WO2020083279A1 - 一种液固轴向移动床反应与再生装置和一种固体酸烷基化方法 - Google Patents

一种液固轴向移动床反应与再生装置和一种固体酸烷基化方法 Download PDF

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WO2020083279A1
WO2020083279A1 PCT/CN2019/112517 CN2019112517W WO2020083279A1 WO 2020083279 A1 WO2020083279 A1 WO 2020083279A1 CN 2019112517 W CN2019112517 W CN 2019112517W WO 2020083279 A1 WO2020083279 A1 WO 2020083279A1
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Prior art keywords
catalyst
bed
reaction
regeneration
moving bed
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PCT/CN2019/112517
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English (en)
French (fr)
Inventor
胡立峰
候拴弟
毛俊义
朱振兴
唐晓津
刘铮
李永祥
赵志海
Original Assignee
中国石油化工股份有限公司
中国石油化工股份有限公司石油化工科学研究院
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Priority claimed from CN201811229732.2A external-priority patent/CN111068590B/zh
Priority claimed from CN201811230209.1A external-priority patent/CN111068591B/zh
Application filed by 中国石油化工股份有限公司, 中国石油化工股份有限公司石油化工科学研究院 filed Critical 中国石油化工股份有限公司
Priority to CA3117403A priority Critical patent/CA3117403A1/en
Priority to EP19875447.5A priority patent/EP3871763A4/en
Priority to US17/287,648 priority patent/US11912643B2/en
Publication of WO2020083279A1 publication Critical patent/WO2020083279A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C07C2/54—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition of unsaturated hydrocarbons to saturated hydrocarbons or to hydrocarbons containing a six-membered aromatic ring with no unsaturation outside the aromatic ring
    • C07C2/56—Addition to acyclic hydrocarbons
    • C07C2/58—Catalytic processes
    • C07C2/62—Catalytic processes with acids
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G29/00—Refining of hydrocarbon oils, in the absence of hydrogen, with other chemicals
    • C10G29/20—Organic compounds not containing metal atoms
    • C10G29/205—Organic compounds not containing metal atoms by reaction with hydrocarbons added to the hydrocarbon oil
    • 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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
    • B01J29/084—Y-type faujasite
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J38/00—Regeneration or reactivation of catalysts, in general
    • B01J38/48—Liquid treating or treating in liquid phase, e.g. dissolved or suspended
    • B01J38/50—Liquid treating or treating in liquid phase, e.g. dissolved or suspended using organic liquids
    • B01J38/56—Hydrocarbons
    • 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
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/08—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with moving particles
    • B01J8/085—Feeding reactive fluids
    • 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
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/08—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with moving particles
    • B01J8/12—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with moving particles moved by gravity in a downward flow
    • B01J8/125—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with moving particles moved by gravity in a downward flow with multiple sections one above the other separated by distribution aids, e.g. reaction and regeneration sections
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C07C2/54—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition of unsaturated hydrocarbons to saturated hydrocarbons or to hydrocarbons containing a six-membered aromatic ring with no unsaturation outside the aromatic ring
    • C07C2/56—Addition to acyclic hydrocarbons
    • C07C2/58—Catalytic processes
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G50/00—Production of liquid hydrocarbon mixtures from lower carbon number hydrocarbons, e.g. by oligomerisation
    • 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
    • B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
    • B01J2208/00796—Details of the reactor or of the particulate material
    • B01J2208/00823—Mixing elements
    • B01J2208/00831—Stationary elements
    • B01J2208/00849—Stationary elements outside the bed, e.g. baffles
    • 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
    • B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
    • B01J2208/00796—Details of the reactor or of the particulate material
    • B01J2208/00893—Feeding means for the reactants
    • B01J2208/00929—Provided with baffles
    • 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
    • B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
    • B01J2208/00796—Details of the reactor or of the particulate material
    • B01J2208/00938—Flow distribution elements
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2529/00—Catalysts comprising molecular sieves
    • C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
    • C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • C07C2529/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/20—Characteristics of the feedstock or the products
    • C10G2300/30—Physical properties of feedstocks or products
    • C10G2300/305—Octane number, e.g. motor octane number [MON], research octane number [RON]
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/40—Characteristics of the process deviating from typical ways of processing
    • C10G2300/4006—Temperature
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/40—Characteristics of the process deviating from typical ways of processing
    • C10G2300/4012—Pressure
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/40—Characteristics of the process deviating from typical ways of processing
    • C10G2300/4018—Spatial velocity, e.g. LHSV, WHSV
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/70—Catalyst aspects
    • 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

Definitions

  • the invention relates to the field of solid acid alkylation. Specifically, the present invention relates to a liquid-solid axial moving bed reaction and regeneration device, and a solid acid alkylation method.
  • alkylated oil Under the action of strong acid, the technology of generating alkylated oil from isoparaffins (mainly isobutane) and olefins (C3-C5 olefins) as raw materials provides the possibility of cleaner production of gasoline.
  • Alkylated oils have higher octane number and lower vapor pressure, are mainly composed of saturated hydrocarbons, and do not contain sulfur, nitrogen, olefins and aromatic hydrocarbons, so they are called clean gasoline, which is aviation gasoline and vehicles. Ideal blending components with gasoline.
  • the alkylation technology can be divided into liquid acid alkylation and solid acid alkylation according to the catalyst form.
  • liquid acid alkylation technology sulfuric acid method and hydrofluoric acid method
  • liquid acid alkylation technology is more mature and has better reaction options
  • problems such as the problem of serious equipment corrosion in the process of liquid acid alkylation.
  • sulfuric acid process the process consumes a large amount of acid, and a large amount of waste acid has certain safety risks in transportation and processing.
  • hydrofluoric acid method because hydrofluoric acid has a strong Corrosive and toxic, and easily volatile, will cause great harm to the human body. Therefore, in contrast, the use of solid acid as a catalyst not only does not cause pollution to the environment, but also does not have the problem of equipment corrosion.
  • US8373014 discloses a solid acid alkylation reaction method using a radially-moving bed placed in an overlapping manner as a reactor.
  • a structure similar to the catalytic reforming overlapping radial moving bed is adopted.
  • the single-stage reactor is provided with an annular barrel for the distribution of reaction materials and a central tube for collecting materials and sandwiched between the two.
  • the reaction bed zone of the reactor; between the two reactors, a catalyst material delivery pipe is used to transport the catalyst in the upper catalyst bed to the reaction bed zone of the lower reactor.
  • the effluent material in the intermediate reactor is divided into two parts, a part is pumped back to the upstream reactor and mixed with fresh reaction raw materials through the mixer as the feed of the upstream reactor, this part can be called recycle material; the other part is introduced into the downstream reaction
  • the feed mixer of the reactor is mixed with fresh reaction raw materials before being used as the feed of the downstream reactor. This part is used directly without pump boosting.
  • the circulating material part also needs to pass through a heat exchanger to extract the heat of reaction.
  • CN1879956A discloses a fluidized bed solid acid alkylation technology.
  • the technology mainly includes a riser reactor, a fluidized bed reactor, a loop regenerator and a moving bed regenerator.
  • the liquid velocity range in the riser reactor is 0.1-3m / s
  • the liquid velocity range in the fluidized bed reactor is 0.26-7.68cm / s.
  • the regeneration process can determine the form of the regeneration reactor according to the regeneration time. If the regeneration time is a few seconds to tens of seconds, a loop regenerator can be used alone. If the regeneration time is tens of seconds to tens of minutes, a moving bed regenerator can be used alone, and the liquid velocity of the regeneration liquid is 0.2-3 cm / s.
  • CN1113906A discloses a fluidized bed solid acid aromatic hydrocarbon alkylation process technology.
  • the process mainly includes a liquid-solid ascending reactor, a pending catalyst settling backwash tower, a liquid-solid parallel flow upward regenerator, and a catalyst settling backwash after regeneration tower.
  • the particle size of the catalyst used is required to be 0.05-0.8mm, and the liquid liquid velocity that can carry the catalyst upward in the reactor and regenerator is 1-15 times the sedimentation speed of the particle terminal.
  • bottom-up is used The flowing washing liquid is used to wash and regenerate the catalyst.
  • the flow rate of the washing liquid is 0.5-5 times of the sedimentation speed of the particle terminal.
  • the fixed bed alkylation technology and the fluidized bed alkylation technology disclosed in the prior art require at least two reactor switching operations to achieve continuous and stable operation of the reaction device, and the catalyst in the bed layer is subjected to high temperature at intervals Regeneration, after deep regeneration, the temperature of the high-temperature bed is also cooled. Because the device frequently switches between reaction and regeneration temperature, it causes many problems when it is continuously and stably operated in industrial applications. In addition, in the prior art, it is difficult for the catalyst in the solid acid alkylation reaction device to maintain a stable and high target product selectivity.
  • a solid acid alkylation method is provided.
  • the method provided by the invention can not only realize the continuous and stable operation of the solid acid alkylation reaction, but also improve the target product selectivity.
  • a liquid-solid axial moving bed reaction and regeneration device characterized in that the device includes:
  • the axially moving bed reactor (1), the spent agent receiver (5), the catalyst regenerator (4) and the regenerator agent (6) are connected in sequence, wherein the catalyst outlet of the regenerator agent (6) is connected to The catalyst inlet of the axial moving bed reactor (1) is connected;
  • the axial moving bed reactor (1) is provided with at least two catalyst beds (3) placed above and below and optionally a catalyst regeneration bed, and the axial moving bed reactor (1) is in each catalyst bed ( 3) There is a feeding port (2) above;
  • a catalyst delivery pipe (16) is provided between the adjacent two beds to enable the catalyst to react in the axially moving bed Move from top to bottom in the device (1);
  • a separation member (10) for example, a separation member may be provided in each reaction bed, the space inside the separation member (10) communicates with a catalyst delivery pipe (16), and the separation member (10) is used for an upstream catalyst bed After the reaction, the material and the catalyst are separated, and the catalyst separated by the separation member (10) moves downward through the catalyst delivery pipe (16).
  • the axially moving bed reactor further includes at least one catalyst regeneration bed.
  • the catalyst bed and the catalyst regeneration bed have the same number and the catalyst bed and the catalyst regeneration bed are placed in order, and more preferably, the catalyst The number of regenerated beds is one less than that of catalyst beds, the catalyst beds and the catalyst regenerated beds are placed in order, and the top and bottom of the axially moving bed reactor are set as catalyst reaction beds;
  • the axially moving bed reactor has a catalyst inlet that communicates with the top of the first catalyst bed
  • each catalyst bed has a catalyst inlet and a reaction material inlet.
  • the catalyst inlet of the first reaction bed is the catalyst inlet of the axially moving bed reactor.
  • the catalyst inlet of the subsequent reaction bed communicates with the catalyst delivery pipe ;
  • each catalyst bed has a catalyst outlet and a reaction material outlet that communicate with the catalyst delivery pipeline;
  • the top of the catalyst regeneration bed has a catalyst inlet and a regeneration medium outlet communicating with the catalyst delivery pipeline;
  • the bottom of the catalyst regeneration bed has a catalyst outlet and a regeneration medium inlet that communicate with the catalyst delivery pipeline;
  • the catalyst delivery line for transferring the catalyst from the catalyst regeneration bed to the catalyst bed is provided with an isolation medium inlet;
  • Separator is provided at the bottom of each catalyst bed
  • the beds are communicated with each other through a catalyst delivery line;
  • the bottom of the catalyst bed communicates with the regeneration bed through a catalyst delivery pipe inserted into the regeneration bed.
  • the outlet of the inserted catalyst delivery pipe is lower than the outlet of the regeneration medium in the regeneration bed;
  • the inlet of the isolation medium communicates with the outlet of the reaction material of the catalyst bed in the last stage, so that the reaction material after the pump pressurization is used as the isolation medium;
  • the reaction material outlet of the upstream catalyst bed communicates with the reaction material inlet of the downstream catalyst bed, optionally, through a connection line, and an inlet of fresh reaction raw materials is also provided on the connection line;
  • the outlet of the regeneration medium of the upstream catalyst regeneration bed can be connected to the inlet of the regeneration medium of the downstream catalyst regeneration bed through a pipeline;
  • a separation member (10) is provided between the upstream catalyst bed and the last catalyst bed
  • a separation member may be provided in each reaction bed, and the inner space of the separation member (10) communicates with a catalyst delivery pipe (16).
  • the separation member (10) is used for the materials and materials after the upstream catalyst bed reaction
  • the catalyst separated by the separation member (10) moves downward through the catalyst delivery pipe (16).
  • reaction material baffle (11) is provided between the bed and the last stage of the catalyst regeneration bed, for example, a reaction material baffle can be provided in each catalyst bed, especially in the bed of the reaction bed In the space, the reaction material baffle (11) is used to strengthen the mixing of the reacted material and the liquid fresh reaction raw material fed into the inlet (2).
  • reaction material baffle (11) includes a main shaft (111) and a conveying member (112) extending spirally along the main shaft axis .
  • reaction material baffle (11) includes a plurality of baffles (113) and a plurality of baffles ( 113)
  • the plurality of baffles (113) are staggered with each other to form a flow channel through which the reaction material can pass.
  • the catalyst distribution member includes a cone-shaped distribution baffle (12), which is arranged coaxially with the catalyst delivery tube (16); further preferably, the cone-shaped distribution baffle (12) ) The same number as the catalyst delivery pipe (16);
  • the catalyst distribution member further includes a horizontal distribution baffle (13) disposed below the cone-shaped distribution baffle (12), and the horizontal distribution baffle (13) is provided with holes for the catalyst to pass through .
  • the first particle flow regulator (25) and the second particle flow regulator (33) are each independently an L-shaped or approximately L-shaped material delivery valve group.
  • the liquid-solid axial moving bed reaction and regeneration device according to any one of technical solutions 1-10, wherein the device further includes a catalyst buffer tank (38), and the catalyst buffer tank (38) is disposed on the shaft Between the moving bed reactor (1) and the spent agent receiver (5), the catalyst inlet of the catalyst buffer tank (38) communicates with the catalyst outlet of the axial moving bed reactor (1), and the catalyst buffer tank (38) The catalyst outlet of is connected with the catalyst inlet of the waiting agent receiver (5).
  • a solid acid alkylation method including:
  • This method is carried out in the liquid-solid axial moving bed reaction and regeneration device described in technical solutions 1-11, and the liquid phase raw materials are fed into the axial moving bed reactor from the feed port provided above each catalyst bed layer. Catalyst contact reaction.
  • the mass space velocity of materials entering each catalyst bed in terms of olefin is 0.05-1h -1 ;
  • the molar ratio of isoparaffin to olefin in the material entering each catalyst bed is 200-1000: 1;
  • the residence time of the catalyst in the axial moving bed reactor is 6-72h.
  • the catalyst is a solid acid catalyst
  • the solid acid catalyst contains a molecular sieve and a heat-resistant inorganic oxide, and the total amount of the solid acid catalyst
  • the content of molecular sieve is 65-95% by weight
  • the content of heat-resistant inorganic oxide is 5-35% by weight
  • the molecule is selected from at least one of FAU structure zeolite, BETA structure zeolite and MFI structure zeolite, and the heat-resistant inorganic oxide is alumina and / or silica;
  • the solid acid catalyst further contains a metal active component
  • the metal active component is selected from at least one of Fe, Co, Ni, Pd, and Pt, based on the total amount of the solid acid catalyst, The content of the metal active component is 0.15-2% by weight.
  • a separation member (10) is provided between two adjacent catalyst bed layers (3), for example, the separation member may be provided in each reaction bed In the layer, the space inside the separation member (10) communicates with the catalyst delivery pipe (16).
  • the separation member (10) is used for the separation of the material and the catalyst after the reaction of the upstream catalyst bed.
  • the separation member (10) is obtained by separation The catalyst moves down through the catalyst delivery tube (16).
  • reaction material baffle (11) is provided between two adjacent catalyst beds (3), for example, in each catalyst bed
  • the reaction material baffle can be provided in the bed space of the reaction bed; the reaction material baffle (11) is used to strengthen the fresh liquid fed by the material and the feed port (2) after the reaction Mixing of reaction raw materials;
  • the reaction material baffle (11) includes a main shaft (111) and a conveying member (112) spirally extending along the axial direction of the main shaft;
  • the reaction material baffle (11) includes a plurality of baffles (113), the plurality of baffles (113) are inclinedly arranged along the axial direction of the axial moving bed reactor (1), and a plurality of The baffles (113) are staggered with each other to form a flow channel through which the reaction material can pass.
  • the catalyst distribution member includes a cone-shaped distribution baffle (12), which is arranged coaxially with the catalyst delivery tube (16); further preferably, the cone-shaped distribution baffle (12) ) The same number as the catalyst delivery pipe (16);
  • the catalyst distribution member further includes a horizontal distribution baffle (13) disposed below the cone-shaped distribution baffle (12), and the horizontal distribution baffle (13) is provided with holes for the catalyst to pass through .
  • the apparent flow velocity of the regeneration medium in the catalyst regenerator (4) is 0.003-0.8 m / s, further preferably 0.02-0.5 m / s.
  • the first particle flow regulator (25) and the second particle flow regulator (33) are each independently an L-shaped or approximately L-shaped material delivery valve group.
  • the device further comprises a catalyst buffer tank (38), the catalyst buffer tank (38) is provided in the axial moving bed reactor (1), Between the catalyst receiver (5), the catalyst inlet of the catalyst buffer tank (38) communicates with the catalyst outlet of the axial moving bed reactor (1), and the catalyst outlet of the catalyst buffer tank (38) and the catalyst receiver (5) The catalyst inlet communicates.
  • the regeneration temperature is 50-140 °C
  • the apparent flow velocity of the regeneration medium in the regenerator is 0.01-0.5m / s;
  • the regeneration medium is a liquid hydrocarbon in which hydrogen is dissolved;
  • the liquid hydrocarbon is a C3-C6 (for example C3-C5) saturated alkane or a mixture of the reaction product and the above-mentioned saturated alkane.
  • the liquid hydrocarbon is C3-C6 (for example C3 -C5) a mixture of saturated alkanes and reaction products.
  • the material After the reaction of the fresh raw material with the circulating material or the upstream catalyst bed, the material enters the axial moving bed reactor, and the reaction occurs when the catalyst bed contacts the catalyst; after the reaction, the material enters the next reaction bed through the separation member or finally leaves the reactor.
  • the catalyst that has not passed through the separation member moves down through the catalyst delivery tube into the downstream reaction bed for reaction or enters into the catalyst regeneration bed for low temperature regeneration, and the catalyst after low temperature regeneration moves down through the catalyst delivery tube into the downstream reaction bed.
  • a catalyst distribution piece is provided between two adjacent beds, and the catalyst passing from the upstream bed through the catalyst delivery pipe is dispersed and dropped to the downstream bed under the action of the catalyst distribution piece;
  • the bottom of the axial moving bed reactor is provided with a bottom catalyst collection area; the catalyst passing through the most downstream catalyst bed is sent to the bottom catalyst collection area, and then sent to the receiver of the waiting agent;
  • a first particle flow regulator is arranged on the communication line between the catalyst outlet of the axial moving bed reactor and the catalyst inlet of the to-be-generated agent receiver to adjust the catalyst particle flow;
  • a de-liquid phase material outlet is provided at the bottom of the degenerated liquid receiver, the liquid phase material carried in the catalyst is removed in the deoxidized liquid receiver, and the de-liquid phase material delivery line sent from the de-liquid phase material outlet is provided with a deliquid
  • the filter blocks the fine catalyst powder or fine catalyst particles
  • the catalyst after being deliquored in the raw agent receiver is sent to a catalyst regenerator for regeneration, and the catalyst regenerator is provided with a regeneration medium inlet and a regeneration medium outlet;
  • the regeneration medium is fed into the catalyst regenerator through the regeneration medium inlet to contact the catalyst to regenerate the catalyst, and the regeneration medium is discharged through the regeneration medium outlet;
  • a regeneration medium filter is provided on the regeneration medium delivery line sent from the regeneration medium discharge port to block fine powder or fine particles;
  • the catalyst regenerator is optionally provided with a fresh catalyst feed port for fresh catalyst to enter the catalyst regenerator;
  • the regenerated catalyst flows into the regenerant receiver through the catalyst delivery line at the bottom of the catalyst regenerator.
  • the regenerant receiver is provided with a liquid phase material replenishment inlet, and the liquid phase material is introduced into the regenerant receiver through the liquid phase material replenishment inlet to replace the catalyst gap gas;
  • the regenerated catalyst will return to the axially moving bed reactor through the catalyst delivery pipeline between the regenerant receiver and the axially moving bed reactor to continue participating in the reaction until it is deactivated and then be transferred to the waiting agent receiver;
  • a second particle flow regulator is provided on the communication line between the catalyst outlet of the regenerant receiver and the catalyst inlet of the axial moving bed reactor to adjust the catalyst particle flow.
  • the axial moving bed reactor includes:
  • the layer spacing is placed sequentially, more preferably, the catalyst regeneration bed is one less than the catalyst bed, the catalyst bed and the catalyst regeneration bed are placed sequentially, and the top and bottom ends of the axially moving bed reactor are set as catalysts Reaction bed
  • the axial moving bed reactor has a catalyst inlet that communicates with the top of the first reaction bed
  • each reaction bed has a catalyst inlet and a reaction material inlet.
  • the catalyst inlet of the first reaction bed is the catalyst inlet of the axially moving bed reactor, and the catalyst inlet of the subsequent reaction bed communicates with the catalyst delivery pipe ;
  • each reaction bed there is a catalyst outlet and a reaction material outlet that communicate with the catalyst delivery pipeline;
  • the top of the catalyst regeneration bed has a catalyst inlet and a regeneration medium outlet communicating with the catalyst delivery pipeline;
  • the bottom of the catalyst regeneration bed has a catalyst outlet and a regeneration medium inlet that communicate with the catalyst delivery pipeline;
  • the catalyst delivery line for transferring the catalyst from the catalyst regeneration bed to the reaction bed is provided with an isolation medium inlet;
  • the beds are communicated with each other through a catalyst delivery line;
  • the bottom of the reaction bed communicates with the regeneration bed through a catalyst delivery pipe inserted into the regeneration bed.
  • the outlet of the inserted catalyst delivery pipe is lower than the outlet of the regeneration medium in the regeneration bed;
  • the isolation medium is preferably a circulating material that is pressurized by the pump after the reaction, and the inlet of the isolation medium is in communication with the reaction material outlet of the reaction bed in the last stage;
  • the material enters the next stage of the reaction bed through the separation member or is finally discharged.
  • the catalyst that has not passed through the separation member moves downward through the catalyst delivery pipe;
  • the outlet of the reaction material in the upstream reaction bed communicates with the inlet of the reaction material in the downstream reaction bed, optionally, through a connecting pipeline, and an inlet for fresh reaction raw materials is also provided on the connecting pipeline;
  • the top of the bed refers to a position above 70% of each section of the bed from bottom to top, and the bottom of the bed refers to a position below 20% of each section of the bed from bottom to top;
  • the outlet of the regeneration medium of the upstream catalyst regeneration bed can be connected to the inlet of the regeneration medium of the downstream catalyst regeneration bed through a pipeline;
  • Corresponding material distributors are provided for the reaction material feed port of the reaction bed, the regeneration medium inlet of the catalyst regeneration bed, and the isolation medium inlet provided on the catalyst delivery line for transferring the catalyst from the catalyst regeneration bed to the reaction bed;
  • the material After the fresh reaction raw materials react with the circulating material or the upstream reaction bed, the material enters the reaction bed of the axial moving bed; in the reaction bed, the mixture is distributed through the reaction material distributor and passes through the reaction bed along the axial direction of the reaction bed , The solid acid catalyst contacts and reacts, most of the liquid material after the reaction is discharged through the outlet of the reaction material, and the remaining small part of the liquid material follows the catalyst particles into the next reaction bed or through the reaction bed The inserted pipeline between the catalyst regeneration bed and the catalyst regeneration bed enters;
  • the liquid phase material and fresh reaction raw materials enter the next stage of the reaction bed to continue to participate in the reaction or directly exit the reaction bed, and the alkylated oil product is collected after separation (such as distillation);
  • the catalyst undergoes countercurrent contact (low temperature regeneration) with a liquid-phase regeneration medium in which hydrogen is dissolved under regeneration conditions to convert unsaturated hydrocarbons adsorbed on the catalyst into saturated hydrocarbon molecular bands that are easily desorbed
  • the catalyst regeneration bed is exited to realize partial regeneration of the catalyst; the regenerated catalyst will flow into the next reaction bed through the catalyst delivery line at the bottom of the catalyst regeneration bed; during the process of transferring the catalyst from the bottom of the catalyst regeneration bed to the reaction bed,
  • the isolation medium enters through the isolation medium introduction port provided on the transmission line, and replaces the liquid phase medium traveling down with the catalyst;
  • the catalyst in each bed of the moving bed will gradually increase the degree of deactivation as the reaction progresses and the number of regeneration increases, and it will gradually fall to the lower bed and finally reach the bottom of the moving bed reactor; the final catalyst is sent To the catalyst regenerator for high temperature and deep regeneration, to achieve complete recovery of catalyst activity; the restored catalyst is sent to the first reaction bed of the moving bed reactor to continue to participate in the reaction, and so cycle;
  • the reaction conditions in the reaction bed may include:
  • the reaction temperature is 30-100 °C
  • the reaction pressure is 1.0-3.4MPa, gauge pressure,
  • the apparent flow velocity of liquid materials in the reactor is 0.03-1m / s;
  • the mass space velocity of the mixed olefin feedstock is 0.05-1h -1 ;
  • the molar ratio of alkane to olefin at the entrance of the reaction bed is 200-1000: 1;
  • the average particle diameter of the solid acid catalyst particles is 0.3-3 mm.
  • the regeneration conditions in the catalyst regeneration bed may include:
  • the regeneration temperature is 50-140 °C
  • the apparent flow velocity of the regeneration medium in the regenerator is 0.01-0.5m / s;
  • the regeneration medium is a liquid hydrocarbon in which hydrogen is dissolved;
  • the liquid hydrocarbon is a C3-C6 (for example C3-C5) saturated alkane or a mixture of the reaction product and the above-mentioned saturated alkane.
