, and the carriers of the low-carbon alkane dehydrogenation catalysts are spherical theta-Al 2 O 3 The diameter range is 1.60mm-1.80mm; the content of Pt element was 0.3 mass%, the content of tin, the second metal component element was 0.3 mass%, the content of potassium, the group IA metal component element was 0.9 mass%, and the content of chlorine element was 1.15 mass%, based on the total weight of the carrier;
the filling volume ratio of the low-carbon alkane dehydrogenation catalyst in the first reactor, the second reactor, the third reactor and the fourth reactor is 1:1:1:1.
the lower alkane reaction raw material adopted in the embodiment is propane, and the coking inhibitor is dimethyl disulfide (analytically pure); the ratio relationship between the mass rate R1 of the introduced low-carbon alkane and the mass rate R2 of the introduced coking inhibitor calculated as sulfur element is R1: r2=100: 0.015, wherein the mass rate R2 of the coking inhibitor introduced in elemental sulfur is the sum of the mass rates of the coking inhibitor in elemental sulfur introduced via coking inhibitor line 101, coking inhibitor line 201, and coking inhibitor line 202, and the ratio between the mass rate of the coking inhibitor in elemental sulfur introduced via coking inhibitor line 101, the mass rate of the coking inhibitor in elemental sulfur introduced via coking inhibitor line 201, and the mass rate of the coking inhibitor in elemental sulfur introduced via coking inhibitor line 202 is 1:1:1, a step of;
the operating conditions of the moving bed low-carbon alkane dehydrogenation reaction device are shown in table 1, and the reaction results are shown in table 2.
Example 2
This example employs the process flow shown in fig. 3 for countercurrent moving bed low-carbon alkane dehydrogenation.
The lower alkane dehydrogenation catalyst, lower alkane reaction raw material and coking inhibitor used in this example were the same as in example 1;
the ratio relationship between the mass rate R1 of the introduced low-carbon alkane and the mass rate R2 of the introduced coking inhibitor calculated as sulfur element is R1: r2=100: 0.012, wherein the mass rate R2 of the coking inhibitor as a sulfur element is the sum of the mass rates of the coking inhibitor as a sulfur element introduced through the coking inhibitor line 101, the coking inhibitor line 301, the coking inhibitor line 302, and the coking inhibitor line 303, and the ratio between the mass rate of the coking inhibitor as a sulfur element introduced through the coking inhibitor line 101, the mass rate of the coking inhibitor as a sulfur element introduced through the coking inhibitor line 301, the mass rate of the coking inhibitor as a sulfur element introduced through the coking inhibitor line 302, and the mass rate of the coking inhibitor as a sulfur element introduced through the coking inhibitor line 303 is 1:1:1:1, a step of;
the operating conditions of the moving bed low-carbon alkane dehydrogenation reaction device are shown in table 1, and the reaction results are shown in table 2.
Comparative example 1
This comparative example employs the process flow shown in fig. 1 for countercurrent moving bed low-carbon alkane dehydrogenation.
The lower alkane dehydrogenation catalyst, lower alkane reaction raw material and coking inhibitor used in this comparative example were the same as in example 1;
the ratio relationship between the mass rate R1 of the introduced low-carbon alkane and the mass rate R2 of the introduced coking inhibitor calculated as sulfur element is R1: r2=100: 0.018, wherein said introduced mass rate R2 of said coking inhibitor in elemental sulfur is the mass rate of said coking inhibitor in elemental sulfur introduced via coking inhibitor line 101;
the operating conditions of the moving bed low-carbon alkane dehydrogenation reaction device are shown in table 1, and the reaction results are shown in table 2.
