CN115010569A - Method for synthesizing linear alkyl aromatic hydrocarbon - Google Patents
Method for synthesizing linear alkyl aromatic hydrocarbon Download PDFInfo
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- CN115010569A CN115010569A CN202210619152.4A CN202210619152A CN115010569A CN 115010569 A CN115010569 A CN 115010569A CN 202210619152 A CN202210619152 A CN 202210619152A CN 115010569 A CN115010569 A CN 115010569A
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- catalyst
- temperature
- aromatic hydrocarbon
- reactor
- alkylation
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- 238000000034 method Methods 0.000 title claims abstract description 62
- -1 alkyl aromatic hydrocarbon Chemical class 0.000 title claims abstract description 56
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- 150000001336 alkenes Chemical class 0.000 claims abstract description 139
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 82
- 150000004996 alkyl benzenes Chemical class 0.000 claims description 44
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Classifications
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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
- C07C2/64—Addition to a carbon atom of a six-membered aromatic ring
- C07C2/66—Catalytic processes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/30—Tungsten
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/90—Regeneration or reactivation
- B01J23/92—Regeneration or reactivation of catalysts comprising metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/04—Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst
- B01J38/12—Treating with free oxygen-containing gas
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
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- 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
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- Y02P20/584—Recycling of catalysts
Abstract
The invention discloses a method for synthesizing linear alkyl aromatic hydrocarbon, which comprises the following steps: at the temperature of 100-300 ℃, the pressure of 0.2-10 MPa and the mass space velocity of 0.1-20 h ‑1 Under the condition of (1), reacting the raw materials with WO with a mesoporous structure 3 /ZrO 2 The composite oxide solid acid catalyst contacts to perform the alkylation reaction of the aromatic hydrocarbon and the linear chain olefin to generate a product linear chain alkylAromatic hydrocarbons; a part of the effluent of the alkylation reactor is used as a circulating fluid which is circulated to the reactor, so that the aromatic hydrocarbon-olefin molar ratio of fresh feed of the reactor is reduced, and the load of a distillation separation system is reduced; the method is environment-friendly, and the catalyst has the characteristics of dual functions of alkylation catalysis and product refining, good activity stability, high conversion rate, high selectivity, good product quality and low energy consumption.
Description
Technical Field
The invention relates to a method for synthesizing linear alkyl aromatic hydrocarbon, in particular to a method for synthesizing linear alkyl aromatic hydrocarbon by using WO with a mesoporous structure 3 /ZrO 2 A process for synthesizing straight-chain alkyl arylhydrocarbon by the alkylation reaction of straight-chain olefin and arylhydrocarbon with the solid acid catalyst of composite oxide.
Background
Straight chain alkyl aromatic hydrocarbon is an important petrochemical raw material and product, is commonly used as an intermediate of a detergent and a surfactant for oil displacement, and is also used for synthesizing lubricating oil, heat conduction oil, a lubricating oil additive, a corrosion inhibitor and the like. The linear alkyl aromatic hydrocarbon is produced by taking linear olefin produced in the processes of liquid wax dehydrogenation, paraffin cracking, Fischer-Tropsch synthesis, ethylene oligomerization and the like as an alkylation reagent and respectively carrying out alkylation reaction with aromatic hydrocarbons such as benzene, toluene, ethylbenzene, xylene, methyl ethyl benzene, propyl benzene, diethylbenzene and the like under the action of an acid catalyst. At present, the industry mainly adopts hydrofluoric acid or aluminum trichloride catalyst to synthesize linear alkyl aromatic hydrocarbon. These catalysts have problems of corrosion of equipment, environmental pollution, difficulty in separation from reaction products, and the like. The development of solid acid catalysts and catalytic reaction processes thereof is an effective way to solve these problems.
A great deal of research has been carried out at home and abroad on the solid acid catalyst and the catalytic reaction process for the linear alkylation of aromatic hydrocarbon, and some research progresses are obtained. Patent CN 1092755A discloses a method for synthesizing linear alkylbenzene by using a silicon aluminum fluoride catalyst in oil products of the world, wherein C is used under the conditions that the temperature is 80-140 ℃ and the molar ratio of benzene to linear olefin is 5: 1-30: 1 6 ～C 20 The linear olefin alkylates benzene, the conversion rate of the olefin is more than 98%, the selectivity of the alkylbenzene is more than 85%, the linearity of the alkylbenzene is more than 90%, and the time for stabilizing the activity of the catalyst is 48 hours. Patent CN 1100401a discloses an improved method for alkylation of aromatic hydrocarbon and straight-chain olefin by oil products from globus, which improves the activity stability of the straight-chain olefin and benzene alkylation solid acid catalyst by adsorption removal treatment of a small amount of aromatic hydrocarbon in the alkane-olefin mixed hydrocarbon, but the developed solid acid alkylation digital process still is that the catalyst undergoes 24 hours reaction and regenerationThe operation is switched frequently. Patent CN1210509A discloses a method for synthesizing linear alkylbenzene with fluorine-containing mordenite catalyst from Hotmann petroleum company, wherein the olefin contains 10-14 carbon atoms, and benzene alkylation reaction can be carried out by reactive distillation. Patent CN 1222134A discloses a two-step process for the alkylation of benzene to form linear alkylbenzenes containing benzene and C 5 ～C 30 The olefin reaction fluid contacts the fluorine-containing mordenite first and then the fluorine-containing clay. The patent CN 1169889A discloses a metal ion exchange and acid treatment HY type molecular sieve catalyst for macro-linked compounds, which is prepared at the temperature of 120-300 ℃, the pressure of 1.0-5.0 MPa and the weight space velocity of 1-20 h -1 The molar ratio of the benzene to the olefin is 0.5-25: 1, and the reaction is carried out by reacting C 10 ～C 14 Alkylation of linear olefins with benzene to produce linear alkylbenzenes, and benzene and alkane flushed catalyst regeneration processes are mentioned. The patent CN 1277894A discloses the use of a supported heteropolyacid catalyst at a temperature of 100-300 ℃, a pressure of 1.0-5.0 MPa and a weight space velocity of 0.5-30 h -1 And the benzene-olefin molar ratio is 1-30: 1, and the reaction time is 10-48 h. The patent CN 1327970A discloses a liquid phase alkylation method of benzene and olefin in Qinghua university, the catalyst is composed of mordenite or ZSM-20 or beta zeolite, 0.1-5% (mass fraction) of fluorine or phosphorus, gamma-Al 2 O 3 The catalyst is washed and regenerated by taking benzene as a solvent. Patent CN 1560001A discloses a method for preparing long-chain alkylbenzene from long-chain olefin and benzene by the university of the general theory of physics, and gamma-Al with a mesopore and macropore double-pore structure 2 O 3 Preparation of AlCl for support 3 The immobilized catalyst reacts under the conditions that the temperature is 0-300 ℃, the pressure is 0.5-5.0 MPa, the molar ratio of benzene to long-chain olefin is 2-20: 1, and the volume ratio of the catalyst to the raw material is 0.05-0.5, wherein the long-chain olefin can be C 6 ＝ ～C 20 ＝ (ii) a Reacting benzene with 1-C at 80 deg.C 12 ＝ After 8 hours of reaction, the catalyst undergoes 5 batch reactions, and the catalyst activity remains unchanged. Patent CN 1657161A discloses a solid acid catalyst of Nanjing industry university for preparing linear alkylbenzene by alkylation of linear olefin and benzene, wherein the catalyst is prepared by oxidizing 0.005-0.1% by mass of alkali metal or/and alkaline earth metal5-25% of WO 3 And the balance of ZrO 2 The composite oxide is formed, the deactivated catalyst is washed and regenerated by hot benzene, and the catalyst is subjected to reaction and regeneration for 6 times under the condition of 85 ℃ batch reaction, so that the performance of the catalyst is slightly deteriorated. These batch alkylation reaction methods are not easy to realize large-scale continuous production, and it is difficult to evaluate the activity stability of the solid acid catalyst. At present, the outstanding problem of synthesizing the linear alkyl aromatic hydrocarbon solid acid catalyst is the problem of poor activity stability.