  • the liquid hydrocarbon is C3-C6 (for example C3 -C5) a mixture of saturated alkanes and reaction products;
  • the regeneration conditions in the catalyst regenerator may include:
  • the regeneration temperature is 180-400 °C
  • the regeneration pressure is 0.5-4.0MPa
  • the regeneration medium is hydrogen or a mixture of hydrogen and low-carbon hydrocarbons (such as C3-C8), preferably a mixture of hydrogen and low-carbon hydrocarbons (such as C3-C8);
  • the main active component of the catalyst is a molecular sieve loaded with a certain amount of metal
  • the molecular sieve is FAU structure zeolite, BETA structure zeolite, MFI structure zeolite and a combination of one or more of them, preferably having FAU structure and BETA structure Zeolite
  • the metal supported on the catalyst is one or a combination of Fe, Co, Ni, Pd and / or Pt, preferably one or a combination of Co, Ni or Pt.
  • the liquid-solid axial moving bed reaction and regeneration device provided by the present invention can realize the life distribution of the catalyst, and can remove part of the deactivated catalyst out of the system, and then add fresh catalyst;
  • the fluidized bed reactor cannot achieve the catalyst life distribution;
  • the liquid-solid axial moving bed reaction and regeneration device uses an axial moving bed reactor, and a single (set) device can meet the requirements, reducing the investment cost of the device, in addition, by deactivating the catalyst particles Leading to the outside of the reactor for deep regeneration, on the premise of not affecting the stable operation of the reaction device, the continuous operation of catalyst reaction and regeneration is realized, the catalyst in the device has a relatively stable balanced activity, and the alkylated oil is improved. Selectivity of target product.
  • the method provided by the present invention can realize the life distribution of the catalyst, and the deactivated part of the catalyst can be removed from the system and then filled with fresh catalyst; while the fluidized bed reactor cannot achieve the catalyst Life distribution
  • the method provided by the present invention uses an axial moving bed reactor, and a single (set) device can meet the requirements, reducing the investment cost of the device.
  • a single (set) device can meet the requirements, reducing the investment cost of the device.
  • the deactivated catalyst particles out of the reactor for deep regeneration in On the premise of not affecting the stable operation of the reaction device, the continuous operation of the catalyst reaction and regeneration is realized, the catalyst in the device has a relatively stable balanced activity, and the selectivity of the target product in the alkylated oil is improved.
  • FIG. 2 is a schematic diagram of a baffle provided by the present invention.
  • FIG. 3 is a liquid-solid axial moving bed reaction and regeneration device according to a specific embodiment provided by the present invention.
  • the directional words such as “upper and lower” generally refer to the upper and lower parts shown with reference to the drawings unless otherwise stated.
  • Orientation words used such as “inside and outside” refer to inside and outside relative to the outline of each component itself.
  • the top, top, etc. of the bed refer to a position above 70% from bottom to top of each section of the bed, and the bottom, etc. of the bed refer to the bottom to top of each section of the bed Less than 20% of the location.
  • the present invention provides a liquid-solid axial moving bed reaction and regeneration device, the device comprising:
  • the axially moving bed reactor 1, the spent agent receiver 5, the catalyst regenerator 4 and the regenerant receiver 6 are connected in sequence, wherein the catalyst outlet of the regenerant receiver 6 and the catalyst inlet of the axial moving bed reactor 1 Connected
  • the axial moving bed reactor 1 is provided with at least two catalyst beds 3 placed up and down, and the axial moving bed reactor 1 is provided with a feed port 2 above each catalyst bed 3;
  • a catalyst delivery tube 16 is provided between two adjacent catalyst bed layers 3 so that the catalyst can move from top to bottom in the axial moving bed reactor 1.
  • the sequential connection means that the catalyst outlet of the axially moving bed reactor 1 is connected to the catalyst inlet of the bioreagent receiver 5 and the catalyst outlet of the bioreactor receiver 5 is connected to the catalyst regenerator 4
  • the catalyst inlet is connected, and the catalyst outlet of the catalyst regenerator 4 is connected to the catalyst inlet of the regenerant receiver 6.
  • the catalyst outlet of the regenerant receiver 6 communicates with the catalyst inlet of the axial moving bed reactor 1 to feed the regenerated catalyst into the axial moving bed reactor 1.
  • the axial moving bed reactor in the present invention refers to a moving bed reactor in which the moving direction of the catalyst is axial.
  • the axial moving bed reactor 1 is provided with at least two catalyst beds placed up and down, preferably 3-8 catalyst beds 3 placed up and down.
  • the thickness of the catalyst bed layer 3 is not particularly limited.
  • the thickness of each catalyst bed layer 3 is independently 10-30% of the height of the axially moving bed reactor 1.
  • the height of the axial moving bed reactor 1 is 7.5 m and the inner diameter is 600 mm as an example for illustration, but the present invention is not limited to this. Those skilled in the art can make appropriate adjustments according to the actual situation.
  • the axial moving bed reactor 1 has a height of 5-75 meters and an inner diameter of 200-3000 mm.
  • the axially moving bed reactor 1 is provided with a feed port 2 above each catalyst bed 3.
  • the liquid fresh reaction raw materials are fed into the axially moving bed reactor 1 from the feed port 2 of the axially moving bed reactor 1 and contact the catalyst packed in the catalyst bed layer 3 for contact reaction.
  • the catalyst in the uppermost catalyst bed 3 of the axially moving bed reactor 1 is in contact reaction with the liquid fresh reaction raw material, while the catalyst in the other catalyst bed 3 reacts with the liquid fresh reaction raw material and the material from the upstream catalyst bed 3 The mixture is contacted.
  • liquid fresh reaction raw materials can be sent into the axial moving bed reactor 1 through different feed ports 2, which is more conducive to controlling temperature rise.
  • the catalyst delivery pipe 16 is not particularly limited, as long as the catalyst can be moved from top to bottom in the axial moving bed reactor 1.
  • the catalyst delivery tube may be cylindrical.
  • One catalyst delivery pipe 16 may be provided between two adjacent catalyst bed layers 3, or two or more catalyst delivery pipes 16 may be provided.
  • the inner diameter and number of the catalyst delivery pipe 16 are appropriately selected according to the inner diameter of the axial moving bed reactor 1.
  • 2-5 catalyst delivery tubes 16 may be provided between two adjacent catalyst bed layers 3, and the inner diameter of the catalyst delivery tube 16 may be 15-50 mm.
  • the height of the axially moving bed reactor 1 is 5-75 meters
  • the inner diameter is 200-3000 mm
  • 2-5 catalyst delivery pipes 16 may be provided between two adjacent catalyst bed layers 3.
  • the inner diameter of the delivery tube 16 may be 5-150 mm.
  • the reaction material outlet (preferably provided at the bottom) of the axial moving bed reactor 1 communicates with the uppermost feed port 2 of the axial moving bed reactor 2 to connect the axial moving bed
  • the reaction material obtained from the reactor 1 is circulated back to the axial moving bed reactor 1.
  • the catalyst bed is also called a reaction bed, and the two adjacent catalyst beds refer to the upstream reaction bed and the downstream reaction bed; when the catalyst regeneration bed is not included, the two adjacent beds A catalyst bed refers to two catalyst beds upstream and downstream, and in the case of including a non-last catalyst regeneration bed, two adjacent catalyst beds refer to the first upstream of the catalyst regeneration bed respectively Catalyst bed (ie, reaction bed) of a non-catalyst regeneration bed and the catalyst bed (ie, reaction bed) of the first non-catalyst regeneration bed downstream of the catalyst regeneration bed.
  • between two adjacent beds refers to any two adjacent beds, including: an upstream catalyst bed (ie, a reaction bed) and a downstream catalyst bed (ie, a reaction bed) Between layers), upstream catalyst bed (i.e. reaction bed) and downstream catalyst regeneration bed, upstream catalyst regeneration bed and downstream catalyst bed (i.e. reaction bed), upstream catalyst Between the regeneration bed and the downstream catalyst regeneration bed.
  • upstream catalyst bed ie. reaction bed
  • downstream catalyst bed i.e. reaction bed
  • upstream catalyst regeneration bed and downstream catalyst bed i.e. reaction bed
  • a separation is provided between two adjacent catalyst beds 3 and, if any, between the upstream catalyst bed (reaction bed) and the last stage of catalyst regeneration bed
  • a piece 10 for example, a separation piece 10 may be provided in each reaction bed layer
  • the space inside the separation piece 10 communicates with a catalyst delivery pipe 16, and the separation piece 10 is used for materials and catalyst after the reaction of the upstream catalyst bed
  • the catalyst separated by the separating member 10 moves downward through the catalyst delivery pipe 16. After the reaction of the upstream catalyst bed, the material and the catalyst are separated by the separation member 10 to obtain the reacted material and the catalyst.
  • the catalyst moves downward through the catalyst delivery pipe 16, and the reacted material is in the space between the two adjacent catalyst beds ( In the present invention, it is referred to as the bed space before the reaction bed), mixed with the liquid fresh reaction raw materials fed into the feed port above the catalyst bed 3, and then flows into the downstream catalyst bed.
  • the separation member 10 may be a mesh screen with pores (the pore diameter may be determined according to the size of the catalyst particles), which allows the material after the reaction to pass through to achieve the separation of the material and the catalyst after the reaction.
  • a reaction material baffle 11 is provided between two adjacent catalyst beds 3, and the reaction material baffle 11 It is used to strengthen the mixing of materials and liquid fresh reaction raw materials fed into the inlet 2 after the reaction.
  • a reaction material baffle may be provided in each catalyst bed, especially in the bed space of the reaction bed.
  • the specific structure of the reaction material baffle 11 is not particularly limited, as long as it can enhance the mixing of the material after the strengthening reaction and the liquid fresh reaction raw material.
  • the reaction material baffle 11 is placed in the bed space in front of the reaction bed, and the number thereof may be one or more than two, preferably 1-6.
  • the reaction material baffle 11 includes a main shaft 111 and a conveying member 112 spirally extending along the axial direction of the main shaft. Specifically, the inlet of the spirally extending flow channel formed by the conveying member 112 is set according to the position of the feed inlet 2 so that the reacted materials and the liquid fresh reaction raw materials flow from the spirally extending flow channel formed by the conveying member 112, thereby achieving mixing .
  • the reaction material baffle 11 includes a plurality of baffles 113, and the plurality of baffles 113 moves along the axial direction of the bed reactor 1 in the axial direction It is arranged obliquely, and a plurality of baffles 113 are staggered with each other to form a flow channel through which the reaction material can pass.
  • the plurality of baffles 113 may be arranged obliquely downward or upwardly along the axial direction of the moving bed reactor 1 (as shown in FIG. 1).
  • the angle between the extension direction of the baffle plate 113 and the horizontal plane is 5-60 degrees, further preferably 10-40 degrees.
  • the staggered arrangement of the baffle plates 113 in the present invention means that the baffle plates 113 do not form a closed area with each other, so that the reaction materials can flow down smoothly.
  • part of the baffle plate 113 is fixedly connected to the wall of the axial moving bed reactor 1
  • part of the baffle plate 113 is fixedly connected to the wall of the catalyst delivery tube 16
  • the baffle plates 113 are arranged parallel to each other.
  • the distance between adjacent baffles 113 is 15-60 mm.
  • a catalyst distributor is provided between the two adjacent beds, said catalyst distributor It is used to disperse the catalyst at the outlet of the catalyst delivery pipe 16. If no catalyst distribution member is provided, the catalyst at the outlet of the catalyst delivery pipe 16 is likely to form a cone-shaped accumulation in the downstream catalyst bed.
  • the catalyst distribution member includes a cone-shaped distribution baffle 12 which is arranged coaxially with the catalyst delivery tube 16. The catalyst at the outlet of the catalyst delivery tube 16 falls on the tip of the cone-shaped distribution baffle 12 by gravity, and is dispersed to the horizontal sides of the catalyst delivery tube 16 by the dispersion of the cone-shaped distribution baffle 12. It is further preferred that the number of cone-shaped distribution baffles 12 and catalyst delivery tubes 16 is the same.
  • the catalyst distribution member further includes a horizontal distribution baffle 13 disposed below the cone-shaped distribution baffle 12, and the horizontal distribution baffle 13 is provided with holes for the catalyst to pass through .
  • the number of the horizontal distribution baffles 13 is not particularly limited, and may be one, or may be more than two, and are preferably provided at the radial intermediate positions of two adjacent cone-shaped distribution baffles 12 (and Axial downward position).
  • the radial and axial directions refer to the radial and axial directions of the axial moving bed reactor 1.
  • the holes in the horizontal distribution baffle 13 gradually become larger in the horizontally outward direction of the center of the axially moving bed reactor 1.
  • the part of the catalyst dispersed through the cone-shaped distribution baffle 12 near the center of the axially moving bed reactor 1 passes through the holes of the horizontal distribution baffle 13, and part of the catalyst that cannot pass is dispersed to The edge position of the axially moving bed reactor 1 is more conducive to ensuring uniform dispersion of the catalyst.
  • the horizontal distribution baffle 13 may be a circular distribution plate with a low aperture ratio in the middle region and a high aperture ratio at the side walls.
  • each catalyst bed of the axial moving bed reactor 1 will gradually deactivate as the reaction progresses, and it will gradually fall to the catalyst bed (reaction bed) or catalyst regeneration bed further downstream, and finally reach The bottom of the axially moving bed reactor 1 is then transported to the to-be-generated agent receiver 5 through a catalyst transport line.
  • the bottom of the axially moving bed reactor 1 is provided with a bottom catalyst collection zone 37.
  • the catalyst passing through the most downstream catalyst bed is sent to the bottom catalyst collection area 37, and after being collected in a certain amount, it is sent to the receiver 5 for the raw agent.
  • the axially moving bed reactor 1 and the raw material receiver 5, the raw material receiver 5 and the catalyst regenerator 4, the catalyst regenerator 4 and the regenerant are respectively provided with material line valves between the containers.
  • the raw material receiver 5 (preferably at the bottom) is provided with a liquid discharge outlet 15.
  • the liquid phase material carried in the catalyst can be removed by directly depressurizing or introducing high-pressure hydrogen, nitrogen, etc. in the standby agent receiver 5, and the liquid phase material can be transported out through the outlet 15 for liquid phase withdrawal.
  • a deliquoring filter 7 is provided on the deliquid phase material delivery line sent from the deliquid phase material outlet 15. The deliquoring filter 7 is used to block fine catalyst powder or fine catalyst particles.
  • the catalyst after being deliquored in the biochemical receiver 5 is sent to the catalyst regenerator 4 for regeneration.
  • the catalyst regenerator 4 is provided with a regeneration medium inlet 30 and a regeneration medium outlet 31.
  • the regeneration medium is fed into the catalyst regenerator 4 through the regeneration medium feed port 30 to contact the catalyst to regenerate the catalyst (preferably complete regeneration), and the regeneration medium is discharged through the regeneration medium discharge port 31.
  • a regeneration medium filter 8 is provided on the regeneration medium delivery line sent from the regeneration medium discharge port 31. The filter is used to block the flow of catalyst from the regenerator to the downstream gas circulation pressurization equipment and to collect fine powder or fine particles generated by friction or purge in the regeneration process.
  • the regeneration medium in the present invention may be air or a mixture of air and nitrogen.
  • the catalyst regenerator 4 may also be provided with a fresh catalyst feed port for the fresh catalyst to enter the catalyst regenerator 4.
  • a fresh catalyst feed port in the catalyst regenerator 4 part of the deactivated catalyst or the catalyst that is difficult to restore the initial activity can be replaced with fresh catalyst to ensure the processing capacity of the device.
  • a pump is provided on the fresh catalyst delivery line communicating with the fresh catalyst feed port.
  • the regenerated catalyst will flow into the regenerant receiver 6 through the catalyst delivery line at the bottom of the catalyst regenerator 4.
  • the regenerant receiver 6 is provided with a liquid-phase material replenishment inlet 32.
  • a liquid material such as alkane in the reaction raw material or liquid material after the reaction is introduced into the regenerant receiver 6 through the liquid material supplement inlet 32 to replace the gas in the catalyst gap.
  • the regenerated catalyst will return to the axial moving bed reactor 1 through the catalyst conveying pipeline between the regenerant receiver 6 and the axial moving bed reactor 1 and continue to participate in the reaction until it is deactivated and then delivered to the waiting agent receiver 5
  • the catalyst is circulated according to the above process.
  • the bioreagent receiver 5, the catalyst regenerator 4 and the regenerant receiver 6 are provided in order from top to bottom, and the bioreagent receiver 5, the catalyst regenerator 4 and the regenerant receiver
  • the catalyst circulation line between 6 is set vertically or at an angle of not less than 40 degrees with the horizontal plane.
  • a communication line between the catalyst outlet of the axially moving bed reactor 1 and the catalyst inlet of the to-be-generated agent receiver 5 is provided with a first particle flow regulator 25;
  • a second particle flow regulator 33 is provided on the communication line between the catalyst outlet and the catalyst inlet of the axial moving bed reactor 1.
  • the first particle flow regulator 25 and the second particle flow regulator 33 are not particularly limited as long as the flow rate of the catalyst particles can be adjusted.
  • the first particle flow regulator 25 and the second particle flow regulator 33 are each independently an L-shaped or approximately L-shaped material delivery valve group. Specifically, at least one liquid-phase material feed line is also connected to the L-shaped or nearly L-shaped material delivery valve group.
  • a particle flow regulator can increase the flow resistance of the particulate material.
  • the regulator is connected to at least one liquid material feed line to increase the flow driving force of the particulate material and reduce the flow resistance of the particulate material.
  • the device further includes a catalyst buffer tank 38 which is disposed between the axially moving bed reactor 1 and the receiver 5 for the raw agent, and the catalyst in the catalyst buffer tank 38
  • the inlet is in communication with the catalyst outlet of the axially moving bed reactor 1
  • the catalyst outlet in the catalyst buffer tank 38 is in communication with the catalyst inlet of the to-be-generated agent receiver 5.
  • the catalyst buffer tank 38 is used to store the catalyst discharged from the axially moving bed reactor 1 during the de-liquid phase feed and the catalyst regeneration agent discharging catalyst to ensure the catalyst material in the axially moving bed reactor 1 Continuity of flow and smooth operation of the device.
  • the axial moving bed reactor includes:
  • the catalyst bed and the catalyst regeneration bed are placed in order, and the top of the bed reactor is moved axially.
  • the bottom ends are set as catalyst reaction beds;
  • the axial moving bed reactor has a catalyst inlet 62 which communicates with the top of the first reaction bed;
  • each reaction bed has a catalyst inlet and a reaction material inlet 60.
  • the catalyst inlet of the first reaction bed is the catalyst inlet of the axially moving bed reactor, and the catalyst inlet of the subsequent reaction bed and the catalyst delivery pipe Interlinked
  • the catalyst delivery line for transferring the catalyst from the catalyst regeneration bed to the reaction bed is provided with an isolation medium inlet 70;
  • Separator 72 is provided at the bottom of each reaction bed
  • the beds are communicated with each other through a catalyst delivery line;
  • the bottom of the reaction bed communicates with the regeneration bed through a catalyst delivery pipe inserted into the regeneration bed.
  • the outlet of the inserted catalyst delivery pipe is lower than the outlet of the regeneration medium in the regeneration bed;
  • the isolation medium is preferably a circulating material that is pressurized by the pump after the reaction. Therefore, the isolation medium inlet 70 is in communication with the reaction material outlet 61 of the reaction bed in the last stage;
  • the material enters the next stage of the reaction bed through the separation member 72 or is finally discharged.
  • the catalyst that has not passed through the separation member 72 moves downward through the catalyst delivery pipe;
  • reaction material outlet 59 of the upstream reaction bed layer communicates with the reaction material inlet 60 of the downstream reaction bed layer through a pipeline, and inlets 56 and 57 of fresh reaction raw materials are also provided on this connection line;
  • the top of the bed refers to a position above 70% of each section of the bed from bottom to top, and the bottom of the bed refers to a position below 20% of each section of the bed from bottom to top;
  • the regeneration medium outlet 68 of the upstream catalyst regeneration bed communicates with the regeneration medium inlet 69 of the downstream catalyst regeneration bed through a pipeline;
  • the reaction material feed port 60 of the reaction bed, the regeneration medium inlet of the catalyst regeneration bed, and the isolation medium inlet 70 provided on the catalyst delivery line for transferring the catalyst from the catalyst regeneration bed to the reaction bed set the corresponding material distribution Device.
  • the liquid-solid axial moving bed reaction and regeneration device provided by the invention can realize continuous and stable operation of solid acid alkylation reaction and regeneration of deactivated catalyst, improve the selectivity of the target product and the flexibility of the device operation, and greatly reduce the The investment cost of the catalyst improves the economic competitiveness of the device. Therefore, the invention also provides the application of the liquid-solid axial moving bed reaction and regeneration device in the solid acid alkylation reaction.
  • the present invention provides a solid acid alkylation method, wherein: the method is performed in a liquid-solid axial moving bed reaction and regeneration device, and the liquid-solid axial moving bed reaction and regeneration device includes:
  • the axially moving bed reactor 1, the spent agent receiver 5, the catalyst regenerator 4 and the regenerant receiver 6 are connected in sequence, wherein the catalyst outlet of the regenerant receiver 6 and the catalyst inlet of the axial moving bed reactor 1 Connected
  • the axial moving bed reactor 1 is provided with at least two catalyst beds 3 placed up and down, and the axial moving bed reactor 1 is provided with a feed port 2 above each catalyst bed 3;
  • a catalyst delivery pipe 16 is provided between two adjacent catalyst bed layers 3 so that the catalyst can move from top to bottom in the axial moving bed reactor 1;
  • the liquid-phase raw materials are fed into the axially moving bed reactor 1 from the feed port provided above each catalyst bed layer 3 to contact and react with the catalyst.
  • the sequential connection means that the catalyst outlet of the axially moving bed reactor 1 is connected to the catalyst inlet of the bioreagent receiver 5 and the catalyst outlet of the bioreactor receiver 5 is connected to the catalyst regenerator 4
  • the catalyst inlet is connected, and the catalyst outlet of the catalyst regenerator 4 is connected to the catalyst inlet of the regenerant receiver 6.
  • the catalyst outlet of the regenerant receiver 6 communicates with the catalyst inlet of the axial moving bed reactor 1 to feed the regenerated catalyst into the axial moving bed reactor 1.
  • the axial moving bed reactor in the present invention refers to a moving bed reactor in which the moving direction of the catalyst is axial.
  • the axially moving bed reactor 1 is provided with at least two catalyst beds placed up and down, preferably 3-8 catalyst beds 3 placed up and down.
  • the thickness of the catalyst bed layer 3 is not particularly limited.
  • the thickness of each catalyst bed layer 3 is independently 10-30% of the height of the axially moving bed reactor 1.
  • the height of the axial moving bed reactor 1 is 7.5 m and the inner diameter is 600 mm as an example for illustration, but the present invention is not limited to this. Those skilled in the art can make appropriate adjustments according to the actual situation.
  • the axial moving bed reactor 1 has a height of 5-75 meters and an inner diameter of 200-3000 mm.
  • the liquid-phase raw material described in the present invention may be various raw materials commonly used in the art capable of undergoing solid acid alkylation reaction.
  • the liquid phase feedstock contains isoparaffins and olefins.
  • the isoparaffin may be an isoparaffin commonly used in alkylation reactions, preferably a C4-C6 isoparaffin, and more preferably isobutane.
  • the olefin is preferably a monoolefin, more preferably a C3-C6 monoolefin, and still more preferably a C4 monoolefin.
  • the alkylation feedstock is a hydrocarbon fraction containing olefins and alkanes, preferably a C4 fraction containing C4 olefins and C4 alkanes, and more preferably a mixture of C4 olefins and C4 alkanes.
  • the alkane fraction also includes a light hydrocarbon fraction that passes through the top of the fractionation column and is cooled and returned to the reactor inlet.
  • the alkylation feedstock is a hydrocarbon fraction containing olefins and alkanes, wherein the molar ratio of alkanes to olefins is 5-50: 1, such as 10-40: 1 or 20-30: 1.
  • the alkylation feedstock is a hydrocarbon fraction containing C3-C6 alkane and C3-C6 alkene, wherein the molar ratio of alkane to alkene is 5-50: 1, such as 10-40: 1 or 20-30: 1.
  • the alkylation feedstock is a mixture of C3-C6 alkanes and C3-C6 alkenes, wherein the molar ratio of alkanes to alkenes is 5-50: 1, such as 10-40: 1 or 20-30 :1.
  • the isoparaffins and olefins of the materials entering each catalyst bed can be conventionally selected.
  • the molar ratio (i.e., alkene ratio) of isoparaffin to olefin in the material entering each catalyst bed is 200-1000: 1.
  • the alkylation catalyst can have higher activity stability.
  • the molar ratio of isoparaffin to olefin in the material entering each catalyst bed is 400-750: 1.
  • the reaction temperature in the axial moving bed reactor is preferably lower than the critical temperature of the isoparaffin, more preferably not higher than 120 ° C (such as 30-120 ° C), further preferably not higher than 100 ° C, Even more preferably, it is performed at a temperature of 30-100 ° C, such as 60-80 ° C.
  • the pressure may generally be 1-3.4 MPa, preferably 1.2-3.2 MPa, such as 1.5-3.0 MPa.
  • the pressure is a gauge pressure.
  • the mass space velocity of materials entering each catalyst bed in terms of olefin may be 0.05-1 h -1 , preferably 0.07-0.5 h -1 , for example, 0.08-0.25 h -1 .
  • the residence time of the catalyst in the axial moving bed reactor is 6-72h, preferably 12-72h.
  • the catalyst is not particularly limited, and may be various catalysts conventionally used in the art, for example, solid acid catalysts.
  • the solid acid catalyst contains a molecular sieve and a heat-resistant inorganic oxide. Based on the total amount of the solid acid catalyst, the content of the molecular sieve is 65-95% by weight, further preferably 65-90% by weight, heat-resistant The content of the inorganic oxide is 5-35% by weight, further preferably 10-35% by weight.