TABLE 1
TABLE 2
Project | Example 1 | Example 2 | Comparative example 1 |
Single pass conversion of propane, mass% | 27.4 | 27.6 | 27.0 |
Total yield of propylene product, mass% | 85.8 | 86.3 | 85.1 |
Whether or not coking of the metal walls occurs | Does not occur | Does not occur | Does not occur |
Sulfur content of spent catalyst at outlet of first reactor, mass% | 0.061 | 0.054 | 0.071 |
The sulfur content of the catalyst at the outlet of the second reactor, mass% | 0.077 | 0.068 | 0.088 |
Catalyst sulfur content at outlet of third reactor, mass% | 0.086 | 0.081 | 0.102 |
The sulfur content of the catalyst at the outlet of the fourth reactor, mass% | 0.102 | 0.092 | 0.114 |
The fourth reactor inlet regenerates the sulfur content of the catalyst, mass% | 0.057 | 0.051 | 0.065 |
As is clear from Table 2, in example 1, by injecting dimethyl disulfide as a coking inhibitor into the reaction feed and the lines of the second reactor inlet furnace and the fourth reactor inlet furnace, the conversion per pass of raw propane was increased by 0.4 mass% and the total yield of propylene was increased by 0.7 mass% as compared with comparative example 1, and the respective furnaces and the inner walls of the reactors were sufficiently passivated, and the apparatus was operated smoothly, without coking of the metal walls.
In example 2, compared with comparative example 1, by injecting the coking inhibitor dimethyl disulfide into the reaction feed and the second reactor inlet heating furnace, the third reactor inlet heating furnace and the fourth reactor inlet heating furnace pipelines, the one-pass conversion rate of raw propane is improved by 0.6 mass percent, the total yield of propylene is improved by 1.2 mass percent, the heating furnaces and the inner walls of the reactors are fully passivated, the device runs stably, and metal wall coking does not occur under the condition that the total consumption of the coking inhibitor is reduced by 33 percent compared with comparative example 1.
From the results, the method provided by the invention can sufficiently passivate the inner wall of the reactor, the inner member and the inner wall of the heating furnace tube, inhibit the tendency of metal catalytic coking and prevent shutdown caused by metal catalytic coking; and the total amount of injected coking inhibitor is lower than that of the conventional method which is only injected at the inlet of a reaction feed heat exchanger, so that sulfur on the spent catalyst before entering a regeneration zone is easy to remove, and the activity influence is small.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (19)
1. A countercurrent moving bed process for the dehydrogenation of light alkanes, the process being carried out in a moving bed light alkane dehydrogenation reaction unit comprising:
introducing light alkane from an inlet of a dehydrogenation reaction zone of the moving bed light alkane dehydrogenation reaction device in the presence of hydrogen to make countercurrent contact with a dehydrogenation catalyst, and obtaining a first material flow from an outlet of the dehydrogenation reaction zone; the dehydrogenation reaction zone comprises at least 2 reactors which are sequentially connected in series, so that a gas phase stream in the moving bed low-carbon alkane dehydrogenation reaction device can sequentially pass through each reactor; and
obtaining spent catalyst from the reactor upstream most of the dehydrogenation reaction zone;
introducing the spent catalyst into a catalyst regeneration zone of the moving bed low-carbon alkane dehydrogenation reaction device to sequentially perform regeneration and reduction so as to obtain a regenerated catalyst;
recycling the regenerated catalyst back to the most downstream reactor of the dehydrogenation reaction zone; and
introducing a coking inhibitor into each reactor of the dehydrogenation reaction zone, wherein the coking inhibitor is a sulfur-containing compound; the ratio of the mass rate R1 of the introduced low-carbon alkane to the mass rate R2 of the introduced coking inhibitor calculated as sulfur element is R1: r2=100: 0.001-0.05.
2. The method of claim 1, wherein the ratio between the mass rate of introduction of the lower alkane, R1, and the mass rate of introduction of the coking inhibitor, R2, in elemental sulfur, is R1: r2=100: 0.005-0.04, preferably R1: r2=100: 0.008-0.02.
3. The process of claim 1 or 2, wherein the location of introduction of the coking inhibitor is selected from at least one of an inlet of each reactor of the dehydrogenation reaction zone, an upstream line of an inlet of each reactor.
4. The process of claim 3 wherein the location of introduction of the coking inhibitor is selected from at least one of a reaction feed heat exchanger, an intermediate furnace, a pipeline of the dehydrogenation reaction zone upstream of the inlet of the respective reactor.