In addition, linear alkyl aromatic hydrocarbon is obtained through alkylation reaction and distillation separation operation in industry, and then is adsorbed and refined by activated clay to produce linear alkyl aromatic hydrocarbon products with the standard bromine index. Part of linear alkyl aromatic hydrocarbon is lost in activated clay adsorption refining, and because the spent activated clay cannot be regenerated and needs to be deeply buried for disposal, the environment is polluted. The method improves the activity stability and the olefin alkylation reaction depth of the solid acid catalyst by optimizing the design of the solid acid catalyst with larger pores and optimizing the alkylation reaction conditions, obtains the linear alkyl aromatic hydrocarbon meeting the bromine index requirement of the product, and is a development direction for developing a solid acid catalytic synthesis process of the linear alkyl aromatic hydrocarbon.
Disclosure of Invention
The invention prepares WO with proper surface acidity and larger pore diameter 3 /ZrO 2 The composite oxide solid acid catalyst develops a method for synthesizing linear alkyl aromatic hydrocarbon, which is environment-friendly, good in catalyst activity stability, high in conversion rate, high in selectivity, high in product linearity, low in bromine index and low in energy consumption.
During the catalytic reaction process of the linear olefin and the aromatic alkylation solid acid, a coking side reaction occurs, and the generated coke is deposited on the surface of the catalyst, so that the solid acid catalyst is coked and deactivated. The invention adopts a coprecipitation method to prepare WO with a mesoporous structure and surface acidity 3 /ZrO 2 The solid acid catalyst is prepared by extruding and molding the composite oxide. The catalyst has the properties of larger mesopores and adjustable surface acidity, improves the in-pore diffusion of alkylation raw materials and products, and increases the alkylation reaction opportunity of linear chain olefin and aromatic hydrocarbon, thereby inhibiting the olefin polymerizationThe reaction reduces the coking rate, inhibits the coking and inactivation of the catalyst, and improves the activity stability of the catalyst.
Because the linear chain olefin raw material often contains a small amount of diene, the olefin and the diene are respectively alkylated with aromatic hydrocarbon to generate linear chain alkyl aromatic hydrocarbon and aromatic hydrocarbon olefin, the aromatic hydrocarbon olefin is difficult to further carry out alkylation reaction with the aromatic hydrocarbon due to the limitation of the aperture of the catalyst, so that the synthesized linear chain alkyl aromatic hydrocarbon product contains a small amount of aromatic hydrocarbon, or the bromine index of the synthesized linear chain alkyl aromatic hydrocarbon is higher, and the product quality and the subsequent processing performance are deteriorated. WO prepared by the invention 3 /ZrO 2 The composite oxide catalyst has the property of larger mesopores, and when the alkylation reaction is respectively carried out on the olefin and the diene and the aromatic hydrocarbon, the deep alkylation reaction is carried out on the aromatic hydrocarbon and the aromatic hydrocarbon, so that the bromine index of a linear alkyl aromatic hydrocarbon product is reduced.
In addition, the catalyst bed layer filled into the reactor is subjected to hot nitrogen purging pretreatment to remove part of water absorbed by the catalyst, and air in the reactor is replaced, so that the catalyst has better catalytic performance. The method adopts a feeding sequence of firstly inputting aromatic hydrocarbon and filling the reactor, and then inputting alkylation mixed raw materials into the reactor, so that the initial alkylation reaction is carried out under the condition of higher molar ratio of the aromatic hydrocarbon to the olefin, the opportunity of olefin polymerization under the condition of higher activity of the catalyst at the initial reaction stage is reduced, the coking inactivation rate of the catalyst at the initial reaction stage is reduced, and the activity stability of the catalyst is improved. By utilizing the principle of similar intermiscibility, linear alkyl arene or linear alkane solvent is added into reaction raw materials to dilute linear olefin and reduce the contact chance between linear olefin molecules, thereby inhibiting olefin polymerization reaction, reducing the coking rate and improving the activity stability of the catalyst. The alkylation reactor is recycled in part of its effluent, as one of the feeds to the reactor, which contains mainly the remaining aromatic hydrocarbon, linear alkylaromatic hydrocarbon and/or linear alkane, the remaining aromatic hydrocarbon being used mainly to ensure the aromatic hydrocarbon to linear olefin molar ratio of the alkylation reactor feed, while the other feed to the reactor is a fresh feed or referred to as the total feed, whose aromatic hydrocarbon to linear olefin molar ratio may be less than 10:1, even close to the stoichiometric molar ratio1:1, reduces the input amount of aromatic hydrocarbon of the reactor, reduces the load of a distillation separation system, and is beneficial to energy conservation. Through the reaction with WO having a mesoporous structure 3 /ZrO 2 The linear chain olefin and aromatic alkylation reaction conditions matched with the performance of the composite oxide solid acid catalyst are optimized, and the activity stability, the linear chain alkyl aromatic selectivity and the product linearity of the catalyst are improved.
The technical scheme adopted by the invention is as follows:
a method of synthesizing a linear alkyl aromatic hydrocarbon, the method comprising:
firstly, inputting raw material aromatic hydrocarbon into a fixed bed alkylation reactor, and filling the fixed bed alkylation reactor with the raw material aromatic hydrocarbon; then raw material aromatic hydrocarbon and raw material C are mixed 6 ～C 24 The mixture of the linear olefin and the additive is input into a fixed bed reactor and is mixed with the mesoporous WO 3 /ZrO 2 The composite oxide solid acid catalyst is contacted with the mixture at the temperature of 100-300 ℃, the pressure of 0.2-10.0 MPa and the total mass airspeed of the feeding of 0.1-20.0 h -1 Performing alkylation reaction on the aromatic hydrocarbon and the linear chain olefin under the liquid phase reaction conditions that the amount ratio of the aromatic hydrocarbon to the linear chain olefin is 2-50: 1 and the amount ratio of the additive to the linear chain olefin is 0-20: 1 to generate a product linear chain alkyl aromatic hydrocarbon;
taking one part of the effluent of the alkylation reactor as a circulating fluid which is circulated to the reactor, taking the other part of the effluent as an effluent fluid which is used for separating excessive raw materials and products (aromatic hydrocarbon, linear alkyl aromatic hydrocarbon and the like) by a distillation separation system, wherein the circulation ratio of the volume flow rate of the circulating fluid to the volume flow rate of the effluent fluid is 0-80;
the catalyst is regenerated after deactivation by burning and can be recycled.
The method comprises the following steps:
the raw material aromatic hydrocarbon is one or a mixture of more than two of benzene, toluene, ethylbenzene, xylene, methyl ethyl benzene, propyl benzene and diethyl benzene in any proportion;
raw material C 6 ～C 24 The linear olefin is preferably linear olefin obtained by the processes of liquid wax dehydrogenation, paraffin cracking, Fischer-Tropsch synthesis, ethylene oligomerization and propylene polymerization;
the additive is a straight-chain alkyl aromatic hydrocarbon solvent or straight-chain alkaneA hydrocarbon solvent; the linear alkyl aromatic hydrocarbon solvent is selected from C 6 ～C 24 One or a mixture of more than two of linear alkyl benzene, toluene, ethylbenzene, xylene, methyl ethyl benzene, propyl benzene and diethyl benzene in any proportion; the straight-chain alkane solvent is selected from C 6 ～C 24 One or a mixture of more than two of linear alkanes in any proportion, preferably C 10 ～C 13 And (4) liquid wax.