  • the molecular sieve is selected from at least one of FAU structure zeolite, BETA structure zeolite and MFI structure zeolite.
  • the heat-resistant inorganic oxide refers to an inorganic oxide with a maximum service temperature of not less than 600 ° C.
  • the heat-resistant inorganic oxide may be alumina and / or silica.
  • the solid acid catalyst further contains a metal active component, and the metal active component is selected from at least one of Fe, Co, Ni, Pd, and Pt. Based on the total amount of the solid acid catalyst, the content of the metal active component is 0.15-2% by weight.
  • the average particle size of the catalyst may be 0.3-3 mm.
  • the catalyst bed is also called a reaction bed, and the two adjacent catalyst beds refer to the upstream reaction bed and the downstream reaction bed; when the catalyst regeneration bed is not included, the two adjacent beds A catalyst bed refers to two catalyst beds upstream and downstream, and in the case of including a non-last catalyst regeneration bed, two adjacent catalyst beds refer to the first upstream of the catalyst regeneration bed respectively Catalyst bed (ie, reaction bed) of a non-catalyst regeneration bed and the catalyst bed (ie, reaction bed) of the first non-catalyst regeneration bed downstream of the catalyst regeneration bed.
  • between two adjacent beds refers to any two adjacent beds, including: an upstream catalyst bed (ie, a reaction bed) and a downstream catalyst bed (ie, a reaction bed) Between layers), upstream catalyst bed (i.e. reaction bed) and downstream catalyst regeneration bed, upstream catalyst regeneration bed and downstream catalyst bed (i.e. reaction bed), upstream catalyst Between the regeneration bed and the downstream catalyst regeneration bed.
  • upstream catalyst bed ie. reaction bed
  • downstream catalyst bed i.e. reaction bed
  • upstream catalyst regeneration bed and downstream catalyst bed i.e. reaction bed
  • a separation is provided between two adjacent catalyst beds 3 and, if any, between the upstream catalyst bed (reaction bed) and the last stage of catalyst regeneration bed
  • a separation member 10 may be provided in each reaction bed.
  • the space inside the separation member 10 communicates with the catalyst delivery pipe 16.
  • the separation member 10 is used for the material and catalyst after the reaction of the upstream catalyst bed. After separation, the catalyst separated by the separation member 10 moves downward through the catalyst delivery pipe 16. After the reaction of the upstream catalyst bed, the material and the catalyst are separated by the separation member 10 to obtain the reacted material and the catalyst.
  • the catalyst moves downward through the catalyst delivery pipe 16, and the reacted material is in the space between the two adjacent catalyst beds ( In the present invention, it is referred to as the bed space before the reaction bed), mixed with the liquid fresh reaction raw materials fed into the feed port above the catalyst bed 3, and then flows into the downstream catalyst bed.
  • the separation member 10 may be a mesh screen with pores (the pore diameter may be determined according to the size of the catalyst particles), which allows the material after the reaction to pass through to achieve the separation of the material and the catalyst after the reaction.
  • a reaction material baffle 11 is provided between two adjacent catalyst beds 3, and the reaction material baffle 11 It is used to strengthen the mixing of materials and liquid fresh reaction raw materials fed into the inlet 2 after the reaction.
  • a reaction material baffle may be provided in each catalyst bed, especially in the bed space of the reaction bed.
  • the specific structure of the reaction material baffle 11 is not particularly limited, as long as it can enhance the mixing of the material and the liquid fresh reaction raw material after the strengthening reaction.
  • the reaction material baffle 11 is placed in the bed space in front of the reaction bed, and the number thereof may be one or more than two, preferably 1-6.
  • the reaction material baffle 11 includes a main shaft 111 and a conveying member 112 spirally extending along the axial direction of the main shaft. Specifically, the inlet of the spirally extending flow channel formed by the conveying member 112 is set according to the position of the feed inlet 2 so that the reacted materials and the liquid fresh reaction raw materials flow from the spirally extending flow channel formed by the conveying member 112, thereby achieving mixing .
  • the reaction material baffle 11 includes a plurality of baffles 113, and the plurality of baffles 113 moves along the axial direction of the bed reactor 1 in the axial direction It is arranged obliquely, and a plurality of baffles 113 are staggered with each other to form a flow channel through which the reaction material can pass.
  • the plurality of baffles 113 may be arranged obliquely downward or upwardly along the axial direction of the moving bed reactor 1 (as shown in FIG. 1).
  • the angle between the extension direction of the baffle plate 113 and the horizontal plane is 5-60 degrees, further preferably 10-40 degrees.
  • the staggered arrangement of the baffle plates 113 in the present invention means that the baffle plates 113 do not form a closed area with each other, so that the reaction materials can flow down smoothly.
  • part of the baffle plate 113 is fixedly connected to the wall of the axial moving bed reactor 1
  • part of the baffle plate 113 is fixedly connected to the wall of the catalyst delivery tube 16
  • the baffle plates 113 are arranged parallel to each other.
  • the distance between adjacent baffles 113 is 15-60 mm.
  • a catalyst distributor is provided between the two adjacent beds, said catalyst distributor It is used to disperse the catalyst at the outlet of the catalyst delivery pipe 16. If no catalyst distribution member is provided, the catalyst at the outlet of the catalyst delivery pipe 16 is likely to form a cone-shaped accumulation in the downstream catalyst bed.
  • the catalyst distribution member includes a cone-shaped distribution baffle 12 which is arranged coaxially with the catalyst delivery tube 16. The catalyst at the outlet of the catalyst delivery tube 16 falls on the tip of the cone-shaped distribution baffle 12 by gravity, and is dispersed to the horizontal sides of the catalyst delivery tube 16 by the dispersion of the cone-shaped distribution baffle 12. It is further preferred that the number of cone-shaped distribution baffles 12 and catalyst delivery tubes 16 is the same.
  • the catalyst distribution member further includes a horizontal distribution baffle 13 disposed below the cone-shaped distribution baffle 12, and the horizontal distribution baffle 13 is provided with holes for the catalyst to pass through .
  • the number of the horizontal distribution baffles 13 is not particularly limited, and may be one, or may be more than two, and are preferably provided at the radial intermediate positions of two adjacent cone-shaped distribution baffles 12 (and Axial downward position).
  • the radial and axial directions refer to the radial and axial directions of the axial moving bed reactor 1.
  • the holes in the horizontal distribution baffle 13 gradually become larger in the horizontally outward direction of the center of the axially moving bed reactor 1.
  • the part of the catalyst dispersed through the cone-shaped distribution baffle 12 near the center of the axially moving bed reactor 1 passes through the holes of the horizontal distribution baffle 13, and part of the catalyst that cannot pass is dispersed to The edge position of the axially moving bed reactor 1 is more conducive to ensuring uniform dispersion of the catalyst.
  • the horizontal distribution baffle 13 may be a circular distribution plate with a low aperture ratio in the middle region and a high aperture ratio at the side walls.
  • each catalyst bed of the axial moving bed reactor 1 will gradually deactivate as the reaction progresses, and it will gradually fall to the catalyst bed (reaction bed) or catalyst regeneration bed further downstream, and finally reach The bottom of the axially moving bed reactor 1 is then transported to the to-be-generated agent receiver 5 through a catalyst transport line.
  • the bottom of the axially moving bed reactor 1 is provided with a bottom catalyst collection zone 37.
  • the catalyst passing through the most downstream catalyst bed is sent to the bottom catalyst collection area 37, and after being collected in a certain amount, it is sent to the receiver 5 for the raw agent.
  • the axially moving bed reactor 1 and the raw material receiver 5, the raw material receiver 5 and the catalyst regenerator 4, the catalyst regenerator 4 and the regenerant are respectively provided with material line valves between the containers.
  • the raw material receiver 5 (preferably at the bottom) is provided with a liquid discharge outlet 15.
  • the liquid phase material carried in the catalyst can be removed by directly depressurizing or introducing high-pressure hydrogen, nitrogen, etc. in the standby agent receiver 5, and the liquid phase material can be transported out through the outlet 15 for liquid phase withdrawal.
  • a deliquoring filter 7 is provided on the deliquid phase material delivery line sent from the deliquid phase material outlet 15. The deliquoring filter 7 is used to block fine catalyst powder or fine catalyst particles.
  • the catalyst after being deliquored in the biochemical receiver 5 is sent to the catalyst regenerator 4 for regeneration.
  • the catalyst regenerator 4 is provided with a regeneration medium inlet 30 and a regeneration medium outlet 31.
  • the regeneration medium is fed into the catalyst regenerator 4 through the regeneration medium feed port 30 to contact the catalyst to regenerate the catalyst (preferably complete regeneration), and the regeneration medium is discharged through the regeneration medium discharge port 31.
  • a regeneration medium filter 8 is provided on the regeneration medium delivery line sent from the regeneration medium discharge port 31. The filter is used to block the flow of catalyst from the regenerator to the downstream gas circulation pressurization equipment and to collect fine powder or fine particles generated by friction or purge in the regeneration process.
  • the manner of regeneration in the catalyst regenerator 4 is not particularly limited, and can be performed under conventional regeneration conditions.
  • the regeneration medium may be an oxygen-containing atmosphere or a hydrogen-containing atmosphere. Specifically, the regeneration may be performed in a hydrogen-containing atmosphere or an oxygen-containing atmosphere.
  • the oxygen-containing atmosphere contains oxygen and an optional carrier gas.
  • the carrier gas may be selected from inert gases, and specific examples thereof may include, but are not limited to, nitrogen and group zero element gases (such as argon).
  • the content of oxygen may be 0.5-20% by volume.
  • the oxygen content can also be adjusted according to the regeneration process.
  • the hydrogen-containing atmosphere may contain hydrogen and C4 liquefied gas, and the hydrogen content is 70-99% by volume.
  • the regeneration is performed in a hydrogen atmosphere, and regeneration can be performed at a temperature of 100-400 ° C, preferably 180-280 ° C; during regeneration, the pressure in the reactor can be 0.1-5MPa, preferably 0.5-3.5MPa, the pressure is gauge pressure.
  • the regeneration is performed in an oxygen-containing atmosphere, and regeneration can be performed at a temperature of 180-500 ° C; during regeneration, the pressure in the reactor can be 0.01-0.5MPa, and the pressure is gauge .
  • the apparent flow velocity of the regeneration medium in the catalyst regenerator 4 is 0.003-0.8 m / s, further preferably 0.02-0.5 m / s.
  • the regeneration in the catalyst regenerator 4 is also referred to as high-temperature regeneration.
  • the method further includes introducing fresh catalyst into the catalyst regenerator 4.
  • the catalyst regenerator 4 may be provided with a fresh catalyst feed port for the fresh catalyst to enter the catalyst regenerator 4.
  • a fresh catalyst feed port in the catalyst regenerator 4 part of the deactivated catalyst or the catalyst that is difficult to restore the initial activity can be replaced with fresh catalyst to ensure the processing capacity of the device.
  • a pump is provided on the fresh catalyst delivery line communicating with the fresh catalyst feed port.
  • the regenerated catalyst will flow into the regenerant receiver 6 through the catalyst delivery line at the bottom of the catalyst regenerator 4.
  • the method further includes replacing the gas in the catalyst gap in the regenerant receiver 6 with a liquid material.
  • the regenerant receiver 6 is provided with a liquid-phase material replenishment inlet 32.
  • the liquid material is introduced into the regenerant receiver 6 through the liquid material supply inlet 32 to replace the gas in the catalyst gap.
  • the liquid phase material is not particularly limited.
  • it may be an alkane or a reaction product obtained at the bottom of the axially moving bed reactor 1.
  • the regenerated catalyst will return to the axial moving bed reactor 1 through the catalyst conveying pipeline between the regenerant receiver 6 and the axial moving bed reactor 1 and continue to participate in the reaction until it is deactivated and then delivered to the waiting agent receiver 5
  • the catalyst is circulated according to the above process.
  • the bioreagent receiver 5, the catalyst regenerator 4 and the regenerant receiver 6 are provided in order from top to bottom, and the bioreagent receiver 5, the catalyst regenerator 4 and the regenerant receiver
  • the catalyst circulation line between 6 is set vertically or at an angle of not less than 40 degrees with the horizontal plane.
  • a communication line between the catalyst outlet of the axially moving bed reactor 1 and the catalyst inlet of the to-be-generated agent receiver 5 is provided with a first particle flow regulator 25;
  • a second particle flow regulator 33 is provided on the communication line between the catalyst outlet and the catalyst inlet of the axial moving bed reactor 1.
  • the first particle flow regulator 25 and the second particle flow regulator 33 are not particularly limited as long as the flow rate of the catalyst particles can be adjusted.
  • the first particle flow regulator 25 and the second particle flow regulator 33 are each independently an L-shaped or approximately L-shaped material delivery valve group. Specifically, at least one liquid-phase material feed line is also connected to the L-shaped or nearly L-shaped material delivery valve group.
  • a particle flow regulator can increase the flow resistance of the particulate material.
  • the regulator is connected to at least one liquid material feed line to increase the flow driving force of the particulate material and reduce the flow resistance of the particulate material.
  • the device further includes a catalyst buffer tank 38 which is disposed between the axially moving bed reactor 1 and the receiver 5 for the raw agent, and the catalyst in the catalyst buffer tank 38
  • the inlet is in communication with the catalyst outlet of the axially moving bed reactor 1
  • the catalyst outlet in the catalyst buffer tank 38 is in communication with the catalyst inlet of the to-be-generated agent receiver 5.
  • the catalyst buffer tank 38 is used to store the catalyst discharged from the axially moving bed reactor 1 during the de-liquid phase feed and the catalyst regeneration agent discharging catalyst to ensure the catalyst material in the axially moving bed reactor 1 Continuity of flow and smooth operation of the device.
  • the axial moving bed reactor includes:
  • the catalyst bed and the catalyst regeneration bed are placed in order, and the top of the bed reactor is moved axially.
  • the bottom ends are set as catalyst reaction beds;
  • the axial moving bed reactor has a catalyst inlet 62 which communicates with the top of the first reaction bed;
  • each reaction bed has a catalyst inlet and a reaction material inlet 60.
  • the catalyst inlet of the first reaction bed is the catalyst inlet of the axially moving bed reactor, and the catalyst inlet of the subsequent reaction bed and the catalyst delivery pipe Interlinked
  • the catalyst delivery line for transferring the catalyst from the catalyst regeneration bed to the reaction bed is provided with an isolation medium inlet 70;
  • Separator 72 is provided at the bottom of each reaction bed
  • the beds are communicated with each other through a catalyst delivery line;
  • the bottom of the reaction bed communicates with the regeneration bed through a catalyst delivery pipe inserted into the regeneration bed.
  • the outlet of the inserted catalyst delivery pipe is lower than the outlet of the regeneration medium in the regeneration bed;
  • the isolation medium is preferably a circulating material that is pressurized by the pump after the reaction. Therefore, the isolation medium inlet 70 is in communication with the reaction material outlet 61 of the reaction bed in the last stage;
  • the material enters the next stage of the reaction bed through the separation member 72 or is finally discharged.
  • the catalyst that has not passed through the separation member 72 moves downward through the catalyst delivery pipe;
  • reaction material outlet 59 of the upstream reaction bed layer communicates with the reaction material inlet 60 of the downstream reaction bed layer through a pipeline, and inlets 56 and 57 of fresh reaction raw materials are also provided on this connection line;
  • the top of the bed refers to a position above 70% of each section of the bed from bottom to top, and the bottom of the bed refers to a position below 20% of each section of the bed from bottom to top;
  • the regeneration medium outlet 68 of the upstream catalyst regeneration bed communicates with the regeneration medium inlet 69 of the downstream catalyst regeneration bed through a pipeline;
  • the reaction material feed port 60 of the reaction bed, the regeneration medium inlet of the catalyst regeneration bed, and the isolation medium inlet 70 provided on the catalyst delivery line for transferring the catalyst from the catalyst regeneration bed to the reaction bed set the corresponding material distribution Device.
  • the method includes: after the liquid fresh reaction raw material 55 reacts with the circulating material 58 or the upstream reaction bed, the materials are mixed and then enter the reaction bed of the axial moving bed; in the reaction bed, mixing After the material is distributed through the reaction material distributor, it passes through the reaction bed along the axial direction of the reaction bed, contacts with the solid acid catalyst and reacts, and most of the liquid material (> 90vol%, or> 95vol%, or> 96vol) after the reaction %, Or> 97vol%, or> 98vol%, or> 99vol%) exit this section through the set reaction material outlet, and the remaining small part of the liquid material will follow the catalyst particles between the reaction bed and the catalyst regeneration bed
  • the inserted pipeline enters the catalyst regeneration bed; the discharged liquid phase material mixed with fresh reaction raw materials enters the next stage of reaction bed to continue to participate in the reaction or exit the reaction bed, and the alkylated oil product is collected after separation (such as distillation) ; In the catalyst regeneration bed, the catalyst will be adsorbed
  • Unsaturated hydrocarbons on the catalyst are converted into easily desorbed saturated hydrocarbon molecules and taken out of the catalyst regeneration bed to achieve partial regeneration of the catalyst; the regenerated catalyst will flow into the next reaction bed through the catalyst delivery line at the bottom of the catalyst regeneration bed ;
  • the isolation medium enters through the isolation medium inlet provided on the transfer line, replacing the downward liquid medium with the catalyst; in each bed of the moving bed
  • the catalyst in (reaction bed and catalyst regeneration bed) will gradually increase the degree of deactivation as the reaction progresses and the number of regeneration increases, and it will gradually fall to the lower bed (reaction bed or catalyst regeneration bed) )
  • the final catalyst is sent to the catalyst regenerator 4 (high temperature deep regeneration) to achieve complete recovery of catalyst activity; the restored catalyst is sent to the first stage of the moving bed reactor bed
  • the layer continues to participate in the reaction, so cycle;
  • the reaction conditions in the reaction bed may include:
  • the reaction temperature is 30-100 °C
  • the reaction pressure is 1.0-3.4MPa, gauge pressure,
  • the apparent flow velocity of liquid materials in the reactor is 0.03-1m / s;
  • the mass space velocity of the mixed olefin feedstock is 0.05-1h -1 ;
  • the molar ratio of alkane to olefin at the entrance of the reaction bed is 200-1000: 1;
  • the average particle diameter of the solid acid catalyst particles is 0.3-3 mm.
  • the regeneration conditions in the catalyst regeneration bed may include:
  • the regeneration temperature is 50-140 °C
  • the apparent flow velocity of the regeneration medium in the regenerator is 0.01-0.5m / s;
  • the regeneration medium is a liquid hydrocarbon in which hydrogen is dissolved;
  • the liquid hydrocarbon is a C3-C6 (for example C3-C5) saturated alkane or a mixture of the reaction product and the above-mentioned saturated alkane.
  • the liquid hydrocarbon is C3-C6 (for example C3 -C5) a mixture of saturated alkanes and reaction products;
  • the regeneration conditions in the catalyst regenerator may include:
  • the regeneration temperature is 180-400 °C
  • the regeneration pressure is 0.5-4.0MPa
  • the regeneration medium is hydrogen or a mixture of hydrogen and low-carbon hydrocarbons (such as C3-C8), preferably a mixture of hydrogen and low-carbon hydrocarbons (such as C3-C8);
  • the main active component of the catalyst is a molecular sieve loaded with a certain amount of metal
  • the molecular sieve is FAU structure zeolite, BETA structure zeolite, MFI structure zeolite and a combination of one or more of them, preferably having FAU structure and BETA structure Zeolite
  • the metal supported on the catalyst is one or a combination of Fe, Co, Ni, Pd and / or Pt, preferably one or a combination of Co, Ni or Pt.
  • the method provided by the invention adopts a liquid-solid axial moving bed reaction and regeneration device, which can realize the continuous and stable operation of solid acid alkylation reaction and regeneration of deactivated catalyst, improve the selectivity of the target product and the flexibility of the device operation, and greatly reduce The investment cost of the catalyst is improved, and the economic competitiveness of the device is improved.
  • a liquid-solid axial moving bed reaction and regeneration device characterized in that the device includes:
  • the axial moving bed reactor is provided with at least two catalyst beds placed up and down, and the axial moving bed reactor is provided with a feed inlet above each catalyst bed;
  • a catalyst delivery tube is provided between two adjacent catalyst bed layers so that the catalyst can move from top to bottom in the axial moving bed reactor.
  • a separation member is arranged between two adjacent catalyst beds, and the separation member communicates with the catalyst conveying pipe.
  • the separation member is used for separating material and catalyst after the reaction of the upstream catalyst bed.
  • the catalyst separated by the separation member passes through the catalyst The conveyor pipe moves down.
  • reaction material baffle includes a main shaft (111) and a conveying member (112) spirally extending along the axial direction of the main shaft.
  • reaction material baffle includes a plurality of baffles (113), and the plurality of baffles (113) are along the axial direction
  • the axial direction of the moving bed reactor is inclined, and a plurality of baffles (113) are alternately arranged with each other to form a flow channel through which the reaction material can pass.
  • liquid-solid axial moving bed reaction and regeneration device according to any one of technical solutions 1-6, wherein a catalyst distribution member is provided between two adjacent catalyst bed layers, and the catalyst distribution member is used for Disperse the catalyst at the outlet of the catalyst delivery pipe;
  • the catalyst distribution member includes a cone-shaped distribution baffle, which is arranged coaxially with the catalyst delivery tube; further preferably, the number of the cone-shaped distribution baffle is the same as the catalyst delivery tube;
  • the catalyst distribution member further includes a horizontal distribution baffle disposed below the cone-shaped distribution baffle, and the horizontal distribution baffle is provided with holes for the catalyst to pass through.
  • liquid-solid axial moving bed reaction and regeneration device according to any one of technical solutions 1-8, wherein the receiver for the raw agent, the catalyst regenerator, and the receiver for the regenerative agent are provided in order from top to bottom.
  • the catalyst circulation line between the raw material receiver, the catalyst regenerator and the regenerant receiver is arranged vertically or inclined at an angle of not less than 40 degrees to the horizontal plane.
  • liquid-solid axially moving bed reaction and regeneration device according to any one of technical solutions 1-9, wherein the catalyst outlet of the axially moving bed reactor and the catalyst inlet of the to-be-generated agent receiver are on a communication line A first particle flow regulator is provided; a second particle flow regulator is provided on the communication line between the catalyst outlet of the regenerant receiver and the catalyst inlet of the axial moving bed reactor;
  • the first particle flow regulator and the second particle flow regulator are each independently an L-shaped or approximately L-shaped material delivery valve group.
  • the liquid-solid axial moving bed reaction and regeneration device according to any one of technical solutions 1-10, wherein the device further includes a catalyst buffer tank, the catalyst buffer tank is provided in the axial moving bed reactor, The catalyst inlet of the catalyst buffer tank communicates with the catalyst outlet of the axial moving bed reactor between the receivers of the spent agent, and the catalyst outlet of the catalyst buffer tank communicates with the catalyst inlet of the spent agent receiver.
  • a solid acid alkylation method including:
  • the method is carried out in a liquid-solid axial moving bed reaction and regeneration device.
  • the liquid-solid axial moving bed reaction and regeneration device includes an axially moving bed reactor, a standby agent receiver, a catalyst regenerator and a regenerating agent connected in sequence Wherein the catalyst outlet of the regenerant receiver communicates with the catalyst inlet of the axial moving bed reactor; the axial moving bed reactor is provided with at least two catalyst bed layers placed up and down, and the axial moving bed reactor is in each A feed port is provided above the catalyst bed; a catalyst delivery tube is provided between two adjacent catalyst beds so that the catalyst can move from top to bottom in the axial moving bed reactor;
  • the raw materials in the liquid phase are fed into the axially moving bed reactor from the feed port provided above each catalyst bed to contact and react with the catalyst.
  • the mass space velocity of materials entering each catalyst bed in terms of olefin is 0.05-1h -1 ;
  • the molar ratio of isoparaffin to olefin in the material entering each catalyst bed is 200-1000: 1;
  • the residence time of the catalyst in the axial moving bed reactor is 6-72h.
  • the catalyst is a solid acid catalyst
  • the solid acid catalyst contains a molecular sieve and a heat-resistant inorganic oxide, the total amount of the solid acid catalyst
  • the content of molecular sieve is 65-95% by weight
  • the content of heat-resistant inorganic oxide is 5-35% by weight
  • the molecule is selected from at least one of FAU structure zeolite, BETA structure zeolite and MFI structure zeolite, and the heat-resistant inorganic oxide is alumina and / or silica;
  • the solid acid catalyst further contains a metal active component
  • the metal active component is selected from at least one of Fe, Co, Ni, Pd, and Pt, based on the total amount of the solid acid catalyst, The content of the metal active component is 0.15-2% by weight.
  • the reaction material baffle includes a main shaft (111) and a conveying member (112) spirally extending along the axial direction of the main shaft;
  • the reaction material baffle includes a plurality of baffles (113), the plurality of baffles (113) are inclinedly arranged along the axial direction of the axial moving bed reactor, and the plurality of baffles (113) They are staggered with each other to form a flow channel through which the reaction materials can pass.
  • the catalyst distribution member includes a cone-shaped distribution baffle, which is arranged coaxially with the catalyst delivery tube; further preferably, the number of the cone-shaped distribution baffle is the same as the catalyst delivery tube;
  • the catalyst distribution member further includes a horizontal distribution baffle disposed below the cone-shaped distribution baffle, and the horizontal distribution baffle is provided with holes for the catalyst to pass through.
  • the apparent flow velocity of the regeneration medium in the catalyst regenerator is 0.003-0.8 m / s, further preferably 0.02-0.5 m / s.
  • a first particle flow regulator is provided on the communication line between the catalyst outlet of the axially moving bed reactor and the catalyst inlet of the to-be-generated agent receiver;
  • a second particle flow regulator is provided on the communication line between the catalyst outlet of the regenerant receiver and the catalyst inlet of the axial moving bed reactor;
  • the first particle flow regulator and the second particle flow regulator are each independently an L-shaped or approximately L-shaped material delivery valve group.
  • the device further includes a catalyst buffer tank, the catalyst buffer tank is disposed between the axially moving bed reactor and the receiver for the raw agent, the catalyst The catalyst inlet of the buffer tank is in communication with the catalyst outlet of the axial moving bed reactor, and the catalyst outlet of the catalyst buffer tank is in communication with the catalyst inlet of the receiver to be prepared.