5. The method of any of claims 1-4, wherein the regenerating comprises sequentially performing a scorch, an oxychlorination, and a bake.
6. The process according to any one of claims 1 to 5, wherein the sulfur-containing compound is a disulfide, the alkyl group in the disulfide being selected from C 1 -C 3 At least one of the alkyl groups of (a);
preferably, the disulfide is dimethyl disulfide.
7. The process of any of claims 1-6, wherein the dehydrogenation reaction zone comprises 3-5 reactors connected in series in sequence.
8. The method of any of claims 1-7, wherein the reaction conditions in each of the reactors each independently comprise: the reaction temperature is 500-670 ℃, and the reaction pressure is 0.01-1.0Mpa;
preferably, the reaction conditions in each of the reactors each independently comprise: the reaction temperature is 550-650 ℃, and the reaction pressure is 0.02-0.2Mpa;
more preferably, the reaction conditions in each of the reactors each independently comprise: the reaction temperature is 600-650 ℃, and the reaction pressure is 0.03-0.1Mpa.
9. The method of any of claims 1-8, wherein the reaction conditions in the most upstream reactor comprise: the volume ratio of the hydrogen to the low-carbon alkane is 0.5-6:1, the space velocity of the feeding volume is 0.3 to 5h -1 Preferably 0.5-2h -1 。
10. The method according to any one of claims 1 to 9, wherein the dehydrogenation catalyst comprises a carrier and an active component supported on the carrier, the carrier is alumina, and the active component comprises a platinum element, a second metal component element, a group IA metal component element and halogen, and the second metal component element is at least one selected from tin, germanium, lead, indium, gallium and thallium; and the content of the platinum element is 0.1 to 2.0 mass%, the content of the second metal component element is 0.1 to 2.0 mass%, the content of the group IA metal component element is 0.5 to 5.0 mass%, and the content of the halogen is 0.3 to 10.0 mass%, based on the total weight of the carrier.
11. The method of claim 10, wherein the alumina is theta alumina;
preferably, the alumina is spherical;
preferably, the alumina has an average diameter of 1.5-2.0mm.
12. The method of claim 5, wherein the operation of burning comprises: the spent catalyst is contacted with nitrogen having an oxygen content of 0.5 to 5.0% by volume at 480 to 600 ℃.
13. The method of claim 5, wherein the oxychlorination comprises: and contacting the burnt spent catalyst with nitrogen or air at the temperature of 500-520 ℃, wherein the nitrogen contains chlorine and oxygen, and the air contains chlorine.
14. The method of claim 5, wherein the firing operation comprises: and roasting the spent catalyst which is subjected to the scorching and the oxychlorination in sequence at the temperature of 520-565 ℃.
15. The method of any of claims 1-14, wherein the operation of reducing comprises: the regenerated spent catalyst is contacted with hydrogen at a temperature of 350-550 ℃.
16. According to claims 1-15The method of any one of, wherein the lower alkane is C 3 -C 5 At least one of the paraffins of (a).
17. A countercurrent moving bed system for the dehydrogenation of light alkanes, the system comprising:
a dehydrogenation reaction zone for countercurrent contacting of the lower alkane with a dehydrogenation catalyst therein, the dehydrogenation reaction zone comprising at least 2 reactors connected in series in sequence;
a catalyst regeneration zone in fluid communication with the most upstream and downstream reactors of the dehydrogenation reaction zone, respectively, for sequentially regenerating and reducing spent catalyst from the most upstream reactor therein to obtain regenerated catalyst and recycling the regenerated catalyst back to the most downstream reactor.