Mesoporous WO used in the present invention 3 /ZrO 2 The composite oxide solid acid catalyst is prepared by the following method:
(1) preparation of mesoporous WO by coprecipitation method 3 /ZrO 2 Composite oxide:
respectively preparing a zirconium source aqueous solution and an ammonium metatungstate aqueous solution with the concentrations of 0.1-0.5 mol/L and 0.02-0.2 mol/L, slowly adding the ammonium metatungstate aqueous solution into the zirconium source aqueous solution while stirring according to the composition requirements of the composite oxide, and continuously stirring for 5-30 min after the ammonium metatungstate aqueous solution is added, so that the zirconium source aqueous solution and the ammonium metatungstate aqueous solution are uniformly mixed to obtain a mixed solution; dropwise adding ammonia water with the mass fraction of 25-28% into the mixed solution until the pH of the final solution is 9-10, continuously stirring for 30-60 min after dropwise adding, and then aging for 8-48 h at the temperature of 10-100 ℃; filtering after the aging is finished, washing with deionized water, filtering for 0-5 times, and drying for 8-48 h at the temperature of 80-120 ℃; finally, the temperature is programmed to be increased from 5-40 ℃ to 600-850 ℃ at the heating rate of 0.5-10 ℃/min, the mixture is roasted for 1-8 hours at constant temperature, and the WO is obtained after crushing 3 ：ZrO 2 The molar ratio is 0.05-0.2: 1 mesoporous WO 3 /ZrO 2 A composite oxide powder;
the zirconium source is one or a mixture of more than two of the following materials in any proportion: zirconyl nitrate, zirconyl chloride, zirconium hydroxide;
(2) extruding and molding a catalyst:
mixing the composite oxide, the alumina monohydrate and the sesbania powder for 5-30 min according to the mass ratio of the composite oxide to the alumina monohydrate of 0.1-1.8: 1 and the mass ratio of the sesbania powder to the total mass of the composite oxide and the alumina monohydrate of 0.02-0.08: 1 to obtain a solid mixture, and adding the solid mixture into the solid mixtureAdding deionized water with the mass ratio of 0.2-1.0: 1 into the mixture, and stirring and mixing for 5-30 min; then dropwise adding a dilute nitric acid aqueous solution with the mass fraction of 5-10% while stirring, wherein the addition amount of the dilute nitric acid aqueous solution ensures that the mixture can be kneaded into a mud mass, and extruding and forming; standing the strip at the temperature of 5-40 ℃ for 4-24 h, and drying at the temperature of 90-120 ℃ for 5-24 h; then, the temperature is programmed to be increased from 5-40 ℃ to 500-600 ℃ at a heating rate of 0.5-10 ℃/min, and the mixture is roasted at a constant temperature for 1-10 hours to obtain WO 3 /ZrO 2 Molded mesoporous WO with composite oxide mass fraction of 10-70% 3 /ZrO 2 Catalyst, balance Al 2 O 3 。
Further, the mesoporous WO 3 /ZrO 2 After the composite oxide solid acid catalyst is loaded into a reactor, the composite oxide solid acid catalyst is firstly treated at the temperature of 100-500 ℃, the pressure of 0.1-5.0 MPa and the mass ratio of nitrogen flow to the catalyst of 0.01-0.1 m 3 /(h.g) pretreatment with nitrogen purge for 0.5-24 h, then used for alkylation reaction.
Further, the alkylation reaction conditions are as follows: the temperature is 150-280 ℃, the pressure is 0.5-8.0 MPa, and the total mass airspeed of the feed is 0.2-5.0 h -1 The ratio of the amount of aromatic hydrocarbon to the amount of linear olefin material is 5 to 30:1, the ratio of the amount of the additive to the amount of linear olefin material is 1 to 10:1, and the circulation ratio of the volume flow rate of the circulating fluid of the alkylation reactor to the volume flow rate of the effluent fluid of the de-distillation separation system is 1 to 50.
Further, in the operation of adopting two reactors connected in series, when the olefin content of the effluent of the second reactor exceeds the standard, or the total olefin conversion rate is not more than 98%, the second reactor is switched into the first reactor; when the olefin content of the effluent of the first reactor exceeds the standard, such as the olefin conversion rate of the first reactor is not more than 30 percent, the catalyst in the first reactor is regenerated. The regeneration method can be nitrogen or water vapor purging, oxygen-containing gas or air scorching, and can also be nitrogen or water vapor purging, polar solvent washing, oxygen-containing gas or air scorching. The catalyst and operating conditions in the second alkylation reactor may be the same as or different from those in the first alkylation reactor.
If the olefin conversion decreases significantly with extended duration or the olefin conversion requirement is not met, the alkylation reaction temperature may be increased, or the space velocity decreased, or the catalyst regenerated. The regeneration method comprises the steps of stopping feeding the linear chain olefin in the reaction raw material, continuing feeding the aromatic hydrocarbon or feeding a mixture of the aromatic hydrocarbon and the additive, and washing and regenerating the catalyst under the operating conditions of the temperature of 10-400 ℃ and the pressure of 0.1-15 MPa for 2-1000 hours.
And, the deactivated alkylation catalyst may be subjected to a coke-burning regeneration process as follows:
after the alkylation reaction raw material is stopped, firstly, nitrogen is input into the reactor, and the ratio of the nitrogen flow to the catalyst mass is 0.01-0.5 m 3 /(h. g), and purging with nitrogen for 1-24 h to complete the nitrogen purging operation; then, the ratio of the air flow and the catalyst mass is 0.05-0.25 m 3 /(h &), raising the temperature of air scorching regeneration from the initial temperature of 100-400 ℃ to the final temperature of 450-650 ℃ at the heating rate of 0.2-5.0 ℃/min, and scorching at the constant temperature of the final temperature for 1.0-24.0 h; finally, nitrogen is input, the ratio of the nitrogen flow to the catalyst mass is 0.01-0.5 m 3 And (h &), reducing the temperature of the catalyst bed layer of the reactor from the final scorching temperature to the alkylation reaction temperature, and continuing nitrogen purging for 1-24 h to finish the scorching regeneration operation of the catalyst. It is also possible to adopt a procedure of several temperature stages from low temperature to high temperature for the coke-burning regeneration process. The deactivated alkylation catalyst may also be subjected to ex-situ coke-burning regeneration.
The arene, the straight chain olefin and the additive can also be input into an alkylation reactor for reaction after being subjected to adsorption refining, and the arene, the straight chain olefin and the additive can be subjected to adsorption refining alone or a mixture of the arene, the straight chain olefin and the additive. The adsorption refining conditions are as follows: the adsorption temperature is 0-280 ℃, the pressure is 0.1-10 MPa, and the mass space velocity is 0.2-20 h -1 Continuously adsorbing for 10-2000 h; the adsorbent is one of the following or a mixture thereof: 5A molecular sieve, 13X molecular sieve, HY molecular sieve, USY molecular sieve, activated clay, activated alumina, WO 3 /Al 2 O 3 、WO 3 -ZrO 2 /Al 2 O 3 、P/Al 2 O 3 、F/Al 2 O 3 Porous silica gel, active carbon, a phosphorus-aluminum molecular sieve or a phosphorus-aluminum molecular sieve composition containing a substituted element, an SBA-15 type molecular sieve or a load modified SBA-15 type molecular sieve, an MCM-41 type molecular sieve or a load modified MCM-41 type molecular sieve, an H beta molecular sieve, an H-Moderite type molecular sieve, an HZSM-20 type molecular sieve or a load modified HZSM-20 type molecular sieve.
The alkylation reactor can be selected from a fixed bed, a moving bed, an expanded bed, a fluidized bed, a stirred tank reactor and a catalytic distillation reactor. The reactor can be provided with one or more feed inlets, and the aromatic hydrocarbon, the linear olefin, or/and the additive linear alkane solvent, or/and the additive linear alkyl aromatic hydrocarbon solvent, or/and the circulating fluid can adopt a feeding mode of mixing and then inputting into the alkylation reactor, or can adopt a feeding mode of independently inputting into the reactor. The alkylation reaction device can be operated by a plurality of reactors in parallel or in series, and each reactor can be filled with the same or different alkylation catalysts; the reaction operating conditions of the reactors can be the same or different; the reactor can adopt an upper end feeding mode and a lower end feeding mode.