  • catalyst beds 3 are provided in the axially moving bed reactor 1, and the standby agent receiver 5, catalyst regenerator 4 and regenerant receiver 6 are provided in order from top to bottom, and the three of them
  • the catalyst circulation line between is set vertically.
  • the fresh olefin feed containing isobutane is introduced from line 17, mixed with the circulating material through the first branch line 19, and then enters the reaction zone of the axially moving bed reactor 1 from the feed port 2 and contacts the first catalyst bed 3 for reaction
  • the fresh olefin feedstock fed through the second branch line 20 and the third branch line 21 is fed from the feed port 2 and reacted with the upstream catalyst bed before the reaction bed of the axial moving bed reactor 1 Mixing in space.
  • a separation member 10 is provided between two adjacent catalyst bed layers 3. After the reaction, the material passes through the separation member 10, and the catalyst that has not passed through the separation member 10 moves downward through the catalyst delivery pipe 16.
  • a reaction material baffle 11 is provided between two adjacent catalyst beds 3, and the reacted materials and fresh reaction raw materials passing through the separation member 10 are intensified and mixed under the action of the reaction material baffle 11.
  • a catalyst distribution member (including a cone-shaped distribution baffle 12 disposed coaxially with the catalyst delivery pipe 16 and a horizontal distribution baffle disposed under the cone-shaped distribution baffle 12 are also provided between two adjacent catalyst bed layers 3 13), the catalyst at the outlet of the catalyst delivery pipe 16 is dispersed and dropped to the downstream catalyst bed 3 under the action of the catalyst distribution member.
  • the lower part of the axially moving bed reactor 1 is provided with a bottom catalyst collection area 37.
  • the catalyst passing through the most downstream catalyst bed is sent to the bottom catalyst collection area 37, and after being collected in a certain amount, it is sent to the receiver 5 for the raw agent.
  • a communication line between the catalyst outlet of the axially moving bed reactor 1 and the catalyst inlet of the to-be-generated agent receiver 5 is provided with a first particle flow regulator 25 to regulate the flow of catalyst particles.
  • the liquid-reducing liquid material outlet 15 is provided at the bottom of the liquid-regenerating agent receiver 5, the liquid-phase material carried in the catalyst is removed in the liquid-regenerating agent receiver 5, and the liquid-reducing material conveying pipeline sent from the liquid-reducing liquid material outlet 15
  • the deliquoring filter 7 is provided above to block the catalyst fine powder or fine catalyst particles.
  • the catalyst to be deliquored in the biochemical receiver 5 is sent to a catalyst regenerator 4 for regeneration.
  • the catalyst regenerator 4 is provided with a regeneration medium inlet 30 and a regeneration medium outlet 31.
  • the regeneration medium is sent into the catalyst regenerator 4 through the regeneration medium feed port 30 to contact the catalyst to regenerate the catalyst, and the regeneration medium is discharged through the regeneration medium discharge port 31.
  • a regeneration medium filter 8 is provided on the regeneration medium delivery line sent from the regeneration medium discharge port 31 to block fine powder or fine particles.
  • the catalyst regenerator 4 may also be provided with a fresh catalyst feed port for the fresh catalyst to enter the catalyst regenerator 4.
  • the regenerated catalyst flows into the regenerant receiver 6 through the catalyst delivery line at the bottom of the catalyst regenerator 4, and the regenerant receiver 6 is provided with a liquid-phase material replenishment inlet 32.
  • the liquid material is introduced into the regenerant receiver 6 through the liquid material supply inlet 32 to replace the gas in the gap between the catalysts.
  • the regenerated catalyst will return to the axial moving bed reactor 1 through the catalyst conveying pipeline between the regenerant receiver 6 and the axial moving bed reactor 1 to continue to participate in the reaction until it is deactivated and then sent to the waiting agent receiver 5,
  • the catalyst is circulated according to the above procedure.
  • a communication line between the catalyst outlet of the regenerant receiver 6 and the catalyst inlet of the axially moving bed reactor 1 is provided with a second particle flow regulator 33 to adjust the catalyst particle flow.
  • the axial moving bed reactor includes reaction bed layers 51 and 53 and catalyst regeneration bed layers 52 and 54 which are sequentially placed at intervals;
  • the axial moving bed reactor has a catalyst inlet 62 which communicates with the top of the first reaction bed;
  • the top of the reaction bed has a catalyst inlet reaction material inlet 60;
  • the catalyst delivery line for transferring the catalyst from the catalyst regeneration bed to the reaction bed is provided with an isolation medium inlet 70;
  • Separator 72 is provided at the bottom of each reaction bed
  • the beds are communicated with each other through a catalyst delivery line;
  • the bottom of the reaction bed communicates with the regeneration bed through a catalyst delivery pipe inserted into the regeneration bed.
  • the outlet of the inserted catalyst delivery pipe is lower than the outlet of the regeneration medium in the regeneration bed;
  • the isolation medium is preferably a circulating material that is pressurized by the pump after the reaction. Therefore, the isolation medium inlet 70 is in communication with the reaction material outlet 61 of the reaction bed in the last stage;
  • the material enters the next stage of the reaction bed through the separation member 72 or is finally discharged.
  • the catalyst that has not passed through the separation member 72 moves downward through the catalyst delivery pipe;
  • reaction material outlet 59 of the upstream reaction bed layer communicates with the reaction material inlet 60 of the downstream reaction bed layer through a pipeline, and inlets 56 and 57 of fresh reaction raw materials are also provided on this connection line;
  • the top of the bed refers to a position above 70% of each section of the bed from bottom to top, and the bottom of the bed refers to a position below 20% of each section of the bed from bottom to top;
  • the regeneration medium outlet 68 of the upstream catalyst regeneration bed communicates with the regeneration medium introduction port 69 of the downstream catalyst regeneration bed through a pipeline;
  • the reaction material feed port 60 of the reaction bed, the regeneration medium inlet of the catalyst regeneration bed, and the isolation medium inlet 70 provided on the catalyst delivery line for transferring the catalyst from the catalyst regeneration bed to the reaction bed set the corresponding material distribution Device.
  • the invention provides a solid acid alkylation reaction and hydrogen regeneration method.
  • the liquid fresh reaction raw material is mixed with the circulating material or the upstream reaction bed, and then the material is mixed into the reaction bed of the axial moving bed; in the reaction bed After the mixture is distributed through the reaction material distributor, it passes through the reaction bed along the axial direction of the reaction bed, contacts the solid acid catalyst and reacts, and most of the reaction is completed (> 90vol%, or> 95vol%, or> 96vol% , Or> 97vol%, or> 98vol%, or> 99vol%)
  • the liquid phase material exits this section through the set reaction material outlet, and the remaining small part of the liquid phase material follows the catalyst particles through the reaction bed and the catalyst regeneration bed
  • the inserted pipeline between the two enters the catalyst regeneration bed; after the reaction, the liquid phase material after the reaction is mixed with the fresh reaction raw material, and then enters the next stage of the reaction bed to continue to participate in the reaction or exit the reaction bed.
  • the catalyst undergoes countercurrent contact with a liquid-phase regeneration medium in which hydrogen is dissolved under regeneration conditions to convert unsaturated hydrocarbons adsorbed on the catalyst into saturated hydrocarbon molecules that are easily desorbed and take it out of the catalyst regeneration bed Layer to achieve partial regeneration of the catalyst; the regenerated catalyst will flow into the next reaction bed through the catalyst delivery line at the bottom of the catalyst regeneration bed; during the transfer of catalyst from the bottom of the catalyst regeneration bed to the reaction bed, the isolation medium passes Enter the isolation medium inlet on the transfer line to replace the downward liquid medium with the catalyst; the catalyst in each bed of the moving bed (reaction bed and catalyst regeneration bed) as the reaction proceeds and the number of regenerations The degree of deactivation will gradually increase, and it will gradually fall to a lower bed (reaction bed or catalyst regeneration bed) and finally reach the bottom of the moving bed reactor; the final catalyst is sent to the catalyst regenerator 4 (go High temperature deep regeneration) to achieve complete recovery of the catalyst activity; the catalyst with the restored activity is sent The reaction bed in the first stage
  • This embodiment is carried out on the liquid-solid axial moving bed reaction and regeneration device shown in FIG. 1.
  • the axially moving bed reactor 1, the to-be-generated agent receiver 5, the catalyst regenerator 4 and the regenerated agent receiver 6 are sequentially connected through a pipeline.
  • the axial diameter of the axially moving bed reactor 1 is 600 mm, and three stages of catalyst beds 3 (respectively referred to as the first catalyst bed, the second catalyst bed, and the third catalyst bed) are provided from top to bottom, each stage of the reaction bed
  • the height of the layer is 1.8m.
  • Two cylindrical catalyst delivery tubes 16 are provided between the first catalyst bed and the second catalyst bed, and between the second catalyst bed and the third catalyst bed, and the inner diameter of the catalyst delivery tube 16 is 20 mm.
  • Separator 10 (wedge filter with a slit width of 0.2 mm) is provided under the first catalyst bed and under the second catalyst bed, respectively.
  • a reaction material baffle 11 as shown in FIG. 2 is provided between each of the first catalyst bed and the second catalyst bed and between the second catalyst bed and the third catalyst bed.
  • the piece 11 includes a main shaft 111 and a conveying member 112 spirally extending along the axial direction of the main shaft.
  • the inlet of the spirally extending flow path formed by the conveying member 112 is located at the feed port 2 of the fresh olefin feedstock of the second branch line 20 and the third branch line 21 below.
  • the reaction material baffle 11 is provided in the annular space between the central area where the catalyst delivery pipe 16 is located and the reactor wall.
  • the horizontal distribution baffle 13 is provided with holes for the catalyst to pass through, moving the bed in the axial direction In the horizontal outward direction of the center of the reactor 1, the holes on the horizontal distribution baffle 13 gradually become larger, the maximum hole diameter is set to 25 mm, and the minimum hole diameter is set to 5 mm.
  • the bottom part of the axial moving bed reactor 1 is provided with a bottom catalyst collection area 37.
  • the bioreagent receiver 5, the catalyst regenerator 4 and the regenerant receiver 6 are arranged in order from top to bottom, and the catalyst circulation line between the bioreagent receiver 5, the catalyst regenerator 4 and the regenerant receiver 6 is arranged vertically .
  • the diameters of the receiver 5, the catalyst regenerator 4 and the regenerator receiver 6 are all 1200mm, and the height of the straight pipe section is 6m.
  • the diameter of the material circulation line is 250mm.
  • the fresh reaction raw materials are a mixture of isobutane, n-butane and butene. After being fed from the fresh feed line 17, it is divided into three ways to enter the corresponding catalyst bed 3 respectively.
  • the mixed material After mixing into the catalyst bed 3, the mixed material has an alkene molar ratio of 700: 1, the flow rate of the circulating material in the reactor is 0.28m / s, the corresponding total fresh feed is 482kg / h, mixed olefin raw materials The mass airspeed is 0.25h -1 .
  • the residence time of the catalyst in the axial moving bed reactor 1 was 72h.
  • the catalyst used is a FAU structured molecular sieve spherical catalyst with an average particle size of 1.8 mm.
  • the preparation method is to adopt NaY type molecular sieve of FAU structure produced by Sinopec Catalyst Branch Company, and remove sodium ions on the molecular sieve through ion exchange and other steps; then mix the molecular sieve and alumina in a weight ratio of 65:35, using oil Ammonia column forming method is used to make pellets, and the catalyst is prepared by further drying and roasting.
  • the reaction temperature in the axial moving bed reactor 1 was 70 ° C, and the reaction pressure was 2.5 MPa.
  • the fresh material and the circulating material are mixed from the feed port 2 into the axial moving bed reactor 1 to contact with the catalyst packed in the first catalyst bed, and the reaction material separated by the separation member 10 is separated from the first branch line
  • the fresh material of 19 is sent to the second catalyst bed through the enhanced mixing of the baffle 11 for reaction, and the catalyst separated by the separation member 10 is dispersed and dropped to the downstream catalyst bed through the catalyst delivery pipe 16 under the action of the catalyst distribution member, and finally the catalyst ⁇ ⁇ ⁇ receive zone 37.
  • the catalyst obtained in the bottom catalyst collecting area 37 is sent to the to-be-generated agent receiver 5 through the catalyst outlet.
  • a communication line between the catalyst outlet of the axial moving bed reactor 1 and the catalyst inlet of the to-be-generated agent receiver 5 is provided with a first particle flow regulator 25 (L-type material delivery valve group), and the L-type material delivery valve The group is also connected with a liquid material feed line to control the flow rate of the catalyst slurry (20kg / h). Nitrogen gas is introduced into the waiting agent receiver 5 to remove the liquid-phase materials carried in the catalyst, and the liquid-phase materials are transported out through the liquid-reducing material outlet 15 and the liquid-reducing material sent from the liquid-reducing material outlet 15
  • the delivery line is provided with a deliquoring filter 7.
  • the catalyst after being deliquored in the biochemical receiver 5 is sent to the catalyst regenerator 4 for regeneration, using a mixture of nitrogen and air (the volume concentration of oxygen is adjusted from 1 to 21% by volume from small to large, and the apparent gas velocity is 0.1m / s) as the catalyst high temperature deep regeneration medium, high temperature (350-480 °C from small to large adjustment), normal pressure deep regeneration cycle is 24h, the mixed gas is fed through the regeneration medium feed port 30, the regeneration medium passes The regeneration medium discharge port 31 is discharged outward, and a regeneration medium filter 8 is provided on the regeneration medium delivery line sent from the regeneration medium discharge port 31.
  • the catalyst regenerator 4 may also be provided with a fresh catalyst feed port for the fresh catalyst to enter the catalyst regenerator 4.
  • the regenerated catalyst flows into the regenerant receiver 6 through the catalyst delivery line at the bottom of the catalyst regenerator 4.
  • the regenerant receiver 6 is provided with a liquid-phase material replenishment inlet 32.
  • the liquid-phase liquid-containing material after the reaction is introduced into the regenerator receiver 6 through the liquid-phase material replenishment inlet 32 to replace the gas in the catalyst gap, and the obtained catalyst slurry is circulated to the axial direction Moving bed reactor 1 top.
  • a communication line between the catalyst outlet of the regenerant receiver 6 and the catalyst inlet of the axial moving bed reactor 1 is provided with a second particle flow regulator 33 (L-type material delivery valve group), and the L-type material delivery valve group
  • the upper part is also connected with a liquid material feed line to control the flow rate of the catalyst slurry (20kg / h).
  • the solid acid alkylation reaction was carried out on the apparatus shown in FIG. 3.
  • the difference from Example 1 is that the device is also provided with a catalyst material buffer tank 38 with a diameter of 500 mm and a straight pipe section of 4.2 m in height between the axially moving bed reactor 1 and the receiver 5 for the raw agent.
  • the catalyst material buffer tank 38 is added to ensure that the catalyst in the reactor still moves at the original speed and slowly moves downward at the original speed during the deliquoring operation and the catalyst transfer to the regenerator. After completion, the catalyst accumulated in the catalyst buffer tank is gradually discharged to the raw material receiver to ensure the continuity of the flow of catalyst material in the axial moving bed reactor 1 and the stability of the device operation.
  • the solid acid alkylation reaction was carried out on the apparatus shown in FIG. The difference is that the reaction material baffle 11 shown in FIG. 2 is replaced with the reaction material baffle 11 as shown in FIG. 1.
  • the reaction material baffle 11 includes eight parallel and staggered baffle plates 113. The angle between the extending direction of the flow plate 113 and the horizontal plane is 25 degrees, the baffle plate 113 is inclined upwards along the axial direction of the axial moving bed reactor 1, and four baffle plates 113 are fixedly connected to the axial moving bed reactor 1 In the wall, four baffles 113 are fixedly connected to the wall of the catalyst delivery tube 16, and the distance between adjacent baffles 113 is 25 mm.
  • This embodiment is carried out in the liquid-solid axial moving bed reactor shown in FIG. 4, in which the spent agent receiver, catalyst regenerator, regenerant receiver and other equipment not mentioned are the same as in embodiment 1. The same or similar.
  • the inner diameter of the shell of the axially moving bed reactor is 600mm, including 2 reaction beds and 2 regenerated catalyst beds.
  • the height of each section of bed is 1.8m, which are arranged at intervals.
  • the outlet of the regeneration medium provided at the top of the catalyst regeneration bed is at a position of 85% of the catalyst regeneration bed from bottom to top, and the inlet of the regeneration medium is at a position of 5% of the catalyst regeneration bed from bottom to top.
  • the outlet of the plug-in pipe is at 80% of the catalyst regeneration bed from bottom to top.
  • the fresh reaction materials are the same as those used in Example 1. After feeding from the fresh material feed line, it is divided into two channels and mixed with the circulating material or the liquid material after the upstream reaction, and then enters the corresponding reaction bed.
  • the molar ratio of alkene in the distribution area of the reactor is 700 ⁇ 100: 1, and the mass space velocity of the mixed olefin feedstock is 0.25h -1 .
  • the reaction temperature in the reaction bed was 70 ° C, and the reaction pressure was 2.5 MPa.
  • the post-reaction liquid phase material containing a part of paraffinic oil dissolved in hydrogen is used as the regeneration medium for the catalyst.
  • the conditions such as regeneration temperature and pressure are similar to the reaction temperature and pressure.
  • the total residence time of the catalyst in the axial moving bed reactor was controlled to 168h.
  • the catalyst that finally lost its activity was introduced into a high-temperature deep regeneration system.
  • deep regeneration was performed using hydrogen containing some low-carbon hydrocarbons to completely restore the catalyst activity.
  • the reactivated catalyst is reintroduced to the fresh catalyst feed port at the top of the reactor to continue to participate in the reaction, thus circulating.
  • the specific operation process is that when the first reactor is in the alkylation reaction, the second reactor performs high temperature deep regeneration operation, two The fixed bed reactors in parallel are switched to use, which enables the device to run continuously and stably.
  • the inner diameter of each fixed bed reactor is 200mm and the height is 2500mm.
  • the preparation method of the catalyst filled in the reactor is the same as that in Example 1, except that the diameter of the pellet is 2.7 mm, the filling amount is 28 kg, and the filling height is 1500 mm.
  • the reaction raw materials are the same as in Example 1, the molar ratio of alkene in the reactor is 800: 1, the feed amount of fresh mixed olefin is 6.3 kg / h, and the mass space velocity relative to the olefin is 0.09 h -1 .
  • the catalyst in the bed needs to be regenerated at a high temperature every 24h, and a mixture of nitrogen and air (same as in Example 1) is used to increase the temperature from normal temperature to 480 ° C under normal pressure.
  • High temperature oxidation regeneration 3h after regeneration, the bed needs to be cooled, the entire regeneration cycle is 24h. After the regeneration is completed, the materials in the reactor in the reaction state are returned to the reactor after regeneration, and the alkylation reaction experiment is continued with the regenerated catalyst, and the reactor with the reacted materials is cut into the regeneration operation, and the cycle is repeated.
  • the octane value of the alkylated oil obtained by the solid acid alkylation method or device provided by the present invention is slightly better than that of the fixed bed technology, and the olefin yield in the alkylated oil is higher And it has higher target product (trimethylpentane) selectivity, and the yield of C9 + product is also lower.
  • Example 2 with a catalyst buffer tank has better product yield and target product selectivity.
  • the device and method provided by the present invention can meet the requirements with a single (set) device, reducing the investment cost of the device, and in addition, the deactivated catalyst particles are led out of the liquid-solid axial moving reactor for deep regeneration, in On the premise of not affecting the stable operation of the reaction device, the continuous operation of the catalyst reaction and regeneration is realized, the catalyst in the device has a relatively stable balanced activity, and the selectivity of the target product in the alkylated oil is improved.
  • Example 4 it can be seen from Example 4 that the octane number of the alkylated oil obtained by the axially moving bed technology with the reaction bed and the catalyst regeneration bed spaced apart in sequence is slightly better than that of the fixed bed technology.
  • the olefin yield is higher, and the target product (trimethylpentane) selectivity is higher, the C9 + product yield is also lower, and the catalyst residence time is extended to one week, indicating that the reaction bed and the catalyst regeneration bed are in order.
  • the spaced axial moving bed technology has higher technical advantages.
  • the axial moving bed solid acid alkylation technology provided by the present invention has better industrial application prospects.