18. The system of claim 17, wherein the dehydrogenation reaction zone comprises 3 to 5 reactors connected in series.
19. The system of claim 17 or 18, wherein the system further comprises:
a reaction feed heat exchanger in fluid communication with the most upstream reactor of the dehydrogenation reaction zone for heat exchange therebetween of the lower alkane and the coking inhibitor and introduction into the most upstream reactor;
an intermediate heating furnace in fluid communication with each of said reactors at each end for heating therein the product stream and coking inhibitors from said reactor upstream and introducing into said reactor downstream adjacent thereto.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202111239994.9A CN116020356B (en) | 2021-10-25 | 2021-10-25 | Method and system for dehydrogenating low-carbon alkane by countercurrent moving bed |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202111239994.9A CN116020356B (en) | 2021-10-25 | 2021-10-25 | Method and system for dehydrogenating low-carbon alkane by countercurrent moving bed |
Publications (2)
Publication Number | Publication Date |
---|---|
CN116020356A true CN116020356A (en) | 2023-04-28 |
CN116020356B CN116020356B (en) | 2024-10-11 |
Family
ID=86079861
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202111239994.9A Active CN116020356B (en) | 2021-10-25 | 2021-10-25 | Method and system for dehydrogenating low-carbon alkane by countercurrent moving bed |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN116020356B (en) |
Citations (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS61166882A (en) * | 1985-01-18 | 1986-07-28 | Hakutou Kagaku Kk | Method of preventing coking of hydrocarbon treatment process |
EP0839782A1 (en) * | 1996-10-30 | 1998-05-06 | Nalco/Exxon Energy Chemicals, L.P. | Process for the inhibition of coke formation in pyrolysis furnaces |
CN101168683A (en) * | 2006-10-26 | 2008-04-30 | 中国石油化工股份有限公司 | Device for inhibiting hydrocarbon-like steam crack and method for inhibiting quenching boiler coke |
CN101445746A (en) * | 2007-11-28 | 2009-06-03 | 中国石油化工股份有限公司 | Pre-passivation method for continuous reforming device |
US20100061902A1 (en) * | 2008-09-05 | 2010-03-11 | Bradley Steven A | Metal-Based Coatings for Inhibiting Metal Catalyed Coke Formation in Hydrocarbon Conversion Processes |
US20100282645A1 (en) * | 2007-10-31 | 2010-11-11 | China Petroleum & Chemical Corporation | Pre-passivation process for a continuous reforming apparatus, and passivation process for a continuous reforming apparatus during the initial reacation |
CN102295954A (en) * | 2010-06-25 | 2011-12-28 | 中国石油化工股份有限公司 | Counter-current moving bed reforming process device and catalyst conveying method thereof |
CN102341483A (en) * | 2009-03-04 | 2012-02-01 | 环球油品公司 | Process for preventing metal catalyzed coking |
JP2014189543A (en) * | 2013-03-28 | 2014-10-06 | Mitsubishi Chemicals Corp | Method for manufacturing conjugated diene |
CN110041965A (en) * | 2018-01-15 | 2019-07-23 | 中国石油化工股份有限公司 | The method of ethene suppressing cracking device from coking |
CN110452085A (en) * | 2018-05-07 | 2019-11-15 | 淄博众森石化工程技术有限公司 | A kind of moving bed C3/C4 alkane dehydrogenation process |
CN110551521A (en) * | 2018-05-30 | 2019-12-10 | 中国石油天然气集团有限公司 | low-carbon olefin preparation system and method |
CN111073693A (en) * | 2018-10-19 | 2020-04-28 | 中国石油化工股份有限公司 | Naphtha modification method |
CN111100667A (en) * | 2018-10-29 | 2020-05-05 | 中国石油化工股份有限公司 | Method for reducing coking of cracking unit |
-
2021
- 2021-10-25 CN CN202111239994.9A patent/CN116020356B/en active Active
Patent Citations (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS61166882A (en) * | 1985-01-18 | 1986-07-28 | Hakutou Kagaku Kk | Method of preventing coking of hydrocarbon treatment process |
EP0839782A1 (en) * | 1996-10-30 | 1998-05-06 | Nalco/Exxon Energy Chemicals, L.P. | Process for the inhibition of coke formation in pyrolysis furnaces |