The linear chain olefin raw material often contains a trace amount of linear chain diene, and the linear chain diene also has alkylation reaction with aromatic hydrocarbon to generate a trace amount of aromatic hydrocarbon group linear chain olefin; the aromatic hydrocarbon group linear chain olefin is difficult to be further alkylated with aromatic hydrocarbon due to the limitation of the aperture of the porous solid acid catalyst, so that the alkylated product contains trace aromatic hydrocarbon group linear chain olefin impurities, the bromine index of the product is higher, and the stability of the product is deviated. In order to strengthen the alkylation reaction of aromatic hydrocarbon olefin and aromatic hydrocarbon and reduce the bromine index of the synthesized linear alkyl aromatic hydrocarbon, mesoporous WO is adopted 3 /ZrO 2 The composite oxide catalyst is used as the alkylation catalyst of the first reactor, the solid acid catalyst with larger aperture is used as the alkylation catalyst of the second reactor, and the two alkylation reactors are connected in series for operation. The solid acid catalyst with larger pore diameter is selected from activated clay, fluorine-containing clay and mesoporous WO 3 /ZrO 2 Composite oxide solid acid catalyst, and supported acidic compoundThe acid compound is one or a mixture of two or more of the following aluminum trioxide, silicon dioxide and montmorillonite in any proportion: ZrO (ZrO) 2 、WO 3 Sulfuric acid, phosphoric acid, hydrofluoric acid, fluoride, phosphotungstic heteropoly acid, silicotungstic heteropoly acid, phosphomolybdic heteropoly acid, phosphotungstic heteropoly acid cobalt salt, silicotungstic heteropoly acid cobalt salt, phosphomolybdic heteropoly acid cobalt salt, boric acid, aluminum chloride, zinc chloride, ferric chloride, copper chloride and chromium chloride, wherein the load mass of the acidic compound accounts for 0.1-50% of the total mass fraction; the second alkylation reactor may be operated under the same or different conditions as the first alkylation reactor. The effluent of the alkylation reactor or the linear alkyl aromatic hydrocarbon fraction obtained by distillation and separation can also be subjected to hydrofining to remove trace olefin impurities, reduce the bromine index of the synthesized linear alkyl aromatic hydrocarbon, and improve the stability and subsequent processing performance of the product.
The invention has the following beneficial effects:
(1) the adopted catalyst is a non-corrosive and environment-friendly solid acid catalyst;
(2) the alkylation catalyst has good activity stability, the stable continuous reaction time is longer than 2000 hours, the conversion rate of long-chain olefin is higher than 98 percent, the selectivity of long-chain alkyl aromatic hydrocarbon is higher than 97 percent, and the scorching regeneration performance of the catalyst is good; the device has long stable operation time, and can avoid frequent switching operation of reaction and regeneration of the reactor;
(3) the long-chain alkyl aromatic hydrocarbon product has good quality, the linearity is higher than 97%, and the bromine index reaches below 10mgBr/100 g;
(4) the reactor can adopt circulating operation, not only the alkylation reaction is kept to operate under a certain aromatic hydrocarbon and long-chain olefin molar ratio, but also the operation load of a distillation separation system is reduced, the investment can be saved, and the energy consumption can be reduced;
(5) the catalyst has the double functions of alkylation catalysis and product refining, omits the activated clay adsorption refining operation of the linear alkyl aromatic hydrocarbon product, or reduces the clay refining load, and avoids or lightens the environmental pollution caused by the disposal of the waste clay.
Drawings
FIG. 1 is N of sample prepared in step (1) of example 1 2 Adsorption/desorption isotherms.
FIG. 2 is a BJH pore size distribution calculated by the BJH method for a sample prepared in step (1) of example 1.
Detailed Description
The invention is further described below by means of specific examples, without the scope of protection of the invention being limited thereto.
The chemical reagents or reaction raw materials used in the examples include: alumina monohydrate, Al 2 O 3 70% by mass, Shandong aluminum industry group company; zirconium oxychloride octahydrate (ZrOCl) 2 ·8H 2 O, molecular mass 322.25g/mol ≧ 99.9%, analytical purity), shanghai alatin biochemistry science & technology company; zirconyl nitrate hydrate (ZrO (NO) 3 ) 2 ·xH 2 O, molecular mass 231.23g/mol ≧ 99.5%, analytical purity), shanghai alatin biochemistry science & ltd; zirconium hydroxide (Zr (OH) 4 159.25g/mol, ≧ 97.0%, analytical purity), Shanghai Allantin Biotech Co., Ltd; ammonium metatungstate (H) 8 N 2 O 4 W, molar mass 283.91g/mol, WO 3 Content ≧ 90.0%, industrial grade), nada nonferrous metals limited company in tezhou city; ammonia (H5NO, molar mass 35.05g/mol, 25-28%, analytical purity), shanghai michelin biochemistry corporation; nitric acid, analytically pure, chekiang Zhongxing chemical reagent, Inc.; sesbania powder, 99%, Jiangsu pleiotte bioengineering GmbH; quartz sand, analytical grade, national chemical group chemical reagents ltd; benzene, industrial grade, pacifying petrochemical companies; toluene, analytically pure, not less than 99.5%, national drug group chemical reagent limited; xylene, analytically pure, not less than 99.0%, national drug group chemical reagents limited; ethylbenzene, analytically pure, not less than 98.5%, chemical reagents of national drug group limited; c 16 ～C 18 Linear olefins, C 16 Olefins and C 18 54% and 44% of olefin by mass, respectively, SIGMA company, usa; c 10 ～C 13 Liquid wax, industrial grade, compliant petrochemical company; c 10 ～C 13 Linear Alkylbenzenes (LAB), industrial grade, compliant petrochemical company;n-dodecane, analytically pure, 98%, aladine reagents inc; n-hexene, 97%, ACROS reagent, usa; n-dodecene, not less than 90%, Fluka reagent company; c 10 ～C 13 Linear olefins, technical grade, compliant petrochemicals corporation. All chemicals or starting materials were not purified prior to use.
An alkylation reaction experimental device, a product analysis method and a data processing method are as follows:
the alkylation reaction experiment of aromatic hydrocarbon and long chain olefin is carried out in a fixed bed reactor, the reactor is made of a stainless steel pipe, the inner diameter of the reactor is 10mm, the outer diameter of the reactor is 14mm, the length of the reactor is 100cm, and thermocouple protective sleeves (the outer diameter of the reactor is 3mm) capable of measuring the temperature of catalyst bed layers at different heights are arranged in the reactor. The catalyst is filled in a constant temperature area in the middle of the reaction tube, quartz sand is filled in the upper end and the lower end of the reaction tube, the catalyst and the quartz sand are separated by quartz wool, and the reaction tube, the quartz wool and the quartz sand are inert to alkylation reaction. The reaction temperature is controlled by a temperature control instrument and displayed by a temperature display instrument, and the reaction pressure is regulated by a nitrogen pressure reducing valve. The reaction raw materials are injected from the lower end of the reactor by a double-plunger metering pump, and the feeding amount of the raw materials is weighed by an electronic balance. The reaction raw material flows through the catalyst bed layer to generate alkylation reaction, the product after the reaction flows out from the upper end of the reactor and enters a product receiving tank, and then a sampling bottle is used for sampling and analyzing.
The bromine indices of the alkylation feed and product were determined using an RPP-200Br bromine index meter, manufactured by Zhonghuan Analyzer, Tezhou City, and the olefin conversion (X) was obtained from the difference between the bromine indices of the feed and product and divided by the bromine index of the feed.
The composition analysis of the alkylated product was carried out using a 7890B gas chromatograph manufactured by agilent scientific shanghai analytical instruments ltd, under the following chromatographic conditions: the chromatographic column is a DB-1 capillary column with the thickness of 50m multiplied by phi 0.32mm multiplied by 0.52 mu m, the detector is an FID (hydrogen flame) detector, the carrier gas is high-purity nitrogen, the combustion-supporting gas is air, the fuel gas is hydrogen, the temperature of the sample injector is 250 ℃, the temperature of the detector is 300 ℃, the temperature programming condition of the column temperature is that the temperature is kept for 1min at 80 ℃, then the temperature is increased to 260 ℃ at the speed of 15 ℃/min, and the temperature is kept for 17 min.