Abstract

一种液固轴向移动床反应与再生装置和使用所述液固轴向移动床反应与再生装置进行固体酸烷基化方法，所述液固轴向移动床反应与再生装置包括：依次连接的轴向移动床反应器(1)、待生剂接收器(5)、催化剂再生器(4)和再生剂接收器(6)，其中，再生剂接收器(6)的催化剂出口与轴向移动床反应器(1)的催化剂入口连通；其中，轴向移动床反应器(1)设置有至少两个上下放置的催化剂床层(3)，轴向移动床反应器(1)在每个催化剂床层(3)的上方设置有进料口(2)；相邻两个催化剂床层(3)之间设置有催化剂输送管(16)使得催化剂能够在轴向移动床反应器(1)中自上而下移动；相邻两个催化剂床层(3)之间，设置有分离件(10)，所述分离件(10)内侧空间与催化剂输送管(16)连通，所述分离件(10)用于上游催化剂床层反应后物料和催化剂的分离，分离件(10)分离得到的催化剂通过催化剂输送管(16)向下移动。

Description

一种液固轴向移动床反应与再生装置和一种固体酸烷基化方法
本申请要求2018年10月22日提交的中国专利申请201811229732.2和201811230209.1的优先权。
技术领域
本发明涉及固体酸烷基化领域。具体来说，本发明涉及一种液固轴向移动床反应与再生装置，以及一种固体酸烷基化方法。
背景技术
目前，炼油工业的最主要任务之一是提供运输燃料，汽油作为一种重要的运输燃料，被广泛的应用于交通运输等行业中。随着汽油消耗量的增加和环保标准的日益严格，围绕着如何解决汽油清洁化生产的问题成为研究和讨论的热点。
在强酸的作用下，以异构烷烃(主要是异丁烷)和烯烃(C3～C5烯烃)为原料生成烷基化油的技术为汽油的清洁化生产提供了可能。烷基化油具有较高的辛烷值和较低的蒸汽压，主要由饱和烃组成，且不含硫、氮、烯烃和芳烃等物质，因而被称为清洁化汽油，是航空汽油和车用汽油理想的调和组分。烷基化技术按催化剂形式可以分为液体酸烷基化和固体酸烷基化。目前，世界范围内约90％的烷基化产能是由液体酸烷基化技术(硫酸法和氢氟酸法)提供的，虽然液体酸烷基化技术比较成熟，且具有较好的反应选择性，但是也存在很多问题，比如液体酸烷基化过程都存在设备腐蚀严重的问题。除此之外，对于硫酸法而言，其过程耗酸量巨大，大量的废酸在运输和处理上都存在一定的安全隐患，对于氢氟酸法而言，由于氢氟酸具有较强的腐蚀性和毒性，而且容易挥发，会对人体造成很大的伤害。因此，与之对比，采用固体酸作为催化剂，不仅不会对环境造成污染，而且不存在设备腐蚀的问题，可以视为一种绿色的烷基化工艺技术，具有很好的发展前景。但是在固体酸烷基化过程中，由于固体酸催化剂容易失活，为了保持一定的反应活性，需要进行频繁的再生操作，因此，开发一种能够实现反应和再生过程连续化的反应器技术，对推动固体酸烷基化技术发展来说是十分重要的。
US8373014公开了一种采用重叠式放置的径向移动床作为反应器的固体酸烷基化反应方法。该方法中，采用了类似催化重整重叠式径向移动床的结构，单段反应器中设有外围起反应物料分布作用的环形桶和起物料收集作用的中心管以及夹在二者之间的反应床层区；两段反应器之间采用催化剂物料输送管将上段催化剂床层中的催化剂输送到下段反应器的反应床层区。处于中间反应器的流出物料被分为两部分，一部分泵回上游反应器与新鲜反应原料经混合器混合后作为上游反应器的进料，此部分可称为循环用料；另一部分引入下游反应器的进料混合器前与新鲜反应原料混合后作为下游反应器的进料，此部分未经泵增压直接使用。此外，循环料部分还需要经过一换热器以引出反应热。
CN1879956A公开了一种流化床固体酸烷基化技术，该工艺技术主要包括提升管反应器、流化床反应器、环流再生器和移动床再生器。其中提升管反应器中液速范围在0.1-3m/s，流化床反应器中液速范围在0.26-7.68cm/s。再生过程可根据再生时间来确定再生反应器的形式，如果再生的时间为几秒到几十秒，可单独采用环流再生器。如果再生时间为几十秒到几十分钟，可单独采用移动床再生器，并且再生液的液速为0.2-3cm/s。
CN1113906A公开了一种流化床固体酸芳烃烷基化工艺技术，该工艺过程主要包括液固上行反应器、待生催化剂沉降返洗塔、液固并流向上再生器、再生后催化剂沉降返洗塔。其中要求所用的催化剂粒径在0.05-0.8mm，反应器和再生器中能够携带催化剂向上流动的液体液速是颗粒终端沉降速度的1-15倍，在沉降返洗塔内，采用自下向上流动的洗涤液对催化剂进行洗涤再生，洗涤液的流速为颗粒终端沉降速度的0.5-5倍。
现有技术公开的固定床烷基化技术和流动床烷基化技术为了实现反应装置的连续稳定进行，至少需要两台以上的反应器切换操作，每隔一段时间对床层内的催化剂进行高温再生，深度再生后还要对高温床层进行降温操作，由于装置频繁的在反应与再生温度之间进行切换，使得其在工业应用中连续稳定运行时带来了很多问题。另外，现有技术中，固体酸烷基化反应装置内的催化剂很难维持稳定的较高的目标产物选择性。
发明内容
本发明为了克服现有技术固体酸烷基化反应无法连续稳定运行，且目标产物选择性有待进一步提高的问题，提供一种固体酸烷基化方法。采用本发明提供的方法不但能够实现固体酸烷基化反应的连续稳定运行，而且能够提高目标产物选择性。
为了实现上述目的，本发明提供了以下的技术方案：
1、一种液固轴向移动床反应与再生装置，其特征在于，该装置包括：
依次连接的轴向移动床反应器(1)、待生剂接收器(5)、催化剂再生器(4)和再生剂接收器(6)，其中，再生剂接收器(6)的催化剂出口与轴向移动床反应器(1)的催化剂入口连通；
其中，轴向移动床反应器(1)设置有至少两个上下放置的催化剂床层(3)和任选地催化剂再生床层，轴向移动床反应器(1)在每个催化剂床层(3)的上方设置有进料口(2)；
相邻两个催化剂床层(3)之间，或者在催化剂再生床层存在的情况下，相邻两个床层之间，设置有催化剂输送管(16)使得催化剂能够在轴向移动床反应器(1)中自上而下移动；
任选地，相邻两个催化剂床层(3)之间以及如果催化剂再生床层作为最后一段床层存在的话，在上游的催化剂床层与最后一段的催化剂再生床层之间，设置有分离件(10)，例如，分离件可以设置在每个反应床层中，所述分离件(10)内侧空间与催化剂输送管(16)连通，所述分离件(10)用于上游催化剂床层反应后物料和催化剂的分离，分离件(10)分离得到的催化剂通过催化剂输送管(16)向下移动。
2、根据技术方案1所述的液固轴向移动床反应与再生装置，其中，轴向移动床反应器(1)的最后一个催化剂床层的反应物料出口与轴向移动床反应器(1)的第一个催化剂床层的的进料口(2)连通以将轴向移动床反应器(1)得到的反应物料循环回轴向移动床反应器(1)。
3、根据技术方案1-2中任意一项所述的液固轴向移动床反应与再生装置，其中，
所述的轴向移动床反应器还包括至少一个催化剂再生床层，优选地，催化剂床层和催化剂再生床层的数目相同并且催化剂床层和催化 剂再生床层间隔依次放置，更优选地，催化剂再生床层比催化剂床层的数目少一个，催化剂床层和催化剂再生床层间隔依次放置，并且轴向移动床反应器的顶端和底端均设置为催化剂反应床层；
轴向移动床反应器具有催化剂入口，其与第一个催化剂床层的顶部相通；
每一个催化剂床层的顶部有催化剂入口和反应物料进料口，第一个反应床层的催化剂入口就是轴向移动床反应器的催化剂入口，之后的反应床层的催化剂入口与催化剂输送管相通；
每一个催化剂床层的底部有与催化剂输送管道相通的催化剂出口和反应物料出口；
催化剂再生床层的顶部有与催化剂输送管道相通的催化剂入口和再生介质出口；
催化剂再生床层的底部有与催化剂输送管道相通的催化剂出口和再生介质入口；
所述的催化剂再生床层向催化剂床层转移催化剂的催化剂输送管线上设置有隔离介质入口；
每个催化剂床层的底部设置有分离件；
各个床层之间通过催化剂输送管线相通；
催化剂床层底部与再生床层之间通过插入再生床层内部的催化剂输送管道相通，所述的插入式催化剂输送管道的出口低于再生床层中的再生介质出口；
隔离介质入口与最后一段的催化剂床层的反应物料出口相通，以将泵增压后的反应物料作为隔离介质使用；
上游的催化剂床层的反应物料出口与下游的催化剂床层的反应物料进料口相连通，任选地，通过连接管线相连通，在此连接管线上还设置有新鲜反应原料的入口；
上游的催化剂再生床层的再生介质出口可以通过管线与下游的催化剂再生床层的再生介质入口相连通；
相邻两个催化剂床层(3)之间以及如果催化剂再生床层作为最后一段床层存在的话，在上游的催化剂床层与最后一段的催化剂再生床层之间，设置有分离件(10)，例如，分离件可以设置在每个反应床层中，所述分离件(10)内侧空间与催化剂输送管(16)连通，所述 分离件(10)用于上游催化剂床层反应后物料和催化剂的分离，分离件(10)分离得到的催化剂通过催化剂输送管(16)向下移动。
4、根据技术方案1-3中任意一项所述的液固轴向移动床反应与再生装置，其中，相邻两个催化剂床层(3)之间以及如果有的话，在上游的催化剂床层与最后一段的催化剂再生床层之间设置有反应物料折流件(11)，例如，在每个催化剂床层中可以设置有反应物料折流件，特别是在反应床层的床层空间中，所述反应物料折流件(11)用于强化反应后物料和进料口(2)送入的液态新鲜反应原料的混合。
5、根据技术方案4所述的液固轴向移动床反应与再生装置，其中，所述反应物料折流件(11)包括主轴(111)和沿主轴轴向螺旋延伸的输送部件(112)。
6、根据技术方案4或5所述的液固轴向移动床反应与再生装置，其中，所述反应物料折流件(11)包括多个折流板(113)，多个折流板(113)沿轴向移动床反应器(1)的轴向倾斜设置，且多个折流板(113)相互之间交错设置以形成能够供反应物料通过的流道。
7、根据技术方案1-6中任意一项所述的液固轴向移动床反应与再生装置，其中，相邻两个催化剂床层(3)之间以及如果存在催化剂再生床层的话，在相邻的两个床层之间设置有催化剂分布件，所述催化剂分布件用于分散催化剂输送管(16)出口的催化剂；
优选地，所述催化剂分布件包括锥型分布挡板(12)，所述锥型分布挡板(12)与催化剂输送管(16)同轴设置；进一步优选地，锥型分布挡板(12)与催化剂输送管(16)的数量相同；
进一步优选地，所述催化剂分布件还包括设置在所述锥型分布挡板(12)下方的水平分布挡板(13)，所述水平分布挡板(13)上设置有供催化剂通过的孔。
8、根据技术方案1-7中任意一项所述的液固轴向移动床反应与再生装置，其中，催化剂再生器(4)设置有新鲜催化剂进料口供新鲜催化剂进入催化剂再生器(4)中。
9、根据技术方案1-8中任意一项所述的液固轴向移动床反应与再生装置，其中，待生剂接收器(5)、催化剂再生器(4)和再生剂接收器(6)依次自上而下设置，待生剂接收器(5)、催化剂再生器(4)和再生剂接收器(6)之间的催化剂流通管线为垂直设置或与水平面间 的夹角不小于40度倾斜设置。
10、根据技术方案1-9中任意一项所述的液固轴向移动床反应与再生装置，其中，轴向移动床反应器(1)的催化剂出口与待生剂接收器(5)的催化剂入口的连通管线上设置有第一颗粒流量调节器(25)；再生剂接收器(6)的催化剂出口与轴向移动床反应器(1)的催化剂入口的连通管线上设置有第二颗粒流量调节器(33)；
优选地，所述第一颗粒流量调节器(25)和第二颗粒流量调节器(33)各自独立地为L型或近似L型的物料输送阀组。
11、根据技术方案1-10中任意一项所述的液固轴向移动床反应与再生装置，其中，该装置还包括催化剂缓冲罐(38)，所述催化剂缓冲罐(38)设置在轴向移动床反应器(1)、待生剂接收器(5)之间，催化剂缓冲罐(38)的催化剂入口与轴向移动床反应器(1)的催化剂出口连通，催化剂缓冲罐(38)的催化剂出口与待生剂接收器(5)的催化剂入口连通。
12、一种固体酸烷基化方法，包括：
该方法在技术方案1-11中所述的液固轴向移动床反应与再生装置中进行，液相原料从每个催化剂床层上方设置的进料口送入轴向移动床反应器中与催化剂接触反应。
13、根据技术方案12所述的方法，其中，该方法还包括：将轴向移动床反应器(1)底部得到的反应产物(即，由最后一段的催化剂床层的反应物料出口得到)循环至最上游催化剂床层的上方与所述液相原料混合后进料。
14、根据技术方案12-13中任意一项所述的方法，其中，轴向移动床反应器中的反应温度为30-100℃，压力为1-3.4MPa；
优选地，以烯烃计的进入各催化剂床层的物料的质量空速为0.05-1h -1；
优选地，进入各催化剂床层的物料的异构烷烃和烯烃的摩尔比为200-1000:1；
优选地，催化剂在轴向移动床反应器中的停留时间为6-72h。
15、根据技术方案12-14中任意一项所述的方法，其中，所述催化剂为固体酸催化剂，所述固体酸催化剂含有分子筛和耐热无机氧化物，以所述固体酸催化剂的总量为基准，分子筛的含量为65-95重量％，耐 热无机氧化物的含量为5-35重量％；
优选地，所述分子筛选自FAU结构沸石、BETA结构沸石和MFI结构沸石中至少一种，所述耐热无机氧化物为氧化铝和/或氧化硅；
进一步优选地，所述固体酸催化剂还含有金属活性组分，所述金属活性组分选自Fe、Co、Ni、Pd和Pt中至少一种，以所述固体酸催化剂的总量为基准，金属活性组分的含量为0.15-2重量％。
16、根据技术方案12-15中任意一项所述的方法，其中，相邻两个催化剂床层(3)之间设置有分离件(10)，例如，分离件可以设置在每个反应床层中，所述分离件(10)内侧空间与催化剂输送管(16)连通，所述分离件(10)用于上游催化剂床层反应后物料和催化剂的分离，分离件(10)分离得到的催化剂通过催化剂输送管(16)向下移动。
17、根据技术方案12-16中任意一项所述的方法，其中，相邻两个催化剂床层(3)之间设置有反应物料折流件(11)，例如，在每个催化剂床层中可以设置有反应物料折流件，特别是在反应床层的床层空间中；所述反应物料折流件(11)用于强化反应后物料和进料口(2)送入的液态新鲜反应原料的混合；
优选地，所述反应物料折流件(11)包括主轴(111)和沿主轴轴向螺旋延伸的输送部件(112)；
优选地，所述反应物料折流件(11)包括多个折流板(113)，多个折流板(113)沿轴向移动床反应器(1)的轴向倾斜设置，且多个折流板(113)相互之间交错设置以形成能够供反应物料通过的流道。
18、根据技术方案12-17中任意一项所述的方法，其中，相邻两个催化剂床层(3)之间设置有催化剂分布件，所述催化剂分布件用于分散催化剂输送管(16)出口的催化剂；
优选地，所述催化剂分布件包括锥型分布挡板(12)，所述锥型分布挡板(12)与催化剂输送管(16)同轴设置；进一步优选地，锥型分布挡板(12)与催化剂输送管(16)的数量相同；
进一步优选地，所述催化剂分布件还包括设置在所述锥型分布挡板(12)下方的水平分布挡板(13)，所述水平分布挡板(13)上设置有供催化剂通过的孔。
19、根据技术方案12-18中任意一项所述的方法，其中，轴向移动 床反应器(1)底部的催化剂输送至待生剂接收器(5)中脱除催化剂中携带的液相物料，然后输送至催化剂再生器(4)中进行再生；
优选地，所述再生介质在催化剂再生器(4)中的表观流速为0.003-0.8m/s，进一步优选为0.02-0.5m/s。
20、根据技术方案12-19中任意一项所述的方法，其中，催化剂再生器(4)设置有新鲜催化剂进料口供新鲜催化剂进入催化剂再生器(4)中。
21、根据技术方案12-20中任意一项所述的方法，其中，待生剂接收器(5)、催化剂再生器(4)和再生剂接收器(6)依次自上而下设置，待生剂接收器(5)、催化剂再生器(4)和再生剂接收器(6)之间的催化剂流通管线为垂直设置或与水平面间的夹角不小于40度倾斜设置。
22、根据技术方案12-21中任意一项所述的方法，其中，轴向移动床反应器(1)的催化剂出口与待生剂接收器(5)的催化剂入口的连通管线上设置有第一颗粒流量调节器(25)；再生剂接收器(6)的催化剂出口与轴向移动床反应器(1)的催化剂入口的连通管线上设置有第二颗粒流量调节器(33)；
优选地，所述第一颗粒流量调节器(25)和第二颗粒流量调节器(33)各自独立地为L型或近似L型的物料输送阀组。
23、根据技术方案12-22中任意一项所述的方法，其中，该装置还包括催化剂缓冲罐(38)，所述催化剂缓冲罐(38)设置在轴向移动床反应器(1)、待生剂接收器(5)之间，催化剂缓冲罐(38)的催化剂入口与轴向移动床反应器(1)的催化剂出口连通，催化剂缓冲罐(38)的催化剂出口与待生剂接收器(5)的催化剂入口连通。
24、根据技术方案12-23中任意一项所述的方法，其中，所述轴向移动床反应器(1)设置有催化剂再生床层，其位于一个反应床层之下，离开该反应床层的催化剂进入该催化剂再生床层，在溶解有氢气的液态烃的存在下再生，在催化剂再生床层中的再生条件为：
再生温度为50-140℃，
再生介质在再生器内的表观流速为0.01-0.5m/s；
所述的再生介质为溶解有氢气的液态烃；液态烃为C3-C6(例如C3-C5)的饱和烷烃或反应产物与上述饱和烷烃的混合物，优选的，液 态烃为C3-C6(例如C3-C5)的饱和烷烃与反应产物的混合物。
25、根据技术方案12-24中任意一项所述的方法，其中，
新鲜原料与循环料或上游催化剂床层的反应后物料进入轴向移动床反应器，在催化剂床层与催化剂接触发生反应；反应后物料通过分离件进入下一个反应床层或者最终离开反应器，未通过分离件的催化剂通过催化剂输送管向下移动进入下游的反应床层进行反应或进入催化剂再生床层进行低温再生，低温再生后的催化剂通过催化剂输送管向下移动进入下游的反应床层。
26、根据技术方案12-25中任意一项所述的方法，其中，
通过分离件的反应后物料和新鲜原料在反应物料折流件的作用下强化混合；
相邻两个床层之间设置有催化剂分布件，由上游床层经过催化剂输送管的催化剂在催化剂分布件作用下分散下落至下游床层；
轴向移动床反应器的下部设置有底部催化剂收集区；通过最下游催化剂床层的催化剂送入底部催化剂收集区，然后送至待生剂接收器；
轴向移动床反应器的催化剂出口与待生剂接收器的催化剂入口的连通管线上设置有第一颗粒流量调节器，以调节催化剂颗粒流量；
待生剂接收器底部设置退液相料出口，在待生剂接收器中脱除催化剂中携带的液相物料，从所述退液相料出口送出的退液相料输送管线上设置脱液过滤器以阻隔催化剂细粉或细小的催化剂颗粒；
待生剂接收器中脱液后的催化剂送入催化剂再生器中进行再生，所述催化剂再生器设置有再生介质进料口和再生介质出料口；
再生介质通过再生介质进料口送入催化剂再生器中与催化剂接触对催化剂进行再生，再生介质通过再生介质出料口外排；
从所述再生介质出料口送出的再生介质输送管线上设置再生介质过滤器以阻隔细粉或细小颗粒；
催化剂再生器任选地设置有新鲜催化剂进料口供新鲜催化剂进入催化剂再生器中；
再生后的催化剂通过催化剂再生器底部的催化剂输送管线流入再生剂接收器，再生剂接收器设置有液相料补充入口，通过液相料补充入口向再生剂接收器中引入液相料置换催化剂间隙的气体；
再生后的催化剂会通过再生剂接收器与轴向移动床反应器之间的 催化剂输送管道返回轴向移动床反应器继续参与反应，直至失活后被输送至待生剂接收器；
再生剂接收器的催化剂出口与轴向移动床反应器的催化剂入口的连通管线上设置有第二颗粒流量调节器，以调节催化剂颗粒流量。
27、根据技术方案12-26中任意一项所述的方法，其中，
所述的轴向移动床反应器包括：
至少一个，优选地，至少两个催化剂床层(亦称为反应床层)和至少一个催化剂再生床层，优选地，反应床层和催化剂再生床层的数目相同并且反应床层和催化剂再生床层间隔依次放置，更优选地，催化剂再生床层比催化剂床层的数目少一个，催化剂床层和催化剂再生床层间隔依次放置，并且轴向移动床反应器的顶端和底端均设置为催化剂反应床层；
轴向移动床反应器具有催化剂入口，其与第一个反应床层的顶部相通；
每一个反应床层的顶部有催化剂入口和反应物料进料口，第一个反应床层的催化剂入口就是轴向移动床反应器的催化剂入口，之后的反应床层的催化剂入口与催化剂输送管相通；
每一个反应床层的底部有与催化剂输送管道相通的催化剂出口和反应物料出口；
催化剂再生床层的顶部有与催化剂输送管道相通的催化剂入口和再生介质出口；
催化剂再生床层的底部有与催化剂输送管道相通的催化剂出口和再生介质入口；
所述的催化剂再生床层向反应床层转移催化剂的催化剂输送管线上设置有隔离介质入口；
每个反应床层的底部设置有分离件；
各个床层之间通过催化剂输送管线相通；
反应床层底部与再生床层之间通过插入再生床层内部的催化剂输送管道相通，所述的插入式催化剂输送管道的出口低于再生床层中的再生介质出口；
所述的隔离介质优选为反应后经过泵增压的循环料，隔离介质入口与最后一段的反应床层的反应物料出口相通；
反应后物料通过分离件进入下一段的反应床层或者最终排出，未通过分离件的催化剂通过催化剂输送管向下移动；
上游的反应床层的反应物料出口与下游的反应床层的反应物料进料口相连通，任选地，通过连接管线相连通，在此连接管线上还设置有新鲜反应原料的入口；
所述的床层的顶部是指处于每一段床层由下至上的70％以上的位置，所述的床层的底部是指处于每一段床层由下至上的20％以下的位置；
上游的催化剂再生床层的再生介质出口可以通过管线与下游的催化剂再生床层的再生介质入口相连通；
反应床层的反应物料进料口、催化剂再生床层的再生介质入口以及所述的催化剂再生床层向反应床层转移催化剂的催化剂输送管线上设置的隔离介质入口设置了相应的物料分布器；
新鲜反应原料与循环料或上游反应床层反应后物料进入轴向移动床的反应床层；在反应床层中，混合料通过反应物料分布器分布后沿反应床层轴向穿过反应床层，与固体酸催化剂接触并发生反应，反应完毕的大部分液相料通过设置的反应物料出口排出本段，剩余的小部分液相料则跟随催化剂颗粒进入下一个反应床层或者通过反应床层与催化剂再生床层之间的插入式管道进入催化剂再生床层；
排出的反应后液相物料与新鲜反应原料进入下一段反应床层继续参与反应或直接排出反应床层，经分离(例如蒸馏)后收集烷基化油产品；
在催化剂再生床层中，催化剂通过与溶解有氢气的液相再生介质在再生条件下进行逆流接触(低温再生)，将吸附在催化剂上的不饱和烃类转化为容易脱附的饱和烃分子带出催化剂再生床层，实现催化剂的部分再生；再生后的催化剂会通过催化剂再生床层底部的催化剂输送管线流入下一个反应床层；在催化剂从催化剂再生床层底部向反应床层输送过程中，隔离介质通过设置于输送管线上的隔离介质引入口进入，将与催化剂一起下行的液相介质置换；
处于移动床各床层中的催化剂随着反应的进行以及再生次数的增加失活程度会逐渐增加，同时也会逐渐下落至更低的床层最终到达移动床反应器的底部；最终催化剂被送至催化剂再生器进行高温深度再 生，实现催化剂活性的完全恢复；恢复活性的催化剂被送至移动床反应器的第一段反应床层继续参与反应，如此循环；
在反应床层中的反应条件可以包括：
反应温度为30-100℃，
反应压力为1.0-3.4MPa，表压，
液相物料在反应器内的表观流速为0.03-1m/s；
混合烯烃原料的质量空速为0.05-1h -1；
反应床层入口处的烷烃与烯烃的摩尔比为200-1000:1；
固体酸催化剂颗粒的平均粒径为0.3-3mm。
在催化剂再生床层中的再生条件可以包括：
再生温度为50-140℃，
再生介质在再生器内的表观流速为0.01-0.5m/s；
所述的再生介质为溶解有氢气的液态烃；液态烃为C3-C6(例如C3-C5)的饱和烷烃或反应产物与上述饱和烷烃的混合物，优选的，液态烃为C3-C6(例如C3-C5)的饱和烷烃与反应产物的混合物；
在所述的催化剂再生器(高温深度再生)中的再生条件可以包括：
再生温度为180-400℃，
再生压力为0.5-4.0MPa，
再生介质为氢气或氢气和低碳烃(如C3-C8)的混合物，优选氢气和低碳烃(如C3-C8)的混合物；
所述催化剂的主要活性组分为负载有一定量金属的分子筛，所述分子筛为FAU结构沸石、BETA结构沸石、MFI结构沸石及其中的一种或几种的组合，优选为具有FAU结构和BETA结构沸石，所述催化剂上负载的金属为Fe、Co、Ni、Pd和(或)Pt中的一种或几种的组合，优选为Co、Ni或Pt的一种或几种的组合。
本发明提供的液固轴向移动床反应与再生装置具有如下优势：
1)与固定床烷基化技术相比，仅需要使用一台反应器即可实现反应装置的连续稳定运行；
2)与流动床烷基化技术相比，本发明提供的液固轴向移动床反应与再生装置能够实现催化剂的寿命分布，可以将失活的部分催化剂移出系统，然后补入新鲜的催化剂；而流动床反应器无法实现催化剂的寿命分布；
3)本发明提供的液固轴向移动床反应与再生装置使用轴向移动床反应器，单台(套)设备即可满足要求，减少了装置的投资成本，另外通过将失活的催化剂颗粒引出反应器外进行深度再生，在不影响反应装置稳定运行的前提下，实现了催化剂反应和再生的连续化操作，维持了装置内的催化剂具有较为稳定的平衡活性，提高了烷基化油中目标产物的选择性。
本发明提供的固体酸烷基化方法具有如下优势：
1)与固定床烷基化技术相比，仅需要使用一台反应器即可实现反应装置的连续稳定运行；
2)与流动床烷基化技术相比，本发明提供的方法能够实现催化剂的寿命分布，可以将失活的部分催化剂移出系统，然后补入新鲜的催化剂；而流动床反应器无法实现催化剂的寿命分布；
3)本发明提供的方法使用轴向移动床反应器，单台(套)设备即可满足要求，减少了装置的投资成本，另外通过将失活的催化剂颗粒引出反应器外进行深度再生，在不影响反应装置稳定运行的前提下，实现了催化剂反应和再生的连续化操作，维持了装置内的催化剂具有较为稳定的平衡活性，提高了烷基化油中目标产物的选择性。