CN101168683A (en) * | 2006-10-26 | 2008-04-30 | 中国石油化工股份有限公司 | Device for inhibiting hydrocarbon-like steam crack and method for inhibiting quenching boiler coke |
US20100282645A1 (en) * | 2007-10-31 | 2010-11-11 | China Petroleum & Chemical Corporation | Pre-passivation process for a continuous reforming apparatus, and passivation process for a continuous reforming apparatus during the initial reacation |
CN101445746A (en) * | 2007-11-28 | 2009-06-03 | 中国石油化工股份有限公司 | Pre-passivation method for continuous reforming device |
US20100061902A1 (en) * | 2008-09-05 | 2010-03-11 | Bradley Steven A | Metal-Based Coatings for Inhibiting Metal Catalyed Coke Formation in Hydrocarbon Conversion Processes |
CN102341483A (en) * | 2009-03-04 | 2012-02-01 | 环球油品公司 | Process for preventing metal catalyzed coking |
CN102295954A (en) * | 2010-06-25 | 2011-12-28 | 中国石油化工股份有限公司 | Counter-current moving bed reforming process device and catalyst conveying method thereof |
JP2014189543A (en) * | 2013-03-28 | 2014-10-06 | Mitsubishi Chemicals Corp | Method for manufacturing conjugated diene |
CN110041965A (en) * | 2018-01-15 | 2019-07-23 | 中国石油化工股份有限公司 | The method of ethene suppressing cracking device from coking |
CN110452085A (en) * | 2018-05-07 | 2019-11-15 | 淄博众森石化工程技术有限公司 | A kind of moving bed C3/C4 alkane dehydrogenation process |
CN110551521A (en) * | 2018-05-30 | 2019-12-10 | 中国石油天然气集团有限公司 | low-carbon olefin preparation system and method |
CN111073693A (en) * | 2018-10-19 | 2020-04-28 | 中国石油化工股份有限公司 | Naphtha modification method |
CN111100667A (en) * | 2018-10-29 | 2020-05-05 | 中国石油化工股份有限公司 | Method for reducing coking of cracking unit |
Also Published As
Publication number | Publication date |
---|---|
CN116020356B (en) | 2024-10-11 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN111068587B (en) | Liquid phase hydrogenation reaction device and reaction method | |
WO2016110253A1 (en) | Cold regenerated catalyst circulation method and device therefor | |
CN105985209A (en) | Method of producing aromatic hydrocarbon through catalytic conversion of organic oxides | |
CN204111687U (en) | Hydro carbons continuous reformer (one) | |
CN116020356B (en) | Method and system for dehydrogenating low-carbon alkane by countercurrent moving bed | |
CN109232153B (en) | Method for preparing low-carbon olefin from naphtha | |
US4473658A (en) | Moving bed catalytic cracking process with platinum group metal or rhenium supported directly on the cracking catalyst | |
CN204111688U (en) | Hydro carbons continuous reformer (four) | |
CN105349180A (en) | Continuous reforming technology of hydrocarbons | |
CN204111691U (en) | Hydro carbons continuous reformer (two) | |
CN110452085A (en) | A kind of moving bed C3/C4 alkane dehydrogenation process | |
CN204111693U (en) | Hydro carbons continuous reformer (five) | |
CN114456830B (en) | Continuous reforming method of naphtha countercurrent moving bed | |
CN111068590B (en) | Solid acid alkylation method | |
WO2020083279A1 (en) | Liquid-solid axial moving bed reaction and regeneration device, and solid acid alkylation method | |
CN219879874U (en) | Fluidized bed reactor of low-carbon alkane dehydrogenation riser | |
WO2020088440A1 (en) | Liquid-solid radial moving bed reaction device and solid acid alkylation method | |
CN112876333A (en) | Method and system for cracking olefin through coupling methanol to olefin | |
CN114570437B (en) | Method for removing sulfur in catalyst for moving bed propane dehydrogenation | |
CN105441119B (en) | Hydro carbons continuous reforming process | |
CN108080009A (en) | A kind of alkane isomerization reaction-regenerative device and method | |
CN115746906B (en) | Method and system for preparing chemical product by mixing oxygen-containing compound and light hydrocarbon and catalytically cracking | |
CN205328953U (en) | Continuous reforming unit of hydro carbons | |
CN114286720B (en) | Baffled turbulent/fast fluidized bed reactor for maximizing low carbon olefin yield | |
CN105368488A (en) | Continuous reforming technology of hydrocarbons |
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 |