The linear olefin and the aromatic hydrocarbon are mainly subjected to alkylation reaction to generate linear alkyl aromatic hydrocarbon (LAA); the Linear Olefins (LO) undergo cracking side reactions to produce short chain olefins (SO) which are alkylated with aromatic hydrocarbons to produce short chain alkyl aromatic hydrocarbons (SAA). Assuming that the olefin molecules of each class have the same chromatographic correction factor, f 1 0.5530; each type of alkylaromatic molecule has the same correction factor, f 2 1.0452. The reaction selectivity of the linear alkyl aromatic product to the feedstock olefin conversion (i.e., linear alkyl aromatic selectivity) is:
the linear olefin feed may contain a trace amount of branched olefins, and in the alkylation of linear olefins with aromatics, linear olefins may also undergo a carbon chain isomerization reaction to produce a small amount of branched olefins, which may undergo an alkylation reaction with aromatics to produce a small amount of branched alkyl aromatics (CAA). The linearity (D) of the linear alkyl aromatic hydrocarbon is expressed as:
in the above formula: a. the i Or A j Is the chromatographic peak area fraction of the i or j component; m i Or M j Is the molar mass of the i or j component.
The sustained reaction time when the olefin conversion is less than 98% in the sustained reaction process under the stable reaction conditions is defined as the sustained stable reaction time or the catalyst activity stable time (t) S )。
Example 1: mesoporous WO 3 /ZrO 2 Coprecipitation method for preparing composite oxide
(1) Preparation of composite oxides at different calcination temperatures
Dissolving 0.1mol of zirconyl nitrate in 500mL of deionized water to obtain 0.2mol/L zirconyl nitrate aqueous solution; 0.015mol of ammonium metatungstate is dissolved in 300mL of deionized water to obtain the solution with the concentration of 0.05mol/LAn aqueous solution of ammonium metatungstate; slowly adding the ammonium metatungstate aqueous solution into the zirconyl nitrate aqueous solution while stirring, and continuously stirring for 20min to obtain a mixed solution; dropwise adding ammonia water with the mass fraction of 25-28% into the mixed solution until the pH value of the final solution is 10, and continuously stirring for 60min after dropwise adding; then pouring the mixed solution into a polypropylene plastic bottle, and standing and aging for 24 hours in an oven at the temperature of 30 ℃; filtering after aging is finished, washing with deionized water, filtering for 2 times, and drying at 120 ℃ for 12 hours; finally, heating to 600 ℃, 700 ℃ and 800 ℃ respectively from a program of 20 ℃ at a heating rate of 2 ℃/min, roasting for 3h at constant temperature, and crushing to obtain WO 3 ：ZrO 2 The molar ratio is 0.15: 1 WO 3 /ZrO 2 The composite oxide powders are respectively marked as WZ-0.15-N-600, WZ-0.15-N-700 and WZ-0.15-N-800. 3Flex S/N810 type N of Mimmerrieker instruments Limited 2 N is carried out on composite oxide samples synthesized by adopting different roasting temperatures by using adsorption apparatus 2 Adsorption/desorption and characterization of the pore size distribution, FIG. 1 for N 2 Adsorption/desorption isotherms, FIG. 2 is a BJH pore size distribution plot calculated by the BJH method, and BET specific surface areas of samples prepared at 600 ℃, 700 ℃ and 800 ℃ calcination temperatures are 85, 123 and 24m, respectively 2 G, the total pore volume of the three is 0.0786, 0.1897 and 0.0651cm respectively 3 (ii)/g, average pore diameter is 3.7016, 6.1886 and 10.8204nm respectively. As can be seen, the specific surface area and the total pore volume of the sample prepared at the roasting temperature of 700 ℃ are large, and the average pore diameter is in the middle.
As can be seen from FIG. 1, N of three samples 2 The adsorption/desorption isotherms all belong to type IV isotherms, and a hysteresis loop exists, wherein the hysteresis loop represents a capillary condensation phenomenon in mesopores, which indicates that an ordered mesopore structure exists in a sample. FIG. 2 shows that the pores of the three samples are mainly distributed>The mesoporous range of 2.0nm belongs to mesoporous materials.
(2) Preparation of composite oxides with different sources of zirconium
The raw material proportion and the preparation process similar to the WZ-0.15-N-700 prepared in the step (1) are respectively used for preparing the composite oxide by using two zirconium sources of zirconium oxychloride and zirconium hydroxide under the condition of the roasting temperature of 700 ℃, and the components areThe marks are WZ-0.15-Cl-700 and WZ-0.15-H-700. Except that the water washing was performed 5 times after aging in the process of preparing WZ-0.15-Cl-700, while the water washing was not performed after aging in the process of preparing WZ-0.15-H-700. Warp of N 2 Adsorption/desorption and pore size distribution characterization, the samples being composite oxides possessing mesoporous structure.
(3) Preparation of composite oxides with different proportions
A preparation process similar to that of the WZ-0.15-N-700 prepared in the above (1), wherein 0.1mol of zirconyl nitrate is dissolved in 500mL of deionized water using zirconyl nitrate as a zirconium source to obtain an aqueous solution of zirconyl nitrate having a concentration of 0.2 mol/L; respectively dissolving 0.006mol and 0.009mol of ammonium metatungstate in 300mL of deionized water to respectively obtain 0.02mol/L and 0.03mol/L ammonium metatungstate aqueous solutions; slowly adding the ammonium metatungstate aqueous solution into the zirconyl nitrate aqueous solution while stirring, and continuously stirring for 20min to obtain a mixed solution; dropwise adding ammonia water with the mass fraction of 25-28% into the mixed solution until the pH value of the final solution is 10, continuously stirring for 60min after dropwise adding, and then standing and aging for 24h at the temperature of 30 ℃; filtering after the aging is finished, washing with deionized water, filtering for 2 times, and drying at 120 ℃ for 12 h; finally, the temperature is programmed to 700 ℃ from 20 ℃ at the heating rate of 2 ℃/min, and the mixture is roasted for 5 hours at constant temperature, and is crushed to respectively obtain WO 3 ：ZrO 2 The molar ratio is 0.06: 1. 0.09: 1 WO of 3 /ZrO 2 The composite oxide powders are respectively marked as WZ-0.06-N-700 and WZ-0.09-N-700. Warp of N 2 Adsorption/desorption and pore size distribution characterization, the samples being composite oxides possessing mesoporous structure.
(4) Preparation of composite oxides under different aging conditions
Dissolving 0.1mol of zirconyl nitrate in 500mL of deionized water to obtain 0.2mol/L aqueous solution of zirconyl nitrate; dissolving 0.015mol of ammonium metatungstate in 300mL of deionized water to obtain 0.05mol/L ammonium metatungstate aqueous solution; slowly adding the ammonium metatungstate aqueous solution into the zirconyl nitrate aqueous solution while stirring, and continuously stirring for 30min to obtain a mixed solution; then adding 25-28% ammonia water into the mixed solution dropwise until the pH value of the final solution is 9,after the dropwise addition is finished, stirring is continued for 40 min; then pouring the mixed solution into a polypropylene plastic bottle, and standing and aging the mixed solution in an oven for 48 hours at the temperature of 60 ℃ and for 10 hours at the temperature of 90 ℃ respectively; filtering after the aging is finished, washing with deionized water, filtering for 2 times, and drying at 100 ℃ for 24 h; finally, heating from 30 ℃ to 700 ℃ at a heating rate of 1 ℃/min, roasting at constant temperature for 1h, and crushing to obtain WO 3 ：ZrO 2 The molar ratio is 0.15: 1 WO 3 /ZrO 2 The composite oxide powders are respectively marked as WZ60-0.15-N-700 and WZ 90-0.15-N-700. Warp of N 2 Adsorption/desorption and pore size distribution characterization, the samples being composite oxides possessing mesoporous structure.