附图说明
图1是本发明提供的一种具体实施方式的液固轴向移动床反应与再生装置；
图2是本发明提供的一种折流件的示意图；
图3是本发明提供的一种具体实施方式的液固轴向移动床反应与再生装置。
图4是本发明提供的一种具体实施方式的液固轴向移动床反应器。
附图标记说明
1                轴向移动床反应器
2                进料口
3                催化剂床层
4                催化剂再生器
5                待生剂接收器
6                再生剂接收器
7                脱液过滤器
8                再生后介质过滤器
10               分离件
11               反应物料折流件
111              主轴
112              输送部件
113              折流板
12               锥型分布挡板
13               水平分布挡板
15               退液相料出口
16               催化剂输送管
17               管线
19               第一分支管线
20               第二分支管线
21               第三分支管线
25               第一颗粒流量调节器
30               再生介质进料口
31               再生后介质出料口
32               液相料补充入口
33               第二颗粒流量调节器
37               底部催化剂收集区
38               催化剂缓冲罐
51、53           反应床层
52、54           催化剂再生床层
55               新鲜反应原料
56、57           新鲜反应原料的入口
58               循环料
59、61           反应物料出口
60               反应物料进料口
62               催化剂入口
63、64、65、66   催化剂输送管道
67、69           再生介质入口
68、71            再生介质出口
70                隔离介质入口
72                分离件
具体实施方式
在本文中所披露的范围的端点和任何值都不限于该精确的范围或值，这些范围或值应当理解为包含接近这些范围或值的值。对于数值范围来说，各个范围的端点值之间、各个范围的端点值和单独的点值之间，以及单独的点值之间可以彼此组合而得到一个或多个新的数值范围，这些数值范围应被视为在本文中具体公开。
本发明中，在未作相反说明的情况下，使用的方位词如“上、下”通常是指通常是指参考附图所示的上和下。使用的方位词如“内、外”是指相对于各部件本身的轮廓的内、外。
在本发明中，所述的床层的上方、顶部等是指处于每一段床层由下至上的70％以上的位置，所述的床层的底部等是指处于每一段床层由下至上的20％以下的位置。
在一个方面中，本发明提供了一种液固轴向移动床反应与再生装置，该装置包括：
依次连接的轴向移动床反应器1、待生剂接收器5、催化剂再生器4和再生剂接收器6，其中，再生剂接收器6的催化剂出口与轴向移动床反应器1的催化剂入口连通；
其中，轴向移动床反应器1设置有至少两个上下放置的催化剂床层3，轴向移动床反应器1在每个催化剂床层3的上方设置有进料口2；
相邻两个催化剂床层3之间设置有催化剂输送管16使得催化剂能够在轴向移动床反应器1中自上而下移动。
在本发明中，所述的依次连接是指，轴向移动床反应器1的催化剂出口与待生剂接收器5的催化剂入口连接，待生剂接收器5的催化剂出口与催化剂再生器4的催化剂入口连接，催化剂再生器4的催化剂出口与再生剂接收器6的催化剂入口连接。再生剂接收器6的催化剂出口与轴向移动床反应器1的催化剂入口连通，以将再生催化剂送入轴向移动床反应器1中。
本发明所述轴向移动床反应器是指催化剂的移动方向为轴向的移 动床反应器。
根据本发明提供的装置，轴向移动床反应器1设置有至少两个上下放置的催化剂床层，优选设置3-8个上下放置的催化剂床层3。本发明对催化剂床层3的厚度没有特别的限定，优选地，各个催化剂床层3的厚度各自独立地为轴向移动床反应器1高度的10-30％。
本发明实施例中以轴向移动床反应器1的高度为7.5m，内径为600mm为例进行示例性说明，但本发明并不限于此。本领域技术人员可以根据实际情况进行适当调整。在一种实施方案中，轴向移动床反应器1的高度为5-75米，内径为200-3000mm。
根据本发明提供的装置，轴向移动床反应器1在每个催化剂床层3的上方设置有进料口2。液态新鲜反应原料从轴向移动床反应器1的进料口2送入轴向移动床反应器1中与催化剂床层3中装填的催化剂进行接触反应。轴向移动床反应器1的最上层催化剂床层3中的催化剂与液态新鲜反应原料进行接触反应，而其它催化剂床层3中的催化剂与液态新鲜反应原料和来自上游催化剂床层3反应后物料的混合物进行接触反应。采用本发明提供的装置，可以将液态新鲜反应原料通过不同的进料口2送入轴向移动床反应器1中，更有利于控制温升。
本发明对所述催化剂输送管16没有特别的限制，只要能够使得催化剂能够在轴向移动床反应器1中自上而下移动即可。具体地，催化剂输送管可以为圆柱形。相邻两个催化剂床层3之间可以设置一个催化剂输送管16，也可以设置两个以上催化剂输送管16。催化剂输送管16的内径和数量根据轴向移动床反应器1的内径进行适当的选择。例如，相对于内径为600mm的轴向移动床反应器1，相邻两个催化剂床层3之间可以设置2-5个催化剂输送管16，催化剂输送管16的内径可以为15-50mm。在一种实施方案中，轴向移动床反应器1的高度为5-75米，内径为200-3000mm，相邻两个催化剂床层3之间可以设置2-5个催化剂输送管16，催化剂输送管16的内径可以为5-150mm。
根据本发明的一种优选实施方式，轴向移动床反应器1的反应物料出口(优选设置在底部)与轴向移动床反应器2的最上方的进料口2连通以将轴向移动床反应器1得到的反应物料循环回轴向移动床反应器1。采用该种优选实施方式，更有利于控制各催化剂床层3的烷烯比，且更有利控制催化剂床层3的温升。
在本发明中，催化剂床层又称为反应床层，相邻两个催化剂床层是指上游的反应床层与其下游的反应床层；在不包括催化剂再生床层的情况下，相邻两个催化剂床层就是指上下游的两个催化剂床层，而在包括非最后一段的催化剂再生床层的情况下，相邻两个催化剂床层就是指分别在该催化剂再生床层上游的第一个非催化剂再生床层的催化剂床层(即反应床层)和在该催化剂再生床层下游的第一个非催化剂再生床层的催化剂床层(即反应床层)。
在本发明中，相邻的两个床层之间是指任意两个相邻的床层之间，包括：上游的催化剂床层(即反应床层)和下游的催化剂床层(即反应床层)之间、上游的催化剂床层(即反应床层)和下游的催化剂再生床层之间、上游的催化剂再生床层和下游的催化剂床层(即反应床层)之间、上游的催化剂再生床层和下游的催化剂再生床层之间。
根据本发明的一种优选实施方式，相邻两个催化剂床层3之间以及如果有的话，在上游的催化剂床层(反应床层)与最后一段的催化剂再生床层之间设置有分离件10(例如，在每个反应床层中可以设置有分离件10)，所述分离件10内侧空间与催化剂输送管16连通，所述分离件10用于上游催化剂床层反应后物料和催化剂的分离，分离件10分离得到的催化剂通过催化剂输送管16向下移动。上游催化剂床层反应后物料和催化剂经过分离件10进行分离，得到反应后物料和催化剂，催化剂通过催化剂输送管16向下移动，而反应后物料在相邻两个催化剂床层之间的空间(本发明中称其为反应床层前的床层空间)与催化剂床层3的上方的进料口送入的液态新鲜反应原料混合，然后流入下游催化剂床层。
根据本发明的一种具体实施方式，所述分离件10可以是具有孔的筛网(孔径可以根据催化剂颗粒大小决定)，其允许反应后物料通过，以实现反应后物料和催化剂的分离。
为了使得流入下游催化剂床层的反应后物料和液态新鲜反应原料混合更加均匀，优选地，相邻两个催化剂床层3之间设置有反应物料折流件11，所述反应物料折流件11用于强化反应后物料和进料口2送入的液态新鲜反应原料的混合。例如，在每个催化剂床层中可以设置有反应物料折流件，特别是在反应床层的床层空间中。
本发明对所述反应物料折流件11的具体结构没有特别的限定，只 要能够起到强化强化反应后物料和液态新鲜反应原料的混合即可。具体的，反应物料折流件11放置于反应床层前的床层空间内，其数量可以为1个或者两个以上，优选为1-6个。
根据本发明的第一种优选实施方式，如图2所示，所述反应物料折流件11包括主轴111和沿主轴轴向螺旋延伸的输送部件112。具体地，输送部件112形成的螺旋延伸的流道的入口根据进料口2的位置进行设定使得反应后物料和液态新鲜反应原料从输送部件112形成的螺旋延伸的流道流动，进而实现混合。
根据本发明的第二种优选实施方式，如图1所示，所述反应物料折流件11包括多个折流板113，多个折流板113沿轴向移动床反应器1的轴向倾斜设置，且多个折流板113相互之间交错设置以形成能够供反应物料通过的流道。所述多个折流板113沿轴向移动床反应器1的轴向可以是倾斜向下设置，也可以是倾斜向上设置(如图1所示)。优选地，折流板113的延伸方向与水平面的夹角在5-60度，进一步优选为10-40度。
本发明中所述的折流板113相互之间交错设置是指折流板113相互之间不形成封闭区域，使得反应物料能够顺利的向下流动。根据本发明的一种具体实施方式，如图1所示，部分折流板113固定连接于轴向移动床反应器1的器壁，部分折流板113固定连接于催化剂输送管16的管壁，且折流板113相互之间平行设置。优选地，相邻折流板113之间的距离为15-60mm。
根据本发明的一种优选实施方式，相邻两个催化剂床层3之间以及如果存在催化剂再生床层的话，在相邻的两个床层之间设置有催化剂分布件，所述催化剂分布件用于分散催化剂输送管16出口的催化剂。如果不设置催化剂分布件，催化剂输送管16出口的催化剂容易在下游催化剂床层形成锥状堆积。优选所述催化剂分布件包括锥型分布挡板12，所述锥型分布挡板12与催化剂输送管16同轴设置。催化剂输送管16出口的催化剂依靠重力作用，落于锥型分布挡板12的尖端，通过锥型分布挡板12的分散作用，向催化剂输送管16的水平两侧分散。进一步优选地，锥型分布挡板12与催化剂输送管16的数量相同。
根据本发明的一种优选实施方式，所述催化剂分布件还包括设置在所述锥型分布挡板12下方的水平分布挡板13，所述水平分布挡板 13上设置有供催化剂通过的孔。本发明对所述水平分布挡板13的数量没有特别的限定，可以为1个，也可以为两个以上，优选分别设置在相邻两个锥型分布挡板12的径向中间位置(且轴向下方位置)。所述径向和轴向指的是轴向移动床反应器1的径向和轴向。
进一步优选地，沿轴向移动床反应器1的中心水平向外方向上，所述水平分布挡板13上的孔逐步变大。采用该种优选实施方式，靠近轴向移动床反应器1的中心位置通过锥型分布挡板12的分散的催化剂部分从所述水平分布挡板13孔通过，部分不能够通过的催化剂被分散至轴向移动床反应器1的边缘位置，更有利于保证催化剂的均匀分散。
进一步优选地，所述水平分布挡板13可为中间区域开孔率低、边壁处开孔率高的圆形分布板。
处于轴向移动床反应器1各催化剂床层中的催化剂随着反应的进行会逐渐失活的同时也会逐渐下落至更下游的催化剂床层(反应床层)或催化剂再生床层，最终到达轴向移动床反应器1底部，随后通过催化剂输送管线输送至待生剂接收器5。
根据本发明的一种优选实施方式，轴向移动床反应器1下部设置有底部催化剂收集区37。通过最下游催化剂床层的催化剂送入底部催化剂收集区37，收集一定量后送至待生剂接收器5。
根据本发明的一种具体实施方式，如图1所示，轴向移动床反应器1与待生剂接收器5、待生剂接收器5与催化剂再生器4、催化剂再生器4与再生剂接收器6、再生剂接收器6与轴向移动床反应器1的连通管线上分别设置有容器间的物料管线阀。
根据本发明的一种优选实施方式，待生剂接收器5(优选底部)设置退液相料出口15。本发明可以在待生剂接收器5中通过直接减压或引入高压氢气、氮气等充压的方式脱除催化剂中携带的液相物料，液相物料可以通过退液相料出口15外输。优选地，从所述退液相料出口15送出的退液相料输送管线上设置有脱液过滤器7。所述脱液过滤器7用于阻隔催化剂细粉或细小的催化剂颗粒。
待生剂接收器5中脱液后的催化剂送入催化剂再生器4中进行再生。所述催化剂再生器4设置有再生介质进料口30和再生介质出料口31。再生介质通过再生介质进料口30送入催化剂再生器4中与催化剂接触对催化剂进行再生(优选完全再生)，再生介质通过再生介质出 料口31外排。优选地，从所述再生介质出料口31送出的再生介质输送管线上设置有再生介质过滤器8。该过滤器用于阻隔再生器的催化剂流入下游的气体循环增压设备以及收集再生过程因摩擦或吹扫产生的细粉或细小颗粒。
本发明所述的再生介质可以为空气或空气与氮气的混合气。
根据本发明的一种优选实施方式，催化剂再生器4还可以设置有新鲜催化剂进料口供新鲜催化剂进入催化剂再生器4中。通过在催化剂再生器4上设置新鲜催化剂进料口，可将部分失去活性的催化剂或难以恢复初始活性的催化剂置换为新鲜催化剂，保证装置的处理能力。具体地，与新鲜催化剂进料口连通的新鲜催化剂输送管线上设置有泵。
再生后的催化剂会通过催化剂再生器4底部的催化剂输送管线流入再生剂接收器6中。
优选地，再生剂接收器6设置有液相料补充入口32。通过液相料补充入口32向再生剂接收器6中引入反应原料中的烷烃或反应后液相物料等液相料置换催化剂间隙的气体。
再生后的催化剂会通过再生剂接收器6与轴向移动床反应器1间的催化剂输送管道返回轴向移动床反应器1，继续参与反应，直至失活后被输送至待生剂接收器5，催化剂按照上述流程循环。
根据本发明的一种优选实施方式，待生剂接收器5、催化剂再生器4和再生剂接收器6依次自上而下设置，待生剂接收器5、催化剂再生器4和再生剂接收器6之间的催化剂流通管线为垂直设置或与水平面间的夹角不小于40度倾斜设置。采用该种优选实施方式更便于催化剂颗粒料从上而下的顺畅流通，防止物料堆积或残存在管线中，影响阀门密封性或催化剂再生的效果。
根据本发明的一种优选实施方式，轴向移动床反应器1的催化剂出口与待生剂接收器5的催化剂入口的连通管线上设置有第一颗粒流量调节器25；再生剂接收器6的催化剂出口与轴向移动床反应器1的催化剂入口的连通管线上设置有第二颗粒流量调节器33。本发明对所述第一颗粒流量调节器25和第二颗粒流量调节器33没有特别的限定，只要能够调节催化剂颗粒的流量即可。进一步优选地，所述第一颗粒流量调节器25和第二颗粒流量调节器33各自独立地为L型或近似L型的物料输送阀组。具体地，所述L型或近似L型的物料输送阀组上 还连通至少一路液相物料进料管线。设置颗粒流量调节器可以增加颗粒物料的流通阻力，同时，在该调节器上连通至少一路的液相物料进料管线，用以增加颗粒物料的流动推动力并降低颗粒物料的流动阻力。通过设置L型或近似L型的物料输送阀组，通过改变进入阀组的液相物料流量可调节催化剂的排出速率，从而达到控制和调节处于反应器中的催化剂在各反应床层的下落速率和停留时间。
根据本发明的一种优选实施方式，该装置还包括催化剂缓冲罐38，所述催化剂缓冲罐38设置在轴向移动床反应器1、待生剂接收器5之间，催化剂缓冲罐38的催化剂入口与轴向移动床反应器1的催化剂出口连通，催化剂缓冲罐38的催化剂出口与待生剂接收器5的催化剂入口连通。所述催化剂缓冲罐38用以保存待生剂接收器在退液相料以及向催化剂再生剂排催化剂期间从轴向移动床反应器1排出的催化剂，保证轴向移动床反应器1内催化剂物料流动的连续性和装置操作的平稳性。
在本发明的一种实施方案中，所述的轴向移动床反应器包括：
至少一个，优选地，至少两个催化剂床层(亦称为反应床层)和至少一个催化剂再生床层，优选地，反应床层和催化剂再生床层的数目相同并且反应床层51、53和催化剂再生床层52、54间隔依次放置，更优选地，催化剂再生床层比催化剂床层的数目少一个，催化剂床层和催化剂再生床层间隔依次放置，并且轴向移动床反应器的顶端和底端均设置为催化剂反应床层；
轴向移动床反应器具有催化剂入口62，其与第一个反应床层的顶部相通；
每一个反应床层的顶部有催化剂入口和反应物料进料口60，第一个反应床层的催化剂入口就是轴向移动床反应器的催化剂入口，之后的反应床层的催化剂入口与催化剂输送管相通；
每一个反应床层的底部有与催化剂输送管道63、65相通的催化剂出口和反应物料出口59、61；
催化剂再生床层的顶部有与催化剂输送管道63、65相通的催化剂入口和再生介质出口68、71；
催化剂再生床层的底部有与催化剂输送管道64、66相通的催化剂出口和再生介质入口67、69；
所述的催化剂再生床层向反应床层转移催化剂的催化剂输送管线上设置有隔离介质入口70；
每个反应床层的底部设置有分离件72；
各个床层之间通过催化剂输送管线相通；
反应床层底部与再生床层之间通过插入再生床层内部的催化剂输送管道相通，所述的插入式催化剂输送管道的出口低于再生床层中的再生介质出口；
所述的隔离介质优选为反应后经过泵增压的循环料，因此，隔离介质入口70与最后一段的反应床层的反应物料出口61相通；
反应后物料通过分离件72进入下一段的反应床层或者最终排出，未通过分离件72的催化剂通过催化剂输送管向下移动；
上游的反应床层的反应物料出口59通过管线与下游的反应床层的反应物料进料口60相连通，此连接管线上还设置有新鲜反应原料的入口56、57；
所述的床层的顶部是指处于每一段床层由下至上的70％以上的位置，所述的床层的底部是指处于每一段床层由下至上的20％以下的位置；
上游的催化剂再生床层的再生介质出口68通过管线与下游的催化剂再生床层的再生介质入口69相连通；
反应床层的反应物料进料口60、催化剂再生床层的再生介质入口以及所述的催化剂再生床层向反应床层转移催化剂的催化剂输送管线上设置的隔离介质入口70设置了相应的物料分布器。
通过本发明提供的液固轴向移动床反应与再生装置，可以实现固体酸烷基化反应与失活催化剂再生的连续平稳运行，提高了目标产物的选择性和装置操作的弹性，大大降低了催化剂投资成本，提高了装置的经济竞争力。因此，本发明还提供了上述液固轴向移动床反应与再生装置在固体酸烷基化反应中的应用。
在另一个方面中，本发明提供了一种固体酸烷基化方法，其中：该方法在液固轴向移动床反应与再生装置中进行，液固轴向移动床反应与再生装置包括：
依次连接的轴向移动床反应器1、待生剂接收器5、催化剂再生器4和再生剂接收器6，其中，再生剂接收器6的催化剂出口与轴向移动 床反应器1的催化剂入口连通；
轴向移动床反应器1设置有至少两个上下放置的催化剂床层3，轴向移动床反应器1在每个催化剂床层3的上方设置有进料口2；
相邻两个催化剂床层3之间设置有催化剂输送管16使得催化剂能够在轴向移动床反应器1中自上而下移动；
液相原料从每个催化剂床层3上方设置的进料口送入轴向移动床反应器1中与催化剂接触反应。
在本发明中，所述的依次连接是指，轴向移动床反应器1的催化剂出口与待生剂接收器5的催化剂入口连接，待生剂接收器5的催化剂出口与催化剂再生器4的催化剂入口连接，催化剂再生器4的催化剂出口与再生剂接收器6的催化剂入口连接。再生剂接收器6的催化剂出口与轴向移动床反应器1的催化剂入口连通，以将再生催化剂送入轴向移动床反应器1中。
本发明所述轴向移动床反应器是指催化剂的移动方向为轴向的移动床反应器。
根据本发明提供的方法，轴向移动床反应器1设置有至少两个上下放置的催化剂床层，优选设置3-8个上下放置的催化剂床层3。本发明对催化剂床层3的厚度没有特别的限定，优选地，各个催化剂床层3的厚度各自独立地为轴向移动床反应器1高度的10-30％。
本发明实施例中以轴向移动床反应器1的高度为7.5m，内径为600mm为例进行示例性说明，但本发明并不限于此。本领域技术人员可以根据实际情况进行适当调整。在一种实施方案中，轴向移动床反应器1的高度为5-75米，内径为200-3000mm。
本发明所述的液相原料可以为本领域常规使用的各种能够进行固体酸烷基化反应的原料。例如，所述液相原料含有异构烷烃和烯烃。所述异构烷烃可以为烷基化反应中常用的异构烷烃，优选为C4-C6的异构烷烃，更优选为异丁烷。所述烯烃优选为单烯烃，更优选为C3-C6的单烯烃，进一步优选为C4单烯烃。所述的烷基化原料为含有烯烃和烷烃的烃馏份，优选含有C4烯烃和C4烷烃的C4馏分，更优选为C4烯烃和C4烷烃的混合物。在一种实施方案中，烷烃馏分还包括经过分馏塔顶部经冷却返回至反应器入口的轻质烃类馏分。在一种实施方案中，所述的烷基化原料为含有烯烃和烷烃的烃馏份，其中烷烃与烯烃 的摩尔比5-50:1，例如10-40:1或20-30:1。在一种实施方案中，所述的烷基化原料为含有C3-C6烷烃和C3-C6烯烃的烃馏份，其中烷烃与烯烃的摩尔比5-50:1，例如10-40:1或20-30:1。在一种实施方案中，所述的烷基化原料为C3-C6烷烃和C3-C6烯烃的混合物，其中烷烃与烯烃的摩尔比5-50:1，例如10-40:1或20-30:1。
根据本发明的固体酸烷基化方法，进入各催化剂床层的物料的异构烷烃和烯烃可以为常规选择。优选地，进入各催化剂床层的物料的异构烷烃和烯烃的摩尔比(即，烷烯比)为200-1000:1。这样不仅能使烯烃完全或基本完全转化，而且能获得更高的产物选择性，同时还能使烷基化催化剂具有更高的活性稳定性。优选地，进入各催化剂床层的物料的异构烷烃和烯烃的摩尔比为400-750:1。
根据本发明，轴向移动床反应器中的反应温度优选为低于异构烷烃的临界温度，更优选为不高于120℃(如30-120℃)，进一步优选为不高于100℃，更进一步优选为30-100℃，如60-80℃的温度下进行。烷基化反应条件中，压力一般可以为1-3.4MPa，优选为1.2-3.2MPa，如1.5-3.0MPa。所述压力为表压。
根据本发明，以烯烃计的进入各催化剂床层的物料的质量空速可以为0.05-1h -1，优选为0.07-0.5h -1，例如为0.08-0.25h -1。
根据本发明的一种优选实施方式，催化剂在轴向移动床反应器中的停留时间为6-72h，优选为12-72h。
根据本发明提供的方法，对所述催化剂没有特别的限定，可以为本领域常规使用的各种催化剂，例如可以为固体酸催化剂。
优选地，所述固体酸催化剂含有分子筛和耐热无机氧化物，以所述固体酸催化剂的总量为基准，分子筛的含量为65-95重量％，进一步优选为65-90重量％，耐热无机氧化物的含量为5-35重量％，进一步优选为10-35重量％。
进一步优选地，所述分子筛选自FAU结构沸石、BETA结构沸石和MFI结构沸石中至少一种。
本发明中，所述耐热无机氧化物是指最高使用温度不低于600℃的无机氧化物。所述耐热无机氧化物可以为氧化铝和/或氧化硅。
在本发明的一种更为优选的实施方式中，所述固体酸催化剂还含有金属活性组分，所述金属活性组分选自Fe、Co、Ni、Pd和Pt中至 少一种，以所述固体酸催化剂的总量为基准，金属活性组分的含量为0.15-2重量％。采用根据该优选实施方式的催化剂，在其余条件相同的情况下，能获得更长的周期寿命和使用寿命，同时还能获得更高的产物选择性。
根据本发明，所述催化剂的平均粒径可以为0.3-3mm。
在本发明中，催化剂床层又称为反应床层，相邻两个催化剂床层是指上游的反应床层与其下游的反应床层；在不包括催化剂再生床层的情况下，相邻两个催化剂床层就是指上下游的两个催化剂床层，而在包括非最后一段的催化剂再生床层的情况下，相邻两个催化剂床层就是指分别在该催化剂再生床层上游的第一个非催化剂再生床层的催化剂床层(即反应床层)和在该催化剂再生床层下游的第一个非催化剂再生床层的催化剂床层(即反应床层)。
在本发明中，相邻的两个床层之间是指任意两个相邻的床层之间，包括：上游的催化剂床层(即反应床层)和下游的催化剂床层(即反应床层)之间、上游的催化剂床层(即反应床层)和下游的催化剂再生床层之间、上游的催化剂再生床层和下游的催化剂床层(即反应床层)之间、上游的催化剂再生床层和下游的催化剂再生床层之间。
根据本发明的一种优选实施方式，相邻两个催化剂床层3之间以及如果有的话，在上游的催化剂床层(反应床层)与最后一段的催化剂再生床层之间设置有分离件10，例如，在每个反应床层中可以设置有分离件10，所述分离件10内侧空间与催化剂输送管16连通，所述分离件10用于上游催化剂床层反应后物料和催化剂的分离，分离件10分离得到的催化剂通过催化剂输送管16向下移动。上游催化剂床层反应后物料和催化剂经过分离件10进行分离，得到反应后物料和催化剂，催化剂通过催化剂输送管16向下移动，而反应后物料在相邻两个催化剂床层之间的空间(本发明中称其为反应床层前的床层空间)与催化剂床层3的上方的进料口送入的液态新鲜反应原料混合，然后流入下游催化剂床层。
根据本发明的一种具体实施方式，所述分离件10可以是具有孔的筛网(孔径可以根据催化剂颗粒大小决定)，其允许反应后物料通过，以实现反应后物料和催化剂的分离。
为了使得流入下游催化剂床层的反应后物料和液态新鲜反应原料 混合更加均匀，优选地，相邻两个催化剂床层3之间设置有反应物料折流件11，所述反应物料折流件11用于强化反应后物料和进料口2送入的液态新鲜反应原料的混合。例如，在每个催化剂床层中可以设置有反应物料折流件，特别是在反应床层的床层空间中。