Example 2: mesoporous WO 3 /ZrO 2 Extrusion molding of composite oxide catalyst
40g of each mesoporous WO prepared in example 1 was added 3 /ZrO 2 The composite oxide powder, 24.5g of alumina monohydrate and 2.58g of sesbania powder are stirred and mixed for 15min, the mass ratio of the composite oxide to the alumina monohydrate is 1.63:1, and the ratio of the sesbania powder to the total mass of the composite oxide and the alumina monohydrate is 0.04: 1, a solid mixture; adding deionized water with the mass ratio of 0.8:1 into the solid mixture, and stirring and mixing for 20 min; then, 59.0mL of dilute nitric acid aqueous solution with the mass fraction of 9.0 percent is dripped while stirring, the mixture is kneaded into a mud mass, and a TBL-2 type catalyst molding extrusion device produced by North chemical engineering experiment equipment Limited company of Tianjin university is adopted for extrusion molding; standing the strip-shaped object at the temperature of 30 ℃ for 12h, and drying at the temperature of 120 ℃ for 6 h; then heating to 540 ℃ from 30 ℃ at a heating rate of 1 ℃/min in a muffle furnace, and roasting for 5 hours at constant temperature to obtain WO 3 /ZrO 2 Molding WO of composite oxide mass fraction 70% 3 /ZrO 2 The catalysts are respectively marked as CWZ-0.15-N-600-70, CWZ-0.15-N-700-70, CWZ-0.15-N-800-70, CWZ-0.15-Cl-700-70, CWZ-0.15-H-700-70, CWZ-0.06-N-700-70, CWZ-0.09-N-700-70, CWZ60-0.15-N-700-70 and CWZ90-0.15-N-700-70, the rest of each formed catalyst is Al 2 O 3 。
40g of WZ-0 prepared in example 1 was charged.Stirring and mixing 15-N-700 composite oxide powder, 228.57g of alumina monohydrate and 8.06g of sesbania powder for 30min to obtain a solid mixture with the mass ratio of the composite oxide to the alumina monohydrate of 0.175:1 and the total mass ratio of the sesbania powder to the two oxides of 0.03:1, adding deionized water with the mass ratio of 0.5:1 into the solid mixture, and stirring and mixing for 10 min; then, 235.0mL of dilute nitric acid aqueous solution with the mass fraction of 6.0 percent is dripped while stirring, the mixture is kneaded into a mud mass, and the mud mass is extruded into strips for forming; standing the strip-shaped object at the temperature of 20 ℃ for 8h, and drying at the temperature of 100 ℃ for 12 h; then the temperature is programmed to be increased to 570 ℃ from 20 ℃ in a muffle furnace at the heating rate of 2 ℃/min, and the mixture is roasted for 3 hours at constant temperature to respectively obtain WO 3 /ZrO 2 WO for molding 20% by mass of composite oxide 3 /ZrO 2 The catalyst is marked as CWZ-0.15-N-700-20, and the balance of the formed catalyst is Al 2 O 3 。
40g of the WZ-0.15-N-700 composite oxide powder prepared in example 1, 57.14g of alumina monohydrate and 4.86g of sesbania powder are stirred and mixed for 30min to obtain a solid mixture with the mass ratio of the composite oxide to the alumina monohydrate of 0.7:1 and the total mass ratio of the sesbania powder to the two oxides of 0.05:1, deionized water with the mass ratio of 0.5:1 is added into the solid mixture, and the mixture is stirred and mixed for 10 min; then, 87.5mL of dilute nitric acid aqueous solution with the mass fraction of 6.0 percent is dripped while stirring, the mixture is kneaded into a mud dough, and the mud dough is extruded into strips for forming; standing the strip at 20 ℃ for 8h, and drying at 100 ℃ for 12 h; then the temperature is programmed to be increased to 570 ℃ from 20 ℃ in a muffle furnace at the heating rate of 2 ℃/min, and the mixture is roasted for 3 hours at constant temperature to respectively obtain WO 3 /ZrO 2 Molded WO having 50% by mass of composite oxide 3 /ZrO 2 The catalyst is marked as CWZ-0.15-N-700-50, and the rest of the formed catalyst is Al 2 O 3 。
Example 3: evaluation of alkylation catalytic Performance of Each catalyst
4.0g of the 11 kinds of 20-40 mesh mesoporous WO prepared in example 2 were respectively added 3 /ZrO 2 The composite oxide catalyst is filled in a constant temperature area in the middle of the fixed bed reactor, the upper end and the lower end of the reaction tube are filled with quartz sand, and the catalyst and the quartz sand are filled with quartz woolAnd (4) separating. The ratio of nitrogen flow to catalyst mass at 250 ℃ was 0.03m 3 /(h.g) the catalyst bed was pretreated with a 2h nitrogen purge. Benzene was fed to the reactor at a temperature of 50 ℃ to fill the reactor with benzene. At the temperature of 250 ℃, the pressure of 4.0MPa and the mass space velocity of 1.0h -1 Under the condition of liquid phase reaction, benzene: c 16 ～C 18 Inputting reaction raw materials with a linear chain olefin molar ratio of 20:1 into a reactor, carrying out alkylation reaction to obtain reactor effluent containing linear alkyl benzene (generally called linear alkyl aromatic hydrocarbon), and obtaining reaction experiment results through bromine index determination and gas chromatography composition analysis of the effluent, wherein the reaction experiment results comprise the olefin conversion rate (X) and the linear alkyl aromatic hydrocarbon selectivity (S) of alkylation catalytic reaction of 11 catalysts LAA ) The results of the experiments on the linearity (D) of linear alkylaromatic hydrocarbons are shown in Table 1. In addition, the reaction results of the catalysts are not obviously changed after the continuous reaction of 2000 h.
TABLE 1 benzene and C of the catalysts 16 ～C 18 Experimental results of alkylation reaction of Long-chain olefin
| Catalyst and process for preparing same | X，％ | S LAA ，％ | D，％ |
| CWZ-0.15-N-600-70 | 98.53 | 98.42 | 97.23 |
| CWZ-0.15-N-700-70 | 99.25 | 98.73 | 97.85 |
| CWZ-0.15-N-800-70 | 98.31 | 98.61 | 97.38 |
| CWZ-0.15-Cl-700-70 | 99.16 | 98.72 | 97.46 |
| CWZ-0.15-H-700-70 | 99.22 | 98.05 | 97.32 |
| CWZ-0.06-N-700-70 | 98.83 | 98.23 | 97.36 |
| CWZ-0.09-N-700-70 | 98.92 | 98.67 | 97.31 |
| CWZ60-0.15-N-700-70 | 99.37 | 98.17 | 97.26 |
| CWZ90-0.15-N-700-70 | 99.45 | 98.02 | 97.12 |
| CWZ-0.15-N-700-20 | 98.29 | 98.70 | 97.48 |
| CWZ-0.15-N-700-50 | 98.94 | 98.33 | 97.56 |
As can be seen from Table 1, 11 kinds of mesoporous WO are used respectively 3 /ZrO 2 Benzene and C with composite oxide catalyst 16 ～C 18 The linear olefin alkylation reaction achieves good reaction results, the conversion rate of the olefin is greater than 98%, the selectivity of the linear alkylbenzene is greater than 98%, the linearity of the linear alkylbenzene is greater than 97%, and the performance of the catalyst subjected to the continuous alkylation reaction for 2000 hours is basically unchanged, which shows that the catalysts have good catalytic performance for alkylating benzene and linear olefin, and only the CWZ-0.15-N-700-70 catalyst has better performance.
Example 4: examination of the results of alkylation reactions with different feedstocks
Using a method similar to example 3, 4.0g of the 20-40 mesh CWZ-0.15-N-700-70 catalyst prepared in example 2 was used, and the ratio of the nitrogen flow rate to the catalyst mass was 0.03m at 250 ℃ 3 /(h.g) the catalyst bed was pretreated with a 2h nitrogen purge. The aromatic hydrocarbon is fed to the reactor at a temperature of 50 ℃ to fill the reactor with aromatic hydrocarbon. At the temperature of 250 ℃, the pressure of 4.0MPa and the mass space velocity of 1.0h -1 Respectively carrying out benzene and n-hexylene, toluene and C under the liquid phase reaction condition that the molar ratio of aromatic hydrocarbon to straight-chain olefin raw material is 20:1 16 ～C 18 Straight chain olefins, ethylbenzene and C 16 ～C 18 Linear olefins dimethylBenzene and C 16 ～C 18 Alkylation reaction of linear olefin, olefin conversion rate (X) and linear alkyl aromatic selectivity (S) of different raw materials LAA ) The results of the experiments on the linearity (D) of linear alkylaromatic hydrocarbons are shown in Table 2. In addition, the alkylation reaction was continued for 2000 hours with different starting materials, respectively, and these reaction results did not change significantly.