本发明对所述反应物料折流件11的具体结构没有特别的限定，只要能够起到强化强化反应后物料和液态新鲜反应原料的混合即可。具体的，反应物料折流件11放置于反应床层前的床层空间内，其数量可以为1个或者两个以上，优选为1-6个。
根据本发明的第一种优选实施方式，如图2所示，所述反应物料折流件11包括主轴111和沿主轴轴向螺旋延伸的输送部件112。具体地，输送部件112形成的螺旋延伸的流道的入口根据进料口2的位置进行设定使得反应后物料和液态新鲜反应原料从输送部件112形成的螺旋延伸的流道流动，进而实现混合。
根据本发明的第二种优选实施方式，如图1所示，所述反应物料折流件11包括多个折流板113，多个折流板113沿轴向移动床反应器1的轴向倾斜设置，且多个折流板113相互之间交错设置以形成能够供反应物料通过的流道。所述多个折流板113沿轴向移动床反应器1的轴向可以是倾斜向下设置，也可以是倾斜向上设置(如图1所示)。优选地，折流板113的延伸方向与水平面的夹角在5-60度，进一步优选为10-40度。
本发明中所述的折流板113相互之间交错设置是指折流板113相互之间不形成封闭区域，使得反应物料能够顺利的向下流动。根据本发明的一种具体实施方式，如图1所示，部分折流板113固定连接于轴向移动床反应器1的器壁，部分折流板113固定连接于催化剂输送管16的管壁，且折流板113相互之间平行设置。优选地，相邻折流板113之间的距离为15-60mm。
根据本发明的一种优选实施方式，相邻两个催化剂床层3之间以及如果存在催化剂再生床层的话，在相邻的两个床层之间设置有催化剂分布件，所述催化剂分布件用于分散催化剂输送管16出口的催化剂。如果不设置催化剂分布件，催化剂输送管16出口的催化剂容易在下游催化剂床层形成锥状堆积。优选所述催化剂分布件包括锥型分布挡板12，所述锥型分布挡板12与催化剂输送管16同轴设置。催化剂输送 管16出口的催化剂依靠重力作用，落于锥型分布挡板12的尖端，通过锥型分布挡板12的分散作用，向催化剂输送管16的水平两侧分散。进一步优选地，锥型分布挡板12与催化剂输送管16的数量相同。
根据本发明的一种优选实施方式，所述催化剂分布件还包括设置在所述锥型分布挡板12下方的水平分布挡板13，所述水平分布挡板13上设置有供催化剂通过的孔。本发明对所述水平分布挡板13的数量没有特别的限定，可以为1个，也可以为两个以上，优选分别设置在相邻两个锥型分布挡板12的径向中间位置(且轴向下方位置)。所述径向和轴向指的是轴向移动床反应器1的径向和轴向。
进一步优选地，沿轴向移动床反应器1的中心水平向外方向上，所述水平分布挡板13上的孔逐步变大。采用该种优选实施方式，靠近轴向移动床反应器1的中心位置通过锥型分布挡板12的分散的催化剂部分从所述水平分布挡板13孔通过，部分不能够通过的催化剂被分散至轴向移动床反应器1的边缘位置，更有利于保证催化剂的均匀分散。
进一步优选地，所述水平分布挡板13可为中间区域开孔率低、边壁处开孔率高的圆形分布板。
处于轴向移动床反应器1各催化剂床层中的催化剂随着反应的进行会逐渐失活的同时也会逐渐下落至更下游的催化剂床层(反应床层)或催化剂再生床层，最终到达轴向移动床反应器1底部，随后通过催化剂输送管线输送至待生剂接收器5。
根据本发明的一种优选实施方式，轴向移动床反应器1下部设置有底部催化剂收集区37。通过最下游催化剂床层的催化剂送入底部催化剂收集区37，收集一定量后送至待生剂接收器5。
根据本发明的一种具体实施方式，如图1所示，轴向移动床反应器1与待生剂接收器5、待生剂接收器5与催化剂再生器4、催化剂再生器4与再生剂接收器6、再生剂接收器6与轴向移动床反应器1的连通管线上分别设置有容器间的物料管线阀。
根据本发明的一种优选实施方式，待生剂接收器5(优选底部)设置退液相料出口15。本发明可以在待生剂接收器5中通过直接减压或引入高压氢气、氮气等充压的方式脱除催化剂中携带的液相物料，液相物料可以通过退液相料出口15外输。优选地，从所述退液相料出口15送出的退液相料输送管线上设置有脱液过滤器7。所述脱液过滤器7 用于阻隔催化剂细粉或细小的催化剂颗粒。
待生剂接收器5中脱液后的催化剂送入催化剂再生器4中进行再生。所述催化剂再生器4设置有再生介质进料口30和再生介质出料口31。再生介质通过再生介质进料口30送入催化剂再生器4中与催化剂接触对催化剂进行再生(优选完全再生)，再生介质通过再生介质出料口31外排。优选地，从所述再生介质出料口31送出的再生介质输送管线上设置有再生介质过滤器8。该过滤器用于阻隔再生器的催化剂流入下游的气体循环增压设备以及收集再生过程因摩擦或吹扫产生的细粉或细小颗粒。
根据本发明的方法，对于在催化剂再生器4中的再生的方式没有特别限定，可以在常规的再生条件下进行。所述再生介质可以为含氧气氛或含氢气氛。具体地，所述再生可以在含氢气氛中进行，也可以在含氧气氛中进行。所述含氧气氛含有氧气以及可选的载气，所述载气可以选自非活性气体，其具体实例可以包括但不限于氮气和零族元素气体(如氩气)。所述含氧气氛中，氧气的含量可以为0.5-20体积％。另外，还可以根据再生的进程对氧气的含量进行调整。所述含氢气氛中可以含有氢气和C4液化气，氢气的含量为70-99体积％。
作为在催化剂再生器4中的再生的一个实例，所述再生在氢气气氛中进行，可以在100-400℃、优选180-280℃的温度下进行再生；再生时，反应器内的压力可以为0.1-5MPa，优选为0.5-3.5MPa，所述压力为表压。作为再生的另一个实例，所述再生在含氧气氛中进行，可以在180-500℃的温度下进行再生；再生时，反应器内的压力可以为0.01-0.5MPa，所述压力为表压。
根据本发明，优选地，所述再生介质在催化剂再生器4中的表观流速为0.003-0.8m/s，进一步优选为0.02-0.5m/s。
在本发明中，在催化剂再生器4中的再生也称为高温再生。
根据本发明的一种优选实施方式，该方法还包括：向催化剂再生器4中引入新鲜催化剂。具体地，催化剂再生器4可以设置有新鲜催化剂进料口供新鲜催化剂进入催化剂再生器4中。通过在催化剂再生器4上设置新鲜催化剂进料口，可将部分失去活性的催化剂或难以恢复初始活性的催化剂置换为新鲜催化剂，保证装置的处理能力。具体地，与新鲜催化剂进料口连通的新鲜催化剂输送管线上设置有泵。
再生后的催化剂会通过催化剂再生器4底部的催化剂输送管线流入再生剂接收器6中。
根据本发明的一种优选实施方式，该方法还包括采用液相料置换再生剂接收器6中催化剂间隙的气体。具体地，再生剂接收器6设置有液相料补充入口32。通过液相料补充入口32向再生剂接收器6中引入液相料置换催化剂间隙的气体。本发明对所述液相料没有特别的限定，例如可以为烷烃或轴向移动床反应器1底部得到的反应产物。
再生后的催化剂会通过再生剂接收器6与轴向移动床反应器1间的催化剂输送管道返回轴向移动床反应器1，继续参与反应，直至失活后被输送至待生剂接收器5，催化剂按照上述流程循环。
根据本发明的一种优选实施方式，待生剂接收器5、催化剂再生器4和再生剂接收器6依次自上而下设置，待生剂接收器5、催化剂再生器4和再生剂接收器6之间的催化剂流通管线为垂直设置或与水平面间的夹角不小于40度倾斜设置。采用该种优选实施方式更便于催化剂颗粒料从上而下的顺畅流通，防止物料堆积或残存在管线中，影响阀门密封性或催化剂再生的效果。
根据本发明的一种优选实施方式，轴向移动床反应器1的催化剂出口与待生剂接收器5的催化剂入口的连通管线上设置有第一颗粒流量调节器25；再生剂接收器6的催化剂出口与轴向移动床反应器1的催化剂入口的连通管线上设置有第二颗粒流量调节器33。本发明对所述第一颗粒流量调节器25和第二颗粒流量调节器33没有特别的限定，只要能够调节催化剂颗粒的流量即可。进一步优选地，所述第一颗粒流量调节器25和第二颗粒流量调节器33各自独立地为L型或近似L型的物料输送阀组。具体地，所述L型或近似L型的物料输送阀组上还连通至少一路液相物料进料管线。设置颗粒流量调节器可以增加颗粒物料的流通阻力，同时，在该调节器上连通至少一路的液相物料进料管线，用以增加颗粒物料的流动推动力并降低颗粒物料的流动阻力。通过设置L型或近似L型的物料输送阀组，通过改变进入阀组的液相物料流量可调节催化剂的排出速率，从而达到控制和调节处于反应器中的催化剂在各反应床层的下落速率和停留时间。
根据本发明的一种优选实施方式，该装置还包括催化剂缓冲罐38，所述催化剂缓冲罐38设置在轴向移动床反应器1、待生剂接收器5之 间，催化剂缓冲罐38的催化剂入口与轴向移动床反应器1的催化剂出口连通，催化剂缓冲罐38的催化剂出口与待生剂接收器5的催化剂入口连通。所述催化剂缓冲罐38用以保存待生剂接收器在退液相料以及向催化剂再生剂排催化剂期间从轴向移动床反应器1排出的催化剂，保证轴向移动床反应器1内催化剂物料流动的连续性和装置操作的平稳性。
在本发明的一种实施方案中，所述的轴向移动床反应器包括：
至少一个，优选地，至少两个催化剂床层(亦称为反应床层)和至少一个催化剂再生床层，优选地，反应床层和催化剂再生床层的数目相同并且反应床层51、53和催化剂再生床层52、54间隔依次放置，更优选地，催化剂再生床层比催化剂床层的数目少一个，催化剂床层和催化剂再生床层间隔依次放置，并且轴向移动床反应器的顶端和底端均设置为催化剂反应床层；
轴向移动床反应器具有催化剂入口62，其与第一个反应床层的顶部相通；
每一个反应床层的顶部有催化剂入口和反应物料进料口60，第一个反应床层的催化剂入口就是轴向移动床反应器的催化剂入口，之后的反应床层的催化剂入口与催化剂输送管相通；
每一个反应床层的底部有与催化剂输送管道63、65相通的催化剂出口和反应物料出口59、61；
催化剂再生床层的顶部有与催化剂输送管道63、65相通的催化剂入口和再生介质出口68、71；
催化剂再生床层的底部有与催化剂输送管道64、66相通的催化剂出口和再生介质入口67、69；
所述的催化剂再生床层向反应床层转移催化剂的催化剂输送管线上设置有隔离介质入口70；
每个反应床层的底部设置有分离件72；
各个床层之间通过催化剂输送管线相通；
反应床层底部与再生床层之间通过插入再生床层内部的催化剂输送管道相通，所述的插入式催化剂输送管道的出口低于再生床层中的再生介质出口；
所述的隔离介质优选为反应后经过泵增压的循环料，因此，隔离 介质入口70与最后一段的反应床层的反应物料出口61相通；
反应后物料通过分离件72进入下一段的反应床层或者最终排出，未通过分离件72的催化剂通过催化剂输送管向下移动；
上游的反应床层的反应物料出口59通过管线与下游的反应床层的反应物料进料口60相连通，此连接管线上还设置有新鲜反应原料的入口56、57；
所述的床层的顶部是指处于每一段床层由下至上的70％以上的位置，所述的床层的底部是指处于每一段床层由下至上的20％以下的位置；
上游的催化剂再生床层的再生介质出口68通过管线与下游的催化剂再生床层的再生介质入口69相连通；
反应床层的反应物料进料口60、催化剂再生床层的再生介质入口以及所述的催化剂再生床层向反应床层转移催化剂的催化剂输送管线上设置的隔离介质入口70设置了相应的物料分布器。
在本发明的一种实施方案中，该方法包括：液态新鲜反应原料55与循环料58或上游反应床层反应后物料混合后进入轴向移动床的反应床层；在反应床层中，混合料通过反应物料分布器分布后沿反应床层轴向穿过反应床层，与固体酸催化剂接触并发生反应，反应完毕的大部分液相料(>90vol％，或>95vol％，或>96vol％，或>97vol％，或>98vol％，或>99vol％)通过设置的反应物料出口排出本段，剩余的小部分液相料则跟随催化剂颗粒通过反应床层与催化剂再生床层之间的插入式管道进入催化剂再生床层；排出的反应后液相物料与新鲜反应原料混合后进入下一段反应床层继续参与反应或排出反应床层，经分离(例如蒸馏)后收集烷基化油产品；在催化剂再生床层中，催化剂通过与溶解有氢气的液相再生介质在再生条件下进行逆流接触(在本文中又称为低温再生)，将吸附在催化剂上的不饱和烃类转化为容易脱附的饱和烃分子带出催化剂再生床层，实现催化剂的部分再生；再生后的催化剂会通过催化剂再生床层底部的催化剂输送管线流入下一个反应床层；在催化剂从催化剂再生床层底部向反应床层输送过程中，隔离介质通过设置于输送管线上的隔离介质引入口进入，将与催化剂一起的下行的液相介质置换；处于移动床各床层(反应床层和催化剂再生床层)中的催化剂随着反应的进行以及再生次数的增加失活程度会逐渐增加， 同时也会逐渐下落至更低的床层(反应床层或催化剂再生床层)最终到达移动床反应器的底部；最终催化剂被送至催化剂再生器4(进行高温深度再生)，实现催化剂活性的完全恢复；恢复活性的催化剂被送至移动床反应器的第一段反应床层继续参与反应，如此循环；
在反应床层中的反应条件可以包括：
反应温度为30-100℃，
反应压力为1.0-3.4MPa，表压，
液相物料在反应器内的表观流速为0.03-1m/s；
混合烯烃原料的质量空速为0.05-1h -1；
反应床层入口处的烷烃与烯烃的摩尔比为200-1000:1；
固体酸催化剂颗粒的平均粒径为0.3-3mm。
在催化剂再生床层中的再生条件可以包括：
再生温度为50-140℃，
再生介质在再生器内的表观流速为0.01-0.5m/s；
所述的再生介质为溶解有氢气的液态烃；液态烃为C3-C6(例如C3-C5)的饱和烷烃或反应产物与上述饱和烷烃的混合物，优选的，液态烃为C3-C6(例如C3-C5)的饱和烷烃与反应产物的混合物；
在所述的催化剂再生器(高温深度再生)中的再生条件可以包括：
再生温度为180-400℃，
再生压力为0.5-4.0MPa，
再生介质为氢气或氢气和低碳烃(如C3-C8)的混合物，优选氢气和低碳烃(如C3-C8)的混合物；
所述催化剂的主要活性组分为负载有一定量金属的分子筛，所述分子筛为FAU结构沸石、BETA结构沸石、MFI结构沸石及其中的一种或几种的组合，优选为具有FAU结构和BETA结构沸石，所述催化剂上负载的金属为Fe、Co、Ni、Pd和(或)Pt中的一种或几种的组合，优选为Co、Ni或Pt的一种或几种的组合。
本发明提供的方法采用液固轴向移动床反应与再生装置，可以实现固体酸烷基化反应与失活催化剂再生的连续平稳运行，提高了目标产物的选择性和装置操作的弹性，大大降低了催化剂投资成本，提高了装置的经济竞争力。
另外，本发明提供了一组下列技术方案：
1、一种液固轴向移动床反应与再生装置，其特征在于，该装置包括：
依次连接的轴向移动床反应器、待生剂接收器、催化剂再生器和再生剂接收器，其中，再生剂接收器的催化剂出口与轴向移动床反应器的催化剂入口连通；
其中，轴向移动床反应器设置有至少两个上下放置的催化剂床层，轴向移动床反应器在每个催化剂床层的上方设置有进料口；
相邻两个催化剂床层之间设置有催化剂输送管使得催化剂能够在轴向移动床反应器中自上而下移动。
2、根据技术方案1所述的液固轴向移动床反应与再生装置，其中，轴向移动床反应器的反应物料出口与轴向移动床反应器的最上方的进料口连通以将轴向移动床反应器得到的反应物料循环回轴向移动床反应器。
3、根据技术方案1所述的液固轴向移动床反应与再生装置，其中，
相邻两个催化剂床层之间设置有分离件，所述分离件与催化剂输送管连通，所述分离件用于上游催化剂床层反应后物料和催化剂的分离，分离件分离得到的催化剂通过催化剂输送管向下移动。
4、根据技术方案1-3中任意一项所述的液固轴向移动床反应与再生装置，其中，相邻两个催化剂床层之间设置有反应物料折流件，所述反应物料折流件用于强化反应后物料和进料口送入的液态新鲜原料的混合。
5、根据技术方案4所述的液固轴向移动床反应与再生装置，其中，所述反应物料折流件包括主轴(111)和沿主轴轴向螺旋延伸的输送部件(112)。
6、根据技术方案4所述的液固轴向移动床反应与再生装置，其中，所述反应物料折流件包括多个折流板(113)，多个折流板(113)沿轴向移动床反应器的轴向倾斜设置，且多个折流板(113)相互之间交错设置以形成能够供反应物料通过的流道。
7、根据技术方案1-6中任意一项所述的液固轴向移动床反应与再生装置，其中，相邻两个催化剂床层之间设置有催化剂分布件，所述催化剂分布件用于分散催化剂输送管出口的催化剂；
优选地，所述催化剂分布件包括锥型分布挡板，所述锥型分布挡板与催化剂输送管同轴设置；进一步优选地，锥型分布挡板与催化剂输送管的数量相同；
进一步优选地，所述催化剂分布件还包括设置在所述锥型分布挡板下方的水平分布挡板，所述水平分布挡板上设置有供催化剂通过的孔。
8、根据技术方案1-7中任意一项所述的液固轴向移动床反应与再生 装置，其中，催化剂再生器设置有新鲜催化剂进料口供新鲜催化剂进入催化剂再生器中。
9、根据技术方案1-8中任意一项所述的液固轴向移动床反应与再生装置，其中，待生剂接收器、催化剂再生器和再生剂接收器依次自上而下设置，待生剂接收器、催化剂再生器和再生剂接收器之间的催化剂流通管线为垂直设置或与水平面间的夹角不小于40度倾斜设置。
10、根据技术方案1-9中任意一项所述的液固轴向移动床反应与再生装置，其中，轴向移动床反应器的催化剂出口与待生剂接收器的催化剂入口的连通管线上设置有第一颗粒流量调节器；再生剂接收器的催化剂出口与轴向移动床反应器的催化剂入口的连通管线上设置有第二颗粒流量调节器；
优选地，所述第一颗粒流量调节器和第二颗粒流量调节器各自独立地为L型或近似L型的物料输送阀组。
11、根据技术方案1-10中任意一项所述的液固轴向移动床反应与再生装置，其中，该装置还包括催化剂缓冲罐，所述催化剂缓冲罐设置在轴向移动床反应器、待生剂接收器之间，催化剂缓冲罐的催化剂入口与轴向移动床反应器的催化剂出口连通，催化剂缓冲罐的催化剂出口与待生剂接收器的催化剂入口连通。
12、技术方案1-11中任意一项所述的液固轴向移动床反应与再生装置在固体酸烷基化反应中的应用。
另外，本发明提供了又一组下列技术方案：
1、一种固体酸烷基化方法，包括：
该方法在液固轴向移动床反应与再生装置中进行，液固轴向移动床反应与再生装置包括依次连接的轴向移动床反应器、待生剂接收器、催化剂再生器和再生剂接收器，其中，再生剂接收器的催化剂出口与轴向移动床反应器的催化剂入口连通；轴向移动床反应器设置有至少两个上下放置的催化剂床层，轴向移动床反应器在每个催化剂床层的上方设置有进料口；相邻两个催化剂床层之间设置有催化剂输送管使得催化剂能够在轴向移动床反应器中自上而下移动；
液相原料从每个催化剂床层上方设置的进料口送入轴向移动床反应器中与催化剂接触反应。
2、根据技术方案1所述的方法，其中，该方法还包括：将轴向移动床反应器底部得到的反应产物循环至最上游催化剂床层的上方与所述液相原料混合后进料。
3、根据技术方案1或2所述的方法，其中，轴向移动床反应器中的反应温度为30-100℃，压力为1-3.4MPa；
优选地，以烯烃计的进入各催化剂床层的物料的质量空速为0.05-1h -1；
优选地，进入各催化剂床层的物料的异构烷烃和烯烃的摩尔比为200-1000:1；
优选地，催化剂在轴向移动床反应器中的停留时间为6-72h。
4、根据技术方案1-3中任意一项所述的方法，其中，所述催化剂为固体酸催化剂，所述固体酸催化剂含有分子筛和耐热无机氧化物，以所述固体酸催化剂的总量为基准，分子筛的含量为65-95重量％，耐热无机氧化物的含量为5-35重量％；
优选地，所述分子筛选自FAU结构沸石、BETA结构沸石和MFI结构沸石中至少一种，所述耐热无机氧化物为氧化铝和/或氧化硅；
进一步优选地，所述固体酸催化剂还含有金属活性组分，所述金属活性组分选自Fe、Co、Ni、Pd和Pt中至少一种，以所述固体酸催化剂的总量为基准，金属活性组分的含量为0.15-2重量％。
5、根据技术方案1-4中任意一项所述的方法，其中，相邻两个催化剂床层之间设置有分离件，所述分离件与催化剂输送管连通，所述分离件用于上游催化剂床层反应后物料和催化剂的分离，分离件分离得到的催化剂通过催化剂输送管向下移动。
6、根据技术方案1-5中任意一项所述的方法，其中，相邻两个催化剂床层之间设置有反应物料折流件，所述反应物料折流件用于强化反应后物料和进料口送入的液态新鲜原料的混合；
优选地，所述反应物料折流件包括主轴(111)和沿主轴轴向螺旋延伸的输送部件(112)；
优选地，所述反应物料折流件包括多个折流板(113)，多个折流板(113)沿轴向移动床反应器的轴向倾斜设置，且多个折流板(113)相互之间交错设置以形成能够供反应物料通过的流道。
7、根据技术方案1-6中任意一项所述的方法，其中，相邻两个催化剂床层之间设置有催化剂分布件，所述催化剂分布件用于分散催化剂输送管出口的催化剂；
优选地，所述催化剂分布件包括锥型分布挡板，所述锥型分布挡板与催化剂输送管同轴设置；进一步优选地，锥型分布挡板与催化剂输送管的数量相同；
进一步优选地，所述催化剂分布件还包括设置在所述锥型分布挡板 下方的水平分布挡板，所述水平分布挡板上设置有供催化剂通过的孔。
8、根据技术方案1-7中任意一项所述的方法，其中，轴向移动床反应器底部的催化剂输送至待生剂接收器中脱除催化剂中携带的液相物料，然后输送至催化剂再生器中进行再生；
优选地，所述再生介质在催化剂再生器中的表观流速为0.003-0.8m/s，进一步优选为0.02-0.5m/s。
9、根据技术方案1-8中任意一项所述的方法，其中，催化剂再生器设置有新鲜催化剂进料口供新鲜催化剂进入催化剂再生器中。
10、根据技术方案1-9中任意一项所述的方法，其中，待生剂接收器、催化剂再生器和再生剂接收器依次自上而下设置，待生剂接收器、催化剂再生器和再生剂接收器之间的催化剂流通管线为垂直设置或与水平面间的夹角不小于40度倾斜设置。
11、根据技术方案1-10中任意一项所述的方法，其中，轴向移动床反应器的催化剂出口与待生剂接收器的催化剂入口的连通管线上设置有第一颗粒流量调节器；再生剂接收器的催化剂出口与轴向移动床反应器的催化剂入口的连通管线上设置有第二颗粒流量调节器；
优选地，所述第一颗粒流量调节器和第二颗粒流量调节器各自独立地为L型或近似L型的物料输送阀组。
12、根据技术方案1-11中任意一项所述的方法，其中，该装置还包括催化剂缓冲罐，所述催化剂缓冲罐设置在轴向移动床反应器、待生剂接收器之间，催化剂缓冲罐的催化剂入口与轴向移动床反应器的催化剂出口连通，催化剂缓冲罐的催化剂出口与待生剂接收器的催化剂入口连通。
以下结合附图，举例说明本发明提供的液固轴向移动床反应与再生装置以及固体酸烷基化方法的具体实施方式，但本发明并不限于此。
如图1所示，轴向移动床反应器1中设置有三个催化剂床层3，待生剂接收器5、催化剂再生器4和再生剂接收器6依次自上而下设置，且三者之间的催化剂流通管线为垂直设置。
含有异丁烷的新鲜烯烃原料自管线17引入，通过第一分支管线19与循环料混合后从进料口2进入轴向移动床反应器1的反应区与第一个催化剂床层3接触反应，通过第二分支管线20和第三分支管线21的新鲜烯烃原料从进料口2送入并且与上游催化剂床层的反应后物料 在轴向移动床反应器1的反应床层前的床层空间中进行混合。
相邻两个催化剂床层3之间设置有分离件10，反应后物料通过分离件10，未通过分离件10的催化剂通过催化剂输送管16向下移动。
相邻两个催化剂床层3之间设置反应物料折流件11，通过分离件10的反应后物料以及新鲜反应原料在反应物料折流件11作用下强化混合。
相邻两个催化剂床层3之间还设置有催化剂分布件(包括与催化剂输送管16同轴设置的锥型分布挡板12和设置在所述锥型分布挡板12下方的水平分布挡板13)，催化剂输送管16出口的催化剂在催化剂分布件作用下分散下落至下游催化剂床层3。
轴向移动床反应器1的下部设置有底部催化剂收集区37。通过最下游催化剂床层的催化剂送入底部催化剂收集区37，收集一定量后送至待生剂接收器5。
轴向移动床反应器1的催化剂出口与待生剂接收器5的催化剂入口的连通管线上设置有第一颗粒流量调节器25，以调节催化剂颗粒流量。
待生剂接收器5底部设置退液相料出口15，在待生剂接收器5中脱除催化剂中携带的液相物料，从所述退液相料出口15送出的退液相料输送管线上设置脱液过滤器7以阻隔催化剂细粉或细小的催化剂颗粒。
待生剂接收器5中脱液后的催化剂送入催化剂再生器4中进行再生，所述催化剂再生器4设置有再生介质进料口30和再生介质出料口31。再生介质通过再生介质进料口30送入催化剂再生器4中与催化剂接触对催化剂进行再生，再生介质通过再生介质出料口31外排。从所述再生介质出料口31送出的再生介质输送管线上设置再生介质过滤器8以阻隔细粉或细小颗粒。催化剂再生器4还可以设置有新鲜催化剂进料口供新鲜催化剂进入催化剂再生器4中。通过在催化剂再生器4上设置新鲜催化剂进料口，可将部分失去活性的催化剂或难以恢复初始活性的催化剂置换为新鲜催化剂，保证装置的处理能力。
再生后的催化剂通过催化剂再生器4底部的催化剂输送管线流入再生剂接收器6，再生剂接收器6设置有液相料补充入口32。通过液相料补充入口32向再生剂接收器6中引入液相料置换催化剂间隙的气 体。
再生后的催化剂会通过再生剂接收器6与轴向移动床反应器1间的催化剂输送管道返回轴向移动床反应器1继续参与反应，直至失活后被输送至待生剂接收器5，催化剂按照上述流程循环。再生剂接收器6的催化剂出口与轴向移动床反应器1的催化剂入口的连通管线上设置有第二颗粒流量调节器33，以调节催化剂颗粒流量。
如图4所示，在本发明的液固轴向移动床反应与再生装置中，轴向移动床反应器包括间隔依次放置的反应床层51、53和催化剂再生床层52、54；
轴向移动床反应器具有催化剂入口62，其与第一个反应床层的顶部相通；
反应床层的顶部有催化剂入口反应物料进料口60；
反应床层的底部有与催化剂输送管道63、65相通的催化剂出口和反应物料出口59、61；
催化剂再生床层的顶部有与催化剂输送管道63、65相通的催化剂入口和再生介质出口68、71；
催化剂再生床层的底部有与催化剂输送管道64、66相通的催化剂出口和再生介质引入口67、69；
所述的催化剂再生床层向反应床层转移催化剂的催化剂输送管线上设置有隔离介质引入口70；
每个反应床层的底部设置有分离件72；
各个床层之间通过催化剂输送管线相通；
反应床层底部与再生床层之间通过插入再生床层内部的催化剂输送管道相通，所述的插入式催化剂输送管道的出口低于再生床层中的再生介质出口；
所述的隔离介质优选为反应后经过泵增压的循环料，因此，隔离介质入口70与最后一段的反应床层的反应物料出口61相通；
反应后物料通过分离件72进入下一段的反应床层或者最终排出，未通过分离件72的催化剂通过催化剂输送管向下移动；
上游的反应床层的反应物料出口59通过管线与下游的反应床层的反应物料进料口60相连通，此连接管线上还设置有新鲜反应原料的入口56、57；
所述的床层的顶部是指处于每一段床层由下至上的70％以上的位置，所述的床层的底部是指处于每一段床层由下至上的20％以下的位置；
上游的催化剂再生床层的再生介质出口68通过管线与下游的催化剂再生床层的再生介质引入口69相连通；
反应床层的反应物料进料口60、催化剂再生床层的再生介质入口以及所述的催化剂再生床层向反应床层转移催化剂的催化剂输送管线上设置的隔离介质入口70设置了相应的物料分布器。
本发明提供的一种固体酸烷基化反应与临氢再生方法，液态新鲜反应原料与循环料或上游反应床层反应后物料混合后进入轴向移动床的反应床层；在反应床层中，混合料通过反应物料分布器分布后沿反应床层轴向穿过反应床层，与固体酸催化剂接触并发生反应，反应完毕的大部分(>90vol％，或>95vol％，或>96vol％，或>97vol％，或>98vol％，或>99vol％)液相料通过设置的反应物料出口排出本段，剩余的小部分液相料则跟随催化剂颗粒通过反应床层与催化剂再生床层之间的插入式管道进入催化剂再生床层；排出的反应后液相物料与新鲜反应原料混合后进入下一段反应床层继续参与反应或排出反应床层，经分离(例如蒸馏)后收集烷基化油产品。在催化剂再生床层中，催化剂通过与溶解有氢气的液相再生介质在再生条件下进行逆流接触，将吸附在催化剂上的不饱和烃类转化为容易脱附的饱和烃分子带出催化剂再生床层，实现催化剂的部分再生；再生后的催化剂会通过催化剂再生床层底部的催化剂输送管线流入下一个反应床层；在催化剂从催化剂再生床层底部向反应床层输送过程中，隔离介质通过设置于输送管线上的隔离介质引入口进入，将与催化剂一起的下行的液相介质置换；处于移动床各床层(反应床层和催化剂再生床层)中的催化剂随着反应的进行以及再生次数的增加失活程度会逐渐增加，同时也会逐渐下落至更低的床层(反应床层或催化剂再生床层)最终到达移动床反应器的底部；最终催化剂被送至催化剂再生器4(进行高温深度再生)，实现催化剂活性的完全恢复；恢复活性的催化剂被送至移动床反应器的第一段反应床层继续参与反应，如此循环。
以下将通过实施例对本发明进行详细描述。
实施例1
本实施例在图1所示的液固轴向移动床反应与再生装置上进行。其中，轴向移动床反应器1、待生剂接收器5、催化剂再生器4和再生剂接收器6通过管线依次连接。
轴向移动床反应器1的内径为600mm，从上至下设置三段催化剂床层3(分别记为第一催化剂床层、第二催化剂床层、第三催化剂床层)，每段反应床层的高度为1.8m。
第一催化剂床层、第二催化剂床层之间以及第二催化剂床层、第三催化剂床层之间各设置2个圆柱形催化剂输送管16，催化剂输送管16的内径为20mm。第一催化剂床层下方、第二催化剂床层下方分别设置有分离件10(缝隙宽度为0.2mm的楔形滤网)。第一催化剂床层、第二催化剂床层之间以及第二催化剂床层、第三催化剂床层之间各设置1个如图2所示的反应物料折流件11，所述反应物料折流件11包括主轴111和沿主轴轴向螺旋延伸的输送部件112，输送部件112形成的螺旋延伸的流道的入口位于第二分支管线20和第三分支管线21的新鲜烯烃原料的进料口2的下方。反应物料折流件11设置于催化剂输送管16所在中心区域与反应器壁之间的环隙空间。
第一催化剂床层、第二催化剂床层之间以及第二催化剂床层、第三催化剂床层之间各自还设置有3个与催化剂输送管16同轴设置的锥型分布挡板12(高度为0.1m)，3个设置在所述锥型分布挡板12下方的水平分布挡板13(圆形分布板)，水平分布挡板13上设置有供催化剂通过的孔，沿轴向移动床反应器1的中心水平向外方向上，所述水平分布挡板13上的孔逐步变大，最大的孔孔径设置为25mm，最小的孔孔径设置为5mm。轴向移动床反应器1下部设置有底部催化剂收集区37。
待生剂接收器5、催化剂再生器4和再生剂接收器6依次自上而下设置，待生剂接收器5、催化剂再生器4和再生剂接收器6之间的催化剂流通管线为垂直设置。待生剂接收器5、催化剂再生器4和再生剂接收器6的直径均为1200mm，直管段高均为6m。物料循环管线的直径为250mm。
反应新鲜反应原料为异丁烷、正丁烷和丁烯等的混合物。从新鲜料进料管线17进料后，分为三路进入各自对应的催化剂床层3。
进入各催化剂床层3的混合后物料的烷烯摩尔比为700:1，在反应器内循环物料的流速为0.28m/s，相应的新鲜料总进料量为482kg/h，混合烯烃原料的质量空速为0.25h -1。
催化剂在轴向移动床反应器1中的停留时间为72h。
使用的催化剂为FAU结构分子筛球形催化剂，平均粒径为1.8mm。其制备方法为采用中国石化催化剂分公司生产的FAU结构的NaY型分子筛，通过离子交换等步骤去除分子筛上的钠离子；然后将分子筛与和氧化铝以65：35的重量比例混合均匀，采用油氨柱成型法制成小球，进一步经干燥、焙烧制得所述催化剂。
轴向移动床反应器1中的反应温度为70℃，反应压力为2.5MPa。
新鲜料和循环料混合从进料口2送入轴向移动床反应器1中与第一催化剂床层装填的催化剂进行接触反应，分离件10分离得到的反应后物料经与来自第一分支管线19的新鲜料经过折流件11的强化混合送入第二催化剂床层进行反应，分离件10分离得到的催化剂通过催化剂输送管16在催化剂分布件作用下分散下落至下游催化剂床层，最后催化剂下落至底部催化剂收集区37。底部催化剂收集区37得到的催化剂通过催化剂出口送至待生剂接收器5。轴向移动床反应器1的催化剂出口与待生剂接收器5的催化剂入口的连通管线上设置有第一颗粒流量调节器25(L型的物料输送阀组)，且L型的物料输送阀组上还连通一路液相物料进料管线以控制催化剂浆料的流量(20kg/h)。向待生剂接收器5中通入氮气以脱除催化剂中携带的液相物料，液相物料通过退液相料出口15外输，从所述退液相料出口15送出的退液相料输送管线上设置有脱液过滤器7。
待生剂接收器5中脱液后的催化剂送入催化剂再生器4中进行再生，采用氮气和空气的混合气(氧气的体积浓度为1-21体积％从小至大调整，表观气速为0.1m/s)作为催化剂高温深度再生介质，高温(350-480℃从小至大调整)、常压深度再生的周期为24h，所述混合气通过再生介质进料口30送入，再生介质通过再生介质出料口31外排，从所述再生介质出料口31送出的再生介质输送管线上设置有再生介质过滤器8。催化剂再生器4还可以设置有新鲜催化剂进料口供新鲜催化剂进入催化剂再生器4中。
再生后的催化剂会通过催化剂再生器4底部的催化剂输送管线流 入再生剂接收器6中。再生剂接收器6设置有液相料补充入口32，通过液相料补充入口32向再生剂接收器6中引入反应后含油液相物料置换催化剂间隙的气体，得到的催化剂浆料循环至轴向移动床反应器1顶部。再生剂接收器6的催化剂出口与轴向移动床反应器1的催化剂入口的连通管线上设置有第二颗粒流量调节器33(L型的物料输送阀组)，且L型的物料输送阀组上还连通一路液相物料进料管线以控制催化剂浆料的流量(20kg/h)。
实施例2
在如图3所示的装置上进行固体酸烷基化反应。与实施例1的区别仅在于该装置在轴向移动床反应器1、待生剂接收器5之间还设置有直径为500mm，直管段高为4.2m的催化剂料缓冲罐38。
该实施例增加了催化剂料缓冲罐38保证了待生剂接收器在进行脱液操作和向再生器内转移催化剂时，反应器内的催化剂仍旧保持原有的速度向下缓慢移动，待上述操作完成后，逐步将催化剂缓冲罐内积累的催化剂排至待生剂接收器，保证轴向移动床反应器1内催化剂物料流动的连续性和装置操作的平稳性。
实施例3
在图1所示的装置上进行固体酸烷基化反应。不同的是，将图2所示的反应物料折流件11替换为如图1所述反应物料折流件11，反应物料折流件11包括8个平行且交错设置的折流板113，折流板113的延伸方向与水平面的夹角为25度，折流板113沿轴向移动床反应器1的轴向倾斜向上设置，4个折流板113固定连接于轴向移动床反应器1的器壁，4个折流板113固定连接于催化剂输送管16的管壁，相邻折流板113之间的距离为25mm。
实施例4
本实施例在图4所示的液固轴向移动床反应器中进行，其中所使用的待生剂接收器、催化剂再生器、再生剂接收器和其他未提及的设备与实施例1中的相同或近似。
轴向移动床反应器的壳体内径为600mm，包括2个反应床层和2个再生催化剂床层，每段床层的高度为1.8m，依次间隔设置。
催化剂再生床层顶部设置的再生介质出口处于催化剂再生床层由下至上的85％的位置，再生介质入口处于催化剂再生床层由下至上的5％位置。插入式管道的出口处于催化剂再生床层由下至上的80％的位置。
反应新鲜原料与实施例1中使用的相同。从新鲜料进料管线进料后，分为两路与循环物料或上游反应后液相物料混合后进入各自对应的反应床层。
混合后物料在反应器内分布区的烷烯摩尔比为700±100:1，混合烯烃原料的质量空速为0.25h -1。
使用与实施例1相同的催化剂。
反应床层中的反应温度为70℃，反应压力为2.5MPa。
在催化剂再生床层中，采用溶解有氢气的含有部分烷油的反应后液相物料作为催化剂的再生介质，再生温度、压力等条件与反应温度、压力等条件相近。
控制催化剂在轴向移动床反应器中的总停留时间为168h。
最终失去活性的催化剂被引入高温深度再生系统中，在再生温度为280℃，再生压力为2.5MPa下采用含有部分低碳烃的氢气进行深度再生，以完全恢复催化剂活性。
恢复活性后的催化剂被重新引至反应器顶部的新鲜催化剂进料口继续参与反应，如此循环。
对比例1
在两台并联的固定床中型试验装置上进行固体酸烷基化反应，具体操作过程为，当第一台反应器处于烷基化反应时，第二台反应器进行高温深度再生操作，两台并联的固定床反应器切换使用，进而使得装置可以连续稳定运行。每个固定床反应器的内径为200mm，高2500mm。反应器内装填的催化剂制备方法与实施例1中相同，区别仅为小球的直径为2.7mm，装填量为28kg，装填高度为1500mm。反应原料与实施例1相同，反应器内的烷烯摩尔比为800:1，新鲜混合烯烃的进料量为6.3kg/h，相对于烯烃的质量空速为0.09h -1。每隔24h需要对床层内的催化剂进行一次高温深度再生，采用氮气和空气的混合气(与实施例1相同)在温度从常温升高到480℃，常压下对床层内的催化剂进行高温氧化再生3h，再生后需要对床层进行冷却操作，整个再 生周期24h。再生结束后将处于反应状态的反应器内物料退至再生完毕的反应器，继续用再生后催化剂开展烷基化反应实验，而将退完反应物料的反应器切入再生操作，如此反复循环。
上述实施例和对比例的装置连续稳定运行1000h后，对所得的烷基化油进行测定，试验结果如表1所示。
表1
Figure PCTCN2019112517-appb-000001
从表1中可以看出，采用本发明提供的固体酸烷基化方法或装置所得的烷基化油的辛烷值略优于固定床技术，烷基化油中的烯烃收率更高，且具有更高的目标产物(三甲基戊烷)选择性，C9+产物的收率也更低。
相比于实施例1，带有催化剂缓冲罐的实施例2，具有更优的产品收率和目标产物选择性。
从装置运行角度来看，对于固定床烷基化技术，为了实现反应装置的连续稳定运行，至少需要两台以上的反应器切换操作(如对比例1)，每隔一定时间(24小时)对床层内的催化剂进行高温再生，深度再生后还要对高温床层进行降温操作，由于装置频繁的在反应与再生温度之间进行切换，使得其在工业应用中连续稳定运行时带来了很多问题，而本发明提供的装置和方法单台(套)设备即可满足要求，减少了装置的投资成本，另外通过将失活的催化剂颗粒引出液固轴向移动反应器外进行深度再生，在不影响反应装置稳定运行的前提下，实现了催化剂反应和再生的连续化操作，维持了装置内的催化剂具有较为稳定的平衡活性，提高了烷基化油中目标产物的选择性。
特别地从实施例4可以看出，反应床层和催化剂再生床层依次间隔设置的轴向移动床技术所得的烷基化油的辛烷值略优于固定床技术，烷基化油中的烯烃收率更高，且具有更高的目标产物(三甲基戊烷) 选择性，C9+产物的收率也更低，催化剂的停留时间延长至一周，说明反应床层和催化剂再生床层依次间隔设置的轴向移动床技术具有更高的技术优势。通过将失活的催化剂颗粒引出反应器外进行深度再生，在不影响反应装置稳定运行的前提下，实现了催化剂反应和再生的连续化操作，维持了装置内的催化剂具有较为稳定的平衡活性，提高了烷基化油中目标产物的选择性和装置操作的弹性，降低了催化剂高温深度再生的频次，提高了装置的经济竞争力。
因此本发明所提供的轴向移动床固体酸烷基化技术具有更好的工业应用前景。
以上详细描述了本发明的优选实施方式，但是，本发明并不限于此。在本发明的技术构思范围内，可以对本发明的技术方案进行多种简单变型，包括各个技术特征以任何其它的合适方式进行组合，这些简单变型和组合同样应当视为本发明所公开的内容，均属于本发明的保护范围。

Claims (24)

  1. 一种液固轴向移动床反应与再生装置，其特征在于，该装置包括：
    依次连接的轴向移动床反应器(1)、待生剂接收器(5)、催化剂再生器(4)和再生剂接收器(6)，其中，再生剂接收器(6)的催化剂出口与轴向移动床反应器(1)的催化剂入口连通；
    其中，轴向移动床反应器(1)设置有至少两个上下放置的催化剂床层(3)，轴向移动床反应器(1)在每个催化剂床层(3)的上方设置有进料口(2)；
    相邻两个催化剂床层(3)之间设置有催化剂输送管(16)使得催化剂能够在轴向移动床反应器(1)中自上而下移动；
    相邻两个催化剂床层(3)之间，设置有分离件(10)，所述分离件(10)与催化剂输送管(16)连通，所述分离件(10)用于上游催化剂床层反应后物料和催化剂的分离，分离件(10)分离得到的催化剂通过催化剂输送管(16)向下移动。
  2. 根据权利要求1所述的液固轴向移动床反应与再生装置，其中，轴向移动床反应器(1)的最后一个催化剂床层的反应物料出口与轴向移动床反应器(1)的第一个催化剂床层的的进料口(2)连通以将轴向移动床反应器(1)得到的反应物料循环回轴向移动床反应器(1)。
  3. 根据权利要求1-2中任意一项所述的液固轴向移动床反应与再生装置，其中，
    所述的轴向移动床反应器还包括至少一个催化剂再生床层，优选地，催化剂床层和催化剂再生床层的数目相同并且催化剂床层和催化剂再生床层间隔依次放置，更优选地，催化剂再生床层比催化剂床层的数目少一个，催化剂床层和催化剂再生床层间隔依次放置，并且轴向移动床反应器的顶端和底端均设置为催化剂反应床层；
    轴向移动床反应器具有催化剂入口，其与第一个催化剂床层的顶部相通；
    每一个催化剂床层的顶部有催化剂入口和反应物料进料口，第一个反应床层的催化剂入口就是轴向移动床反应器的催化剂入口，之后的反应床层的催化剂入口与催化剂输送管相通；
    每一个催化剂床层的底部有与催化剂输送管道相通的催化剂出口和反应物料出口；
    催化剂再生床层的顶部有与催化剂输送管道相通的催化剂入口和再生介质出口；
    催化剂再生床层的底部有与催化剂输送管道相通的催化剂出口和再生介质入口；
    所述的催化剂再生床层向催化剂床层转移催化剂的催化剂输送管线上设置有隔离介质入口；
    每个催化剂床层的底部设置有分离件；
    各个床层之间通过催化剂输送管线相通；
    催化剂床层底部与再生床层之间通过插入再生床层内部的催化剂输送管道相通，所述的插入式催化剂输送管道的出口低于再生床层中的再生介质出口；
    隔离介质入口与最后一段的催化剂床层的反应物料出口相通，以将泵增压后的反应物料作为隔离介质使用；
    上游的催化剂床层的反应物料出口与下游的催化剂床层的反应物料进料口相连通，任选地，通过连接管线相连通，在此连接管线上还可以设置有新鲜反应原料的入口；
    上游的催化剂再生床层的再生介质出口可以通过管线与下游的催化剂再生床层的再生介质入口相连通；
    相邻两个催化剂床层(3)之间以及如果催化剂再生床层作为最后一段床层存在的话，在上游的催化剂床层与最后一段的催化剂再生床层之间，设置有分离件(10)，所述分离件(10)内侧空间与催化剂输送管(16)连通，所述分离件(10)用于上游催化剂床层反应后物料和催化剂的分离，分离件(10)分离得到的催化剂通过催化剂输送管(16)向下移动。
  4. 根据权利要求1-3中任意一项所述的液固轴向移动床反应与再生装置，其中，相邻两个催化剂床层(3)之间以及如果有的话，在上游的催化剂床层与最后一段的催化剂再生床层之间设置有反应物料折流件(11)，所述反应物料折流件(11)用于强化反应后物料和进料口(2)送入的液态新鲜反应原料的混合。
  5. 根据权利要求4所述的液固轴向移动床反应与再生装置，其中， 所述反应物料折流件(11)包括主轴(111)和沿主轴轴向螺旋延伸的输送部件(112)。
  6. 根据权利要求4或5所述的液固轴向移动床反应与再生装置，其中，所述反应物料折流件(11)包括多个折流板(113)，多个折流板(113)沿轴向移动床反应器(1)的轴向倾斜设置，且多个折流板(113)相互之间交错设置以形成能够供反应物料通过的流道。
  7. 根据权利要求1-6中任意一项所述的液固轴向移动床反应与再生装置，其中，相邻两个催化剂床层(3)之间以及如果存在催化剂再生床层的话，在相邻的两个床层之间设置有催化剂分布件，所述催化剂分布件用于分散催化剂输送管(16)出口的催化剂；
    优选地，所述催化剂分布件包括锥型分布挡板(12)，所述锥型分布挡板(12)与催化剂输送管(16)同轴设置；进一步优选地，锥型分布挡板(12)与催化剂输送管(16)的数量相同；
    进一步优选地，所述催化剂分布件还包括设置在所述锥型分布挡板(12)下方的水平分布挡板(13)，所述水平分布挡板(13)上设置有供催化剂通过的孔。
  8. 根据权利要求1-7中任意一项所述的液固轴向移动床反应与再生装置，其中，催化剂再生器(4)设置有新鲜催化剂进料口供新鲜催化剂进入催化剂再生器(4)中。
  9. 根据权利要求1-8中任意一项所述的液固轴向移动床反应与再生装置，其中，待生剂接收器(5)、催化剂再生器(4)和再生剂接收器(6)依次自上而下设置，待生剂接收器(5)、催化剂再生器(4)和再生剂接收器(6)之间的催化剂流通管线为垂直设置或与水平面间的夹角不小于40度倾斜设置。
  10. 根据权利要求1-9中任意一项所述的液固轴向移动床反应与再生装置，其中，轴向移动床反应器(1)的催化剂出口与待生剂接收器(5)的催化剂入口的连通管线上设置有第一颗粒流量调节器(25)；再生剂接收器(6)的催化剂出口与轴向移动床反应器(1)的催化剂入口的连通管线上设置有第二颗粒流量调节器(33)；
    优选地，所述第一颗粒流量调节器(25)和第二颗粒流量调节器(33)各自独立地为L型或近似L型的物料输送阀组。
  11. 根据权利要求1-10中任意一项所述的液固轴向移动床反应与 再生装置，其中，该装置还包括催化剂缓冲罐(38)，所述催化剂缓冲罐(38)设置在轴向移动床反应器(1)、待生剂接收器(5)之间，催化剂缓冲罐(38)的催化剂入口与轴向移动床反应器(1)的催化剂出口连通，催化剂缓冲罐(38)的催化剂出口与待生剂接收器(5)的催化剂入口连通。
  12. 一种固体酸烷基化方法，包括：
    该方法在权利要求1-11中所述的液固轴向移动床反应与再生装置中进行，液相原料从每个催化剂床层上方设置的进料口送入轴向移动床反应器中与催化剂接触反应。
  13. 根据权利要求12所述的方法，其中，该方法还包括：将轴向移动床反应器(1)底部得到的反应产物循环至最上游催化剂床层的上方与所述液相原料混合后进料。
  14. 根据权利要求12-13中任意一项所述的方法，其中，轴向移动床反应器中的反应温度为30-100℃，压力为1-3.4MPa；
    优选地，以烯烃计的进入各催化剂床层的物料的质量空速为0.05-1h -1；
    优选地，进入各催化剂床层的物料的异构烷烃和烯烃的摩尔比为200-1000:1；
    优选地，催化剂在轴向移动床反应器中的停留时间为6-72h。
  15. 根据权利要求12-14中任意一项所述的方法，其中，所述催化剂为固体酸催化剂，所述固体酸催化剂含有分子筛和耐热无机氧化物，以所述固体酸催化剂的总量为基准，分子筛的含量为65-95重量％，耐热无机氧化物的含量为5-35重量％；
    优选地，所述分子筛选自FAU结构沸石、BETA结构沸石和MFI结构沸石中至少一种，所述耐热无机氧化物为氧化铝和/或氧化硅；
    进一步优选地，所述固体酸催化剂还含有金属活性组分，所述金属活性组分选自Fe、Co、Ni、Pd和Pt中至少一种，以所述固体酸催化剂的总量为基准，金属活性组分的含量为0.15-2重量％。
  16. 根据权利要求12-15中任意一项所述的方法，其中，相邻两个催化剂床层(3)之间设置有分离件(10)，所述分离件(10)内侧空间与催化剂输送管(16)连通，所述分离件(10)用于上游催化剂床层反应后物料和催化剂的分离，分离件(10)分离得到的催化剂通过 催化剂输送管(16)向下移动。
  17. 根据权利要求12-16中任意一项所述的方法，其中，相邻两个催化剂床层(3)之间设置有反应物料折流件(11)，所述反应物料折流件(11)用于强化反应后物料和进料口(2)送入的液态新鲜反应原料的混合；
    优选地，所述反应物料折流件(11)包括主轴(111)和沿主轴轴向螺旋延伸的输送部件(112)；
    优选地，所述反应物料折流件(11)包括多个折流板(113)，多个折流板(113)沿轴向移动床反应器(1)的轴向倾斜设置，且多个折流板(113)相互之间交错设置以形成能够供反应物料通过的流道。
  18. 根据权利要求12-17中任意一项所述的方法，其中，相邻两个催化剂床层(3)之间设置有催化剂分布件，所述催化剂分布件用于分散催化剂输送管(16)出口的催化剂；
    优选地，所述催化剂分布件包括锥型分布挡板(12)，所述锥型分布挡板(12)与催化剂输送管(16)同轴设置；进一步优选地，锥型分布挡板(12)与催化剂输送管(16)的数量相同；
    进一步优选地，所述催化剂分布件还包括设置在所述锥型分布挡板(12)下方的水平分布挡板(13)，所述水平分布挡板(13)上设置有供催化剂通过的孔。
  19. 根据权利要求12-18中任意一项所述的方法，其中，轴向移动床反应器(1)底部的催化剂输送至待生剂接收器(5)中脱除催化剂中携带的液相物料，然后输送至催化剂再生器(4)中进行再生；
    优选地，所述再生介质在催化剂再生器(4)中的表观流速为0.003-0.8m/s，进一步优选为0.02-0.5m/s。
  20. 根据权利要求12-19中任意一项所述的方法，其中，催化剂再生器(4)设置有新鲜催化剂进料口供新鲜催化剂进入催化剂再生器(4)中。
  21. 根据权利要求12-20中任意一项所述的方法，其中，待生剂接收器(5)、催化剂再生器(4)和再生剂接收器(6)依次自上而下设置，待生剂接收器(5)、催化剂再生器(4)和再生剂接收器(6)之间的催化剂流通管线为垂直设置或与水平面间的夹角不小于40度倾斜设置。
  22. 根据权利要求12-21中任意一项所述的方法，其中，轴向移动床反应器(1)的催化剂出口与待生剂接收器(5)的催化剂入口的连通管线上设置有第一颗粒流量调节器(25)；再生剂接收器(6)的催化剂出口与轴向移动床反应器(1)的催化剂入口的连通管线上设置有第二颗粒流量调节器(33)；
    优选地，所述第一颗粒流量调节器(25)和第二颗粒流量调节器(33)各自独立地为L型或近似L型的物料输送阀组。
  23. 根据权利要求12-22中任意一项所述的方法，其中，该装置还包括催化剂缓冲罐(38)，所述催化剂缓冲罐(38)设置在轴向移动床反应器(1)、待生剂接收器(5)之间，催化剂缓冲罐(38)的催化剂入口与轴向移动床反应器(1)的催化剂出口连通，催化剂缓冲罐(38)的催化剂出口与待生剂接收器(5)的催化剂入口连通。
  24. 根据权利要求12-23中任意一项所述的方法，其中，所述轴向移动床反应器(1)设置有催化剂再生床层，其位于一个反应床层之下，离开该反应床层的催化剂进入该催化剂再生床层，在溶解有氢气的液态烃的存在下再生，
    在催化剂再生床层中的再生条件为：
    再生温度为50-140℃，
    再生介质在再生器内的表观流速为0.01-0.5m/s；
    所述的再生介质为溶解有氢气的液态烃；液态烃为C3-C6(例如C3-C5)的饱和烷烃或反应产物与上述饱和烷烃的混合物，优选的，液态烃为C3-C6(例如C3-C5)的饱和烷烃与反应产物的混合物。
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