TABLE 2 Experimental results of alkylation reactions of different feedstocks
| Reaction raw material | X，％ | S LAA ，％ | D，％ |
| Benzene and n-hexene | 98.32 | 98.51 | 98.13 |
| Toluene and C 16 ～C 18 Straight chain olefins | 99.35 | 98.66 | 97.45 |
| Ethylbenzene and C 16 ～C 18 Straight chain olefins | 99.28 | 98.71 | 97.52 |
| Xylene and C 16 ～C 18 Straight chain olefins | 99.15 | 98.63 | 97.28 |
As can be seen from Table 2, 4 groups of raw material alkylation reactions were carried out with CWZ-0.15-N-700-70 catalysts, and all the reactions gave good results, with an olefin conversion of more than 98%, a linear alkyl aromatic selectivity of more than 98%, a linear alkyl aromatic linearity of more than 97%, and a catalyst performance after 2000 hours of continuous alkylation reactions was essentially unchanged.
Example 5: investigating the influence of the pretreatment temperature of the catalyst bed layer on the performance of the catalyst
By adopting the method similar to the embodiment 3, 4.0g of 20-40 mesh CWZ-0.15-N-700-70 catalyst is loaded into a reactor, the pressure is 0.5MPa, and the mass ratio of nitrogen flow to catalyst is 0.017m 3 /(h.g) the catalyst bed was pretreated with 2h nitrogen purge at different temperatures. Benzene was fed to the reactor at a temperature of 50 ℃ to fill the reactor with benzene. At the temperature of 250 ℃, the pressure of 4.0MPa and the mass space velocity of 1.0h -1 Under the condition of liquid phase reaction, benzene: c 16 ～C 18 Inputting reaction raw materials with the mol ratio of the linear chain olefin being 20:1 into a reactor for alkylation reaction to obtain the conversion rate of the olefin (X) and the selectivity of the linear chain benzene (S) LAA ) The results of the linear alkylbenzene linearity (D) tests are shown in Table 3. In addition, the reaction lasts for 2000h, and the results of the reactions are not obviously changed.
Table 3 reaction experiment results for investigating influence of pretreatment temperature of catalyst bed
| Pretreatment temperature, deg.C | X，％ | S LAA ，％ | D，％ |
| 200 | 98.26 | 98.67 | 98.11 |
| 250 | 99.25 | 98.73 | 97.85 |
| 300 | 98.62 | 98.45 | 97.57 |
| 400 | 98.37 | 98.38 | 97.32 |
As can be seen from Table 3, as the pretreatment temperature of the catalyst bed increases, the conversion rate of the olefin shows a trend of increasing first and then decreasing, which indicates that the activity of the catalyst shows a trend of increasing first and then decreasing, and the catalytic activity of the pretreatment catalyst at 250 ℃ is higher; whereas both the linear alkylbenzenes showed slightly decreasing trend in selectivity and linearity. The reason for this may be that if the pretreatment temperature of the catalyst bed is too low, more water still exists on the surface of the catalyst, covering part of the acid centers, and affecting the activity of the catalyst; the pretreatment temperature is raised, so that the dehydration amount on the surface of the catalyst is increased, and the acid type, the acid density and the acid strength on the surface of the catalyst are changed, thereby causing the change of the catalytic performance. The preferred pretreatment temperature is 250 ℃.
Example 6: inspection of alkylation reactor effluent recycle ratio
The linear alkyl aromatic hydrocarbon is produced through the catalytic reaction of alkylation of aromatic hydrocarbon and linear olefin and the distillation separation process. In order to improve the conversion rate of olefin, the selectivity of linear alkyl aromatic hydrocarbon and the activity stability of the catalyst, a reaction raw material with higher molar ratio of aromatic hydrocarbon to linear olefin is required to be used for liquid phase alkylation reaction, and then excessive aromatic hydrocarbon is separated through a distillation process for recycling, so that the separation energy consumption is higher. If the reactor effluent is divided into a recycle stream to be recycled to the reactor and an effluent stream to be separated into the system, the ratio of the volume flow of the recycle stream to the volume flow of the effluent stream is taken as the recycle ratio (R). The mixture of the aromatic hydrocarbon and the linear olefin mixture and the circulating fluid is used as the feed of the alkylation reactor, and on the premise of meeting the requirement of the molar ratio (such as 20:1) of the aromatic hydrocarbon and the linear olefin fed by the reactor, the larger the value of the circulating ratio R is, the smaller the required molar ratio of the aromatic hydrocarbon and the linear olefin is, the lower the value of the circulating ratio R is can be below 10:1, the load of distillation and separation of the aromatic hydrocarbon is favorably reduced, and the energy consumption in the distillation and separation process is reduced.
In a similar manner to example 3, 4.0g of the 20-40 mesh CWZ-0.15-N-700-70 catalyst prepared in example 2 was charged into a fixed bed reactor. The ratio of nitrogen flow to catalyst mass at 250 ℃ is 0.05m 3 /(h.g) the catalyst bed was pretreated with a 2h nitrogen purge. Benzene was fed to the reactor at a temperature of 60 ℃ to fill the reactor with benzene. At the temperature of 250 ℃, the pressure of 4.0MPa and the mass space velocity of 1.0h -1 Benzene: c 16 ～C 18 Continuous alkylation was carried out under liquid phase reaction conditions with a linear olefin molar ratio of 20:1 using a mixture of benzene, a linear olefin mixture and a recycle fluid as the alkylation reactor feed, and the catalytic reaction results under different recycle ratios R are shown in table 4.
TABLE 4 catalytic reaction results under different recycle ratios R
It is known from table 4 that as the recycle ratio is increased from 0.0 to 50.0, the olefin conversion, the linear alkylbenzene selectivity, and the linear alkylbenzene linearity do not change significantly, more than 98%, 97%, respectively. It is to be noted that as the circulation ratio increases, the catalyst activity stabilization time gradually increases, i.e., the catalyst activity stability gradually becomes better. The reason is that the effluent of the alkylation reactor is circulated, reaction fluids at the heights of catalyst beds of different fixed bed reactors all contain linear alkylbenzene, and according to the principle of similarity and intermiscibility, the linear alkylbenzene dissolves and disperses linear olefin, so that the mutual solubility of the linear olefin and aromatic hydrocarbon is promoted, the chance of olefin polymerization side reaction is reduced, the surface coking and inactivation of the solid acid catalyst are inhibited, and the activity stability of the catalyst is improved. Therefore, the circulation of the effluent of the alkylation reactor not only reduces the load of distillation and separation and reduces the energy consumption of separation, but also is beneficial to improving the activity stability of the catalyst.
Example 7: diluent solvent investigation to improve alkylation catalyst activity stability
Using 4.0g of the 20-40 mesh CWZ-0.15-N-700-70 catalyst prepared in example 2, N-dodecane and C were added to the alkylation reaction raw materials in a similar manner to example 3 10 ～C 13 Liquid wax or C 10 ～C 13 Linear Alkyl Benzene (LAB) diluting solvent, at 250 deg.C, 5.0MPa and mass space velocity of 1.0h -1 Benzene and n-dodecene alkylation reaction is carried out under the liquid phase reaction conditions of the benzene-olefin molar ratio of 15:1 and the dilution solvent-olefin molar ratio (S/O) of 3: 1-8: 1, the influence of the type of the dilution solvent on the activity stability of the catalyst is examined, and the experimental results are listed in Table 5. In addition, the linear alkylbenzene linearity in each reaction product was greater than 97%.
TABLE 5 investigation results of dilution solvent species and dilution ratio influence on catalyst activity stability
| Kind of diluting solvent | S/O | X，％ | S LAA ，％ | t S ，h |
| N-dodecane | 3:1 | 98.82 | 98.43 | 2230 |
| N-dodecane | 8:1 | 98.54 | 98.55 | 2380 |
| C 10 ～C 13 Liquid wax | 3:1 | 98.79 | 98.39 | 2426 |
| C 10 ～C 13 Liquid wax | 8:1 | 98.61 | 98.47 | 2512 |
| C 10 ～C 13 LAB | 3:1 | 98.77 | 98.56 | 2613 |
| C 10 ～C 13 LAB | 8:1 | 98.45 | 98.75 | 2832 |
From the data in Table 5, it is found that as the molar ratio of the diluting solvent to the linear olefin is increased, the reaction stabilization time is gradually prolonged or the catalyst activity stability is gradually improved. The reason is that the increase of the molar ratio of the diluting solvent to the linear olefin reduces the olefin concentration in the reaction fluid, so that the catalyst coking deactivation rate caused by olefin polymerization is reduced, and the improvement of the activity stability of the catalyst is facilitated. In addition, the reaction results of adding n-alkanes (including n-dodecane and liquid wax) to the raw materials and diluting the solvent with LAB showed that the stable reaction time or catalyst activity stability of the latter was better than that of the former. The reason for this is probably that the LAB molecules have both long chain alkyl groups and benzene rings, which dissolve and disperse long chain olefins, promote the mutual solubility of benzene and olefins, reduce the chance of olefin polymerization, and inhibit the coke formation rate; and the coke precursor has good dissolving effect, the coking and inactivation of the catalyst are inhibited, and the activity stability of the catalyst is improved. It can also be seen from table 5 that the addition of n-dodecane, liquid wax or LAB dilution solvent to the feed had little effect on olefin conversion and alkylation selectivity.
Example 8: investigation of the Effect of alkylation reaction conditions
The main reaction conditions for the liquid phase alkylation reaction of aromatic hydrocarbon and straight chain olefin comprise temperature, mass space velocity and molar ratio of aromatic hydrocarbon to olefin. In a manner similar to that of example 3, 4.0g of the 20-40 mesh CWZ-0.15-N-700-70 catalyst prepared in example 2 was charged in a fixed bed reactor, and the ratio of the nitrogen flow rate to the catalyst mass was 0.03m at 250 ℃ 3 /(h.g) the catalyst bed was pretreated with a 2h nitrogen purge. Benzene was fed to the reactor at a temperature of 50 ℃ to fill the reactor with benzene. Adding C to the alkylation reaction raw material 10 ～C 13 Liquid wax diluting solvent, liquid wax and C 16 ～C 18 The linear chain olefin has a molar ratio of 8:1, and comprises benzene, liquid wax and C under the liquid phase reaction condition of 4.0MPa 16 ～C 18 The reaction raw material of linear olefin was fed into the reactor for continuous alkylation reaction, and the influence of reaction temperature, mass space velocity and molar ratio of the raw material benzene to olefin was examined, and the reaction experimental results are shown in table 6.
Table 6 Experimental results for examining the influence of reaction conditions
It can be seen from table 6 that, under the condition of constant mass space velocity and molar ratio of benzene and olefin, as the alkylation reaction temperature is increased from 150 ℃ to 280 ℃, the olefin conversion rate is gradually increased, the catalyst activity stabilization time is gradually prolonged, and the linear alkylbenzene selectivity and linear alkylbenzene linearity are gradually reduced. Under the conditions of 250 ℃ and 20:1 of benzene-olefin molar ratio, the olefin conversion rate, the linear alkylbenzene linearity and the catalyst activity stabilization time are gradually reduced along with the increase of mass space velocity, and the linear alkylbenzene selectivity is gradually increased. In addition, the temperature is 250 ℃ and the mass space velocity is 1.0h -1 The olefin conversion rate, the linear alkyl benzene selectivity and the linear alkyl benzene linearity are increased along with the increase of the benzene-olefin molar ratio of the raw materialThe stability time of the catalyst activity and the degree become good, and only the productivity of the device is reduced and the energy consumption of separation is increased. In general, preferred alkylation reaction conditions include a temperature of 250 ℃ and a mass space velocity of 1.0h -1 And the molar ratio of the raw material benzene to the alkene is 20: 1.
Example 9: burning regeneration condition and regeneration performance investigation of alkylation catalyst
Using 4.0g of the 20-40 mesh CWZ-0.15-N-700-70 catalyst prepared in example 2, C was added to the alkylation reaction raw material in a similar manner to example 3 10 ～C 13 Liquid wax diluting solvent, liquid wax and C 16 ～C 18 The linear olefin molar ratio is 8:1, the temperature is 250 ℃, the pressure is 4.0MPa, and the mass space velocity is 1.0h -1 Benzene and C 16 ～C 18 The continuous alkylation reaction is carried out under the liquid phase reaction condition that the mol ratio of the linear olefin is 20:1, the reaction raw material is stopped to be input when the conversion rate of the olefin is reduced to 85 percent, and the input flow is 0.2m 3 Per hour of nitrogen, the ratio of the nitrogen flow to the catalyst mass being 0.05m 3 /(h.g), nitrogen purge 2h to give coked, deactivated catalyst.
And (4) carrying out coke burning regeneration on the deactivated catalyst. The input flow rate of the catalyst to the reactor containing the deactivated catalyst is 0.2-1.0 m 3 Air/catalyst mass ratio (R) AIR/CAT ) 0.05 to 0.25m 3 /(. h. g), heating at a heating rate of 0.2-5.0 ℃/min, raising the temperature of air scorching regeneration from the initial temperature of 100-400 ℃ to the termination temperature of 480-650 ℃, and scorching at the constant temperature of the final temperature for 1.0-24.0 h; finally, the input flow is 0.2m 3 Per hour of nitrogen, the ratio of the nitrogen flow to the catalyst mass being 0.05m 3 /(h.g), the reactor catalyst bed temperature was reduced from the final scorch temperature to 250 ℃ and nitrogen purge was continued for 2h, completing the catalyst regeneration procedure. Using regenerated catalyst, at 250 deg.C, 4.0MPa and 1.0h of mass space velocity -1 Benzene and C 16 ～C 18 Long chain olefin molar ratio 20:1, liquid wax to C 16 ～C 18 The continuous alkylation reaction is carried out under the liquid phase reaction condition that the mole ratio of the long-chain olefin is 8:1, and the reaction results of the regenerated catalysts under different scorching regeneration conditions are listed inTable 7. In addition, each regenerated catalyst had linear alkylbenzene linearity comparable to that of the fresh catalyst.
TABLE 7 evaluation results of scorch regeneration conditions and regeneration performance of alkylation catalysts
Comparing the data in table 7 with the fresh catalyst reaction results (fresh catalyst olefin conversion of 99.23%, linear alkylbenzene selectivity of 98.45%, activity stabilization time of 2518h) of the corresponding alkylation conditions in table 6, it can be seen that the olefin conversion of the regenerated catalyst obtained by coke-burning regeneration under the conditions in table 8 is slightly lower than that of the fresh catalyst, and the linear alkylbenzene selectivity and the activity stabilization time of the regenerated catalyst are slightly better than those of the fresh catalyst. The reason for this may be that the mesoporous WO is obtained by alkylation reaction and scorch regeneration 3 /ZrO 2 The surface acidity of the composite oxide catalyst is changed, the reaction selectivity is improved, and the coking inactivation rate of the catalyst is reduced. Visible, mesoporous WO 3 /ZrO 2 The composite oxide catalyst has good coke-burning regeneration performance.
Example 10: analysis of the Properties and composition of the alkylated products
4.0g of the 20-40 mesh CWZ-0.15-N-700-70 catalyst prepared in example 2 was charged into the 1 st fixed bed reactor, and 4.0g of the 20-40 mesh CWZ-0.15-N-800-70 catalyst prepared in example 2 having a larger pore size was charged into the 2 nd fixed bed reactor, and these two reactors were operated in series. Using a method similar to example 3, the ratio of the nitrogen flow to the mass of catalyst in each reactor was 0.03m at 250 ℃ 3 /(h. g) the catalyst bed was pre-treated with a 2h nitrogen purge. Benzene was fed to reactor 1 and reactor 2 at a temperature of 50 c, both reactors being filled with benzene. Then, the mixture will contain benzene and C 10 ～C 13 Linear olefins and C 10 ～C 13 The mixed raw material of the liquid wax is input into two reactors connected in series, wherein the molar ratio of the liquid wax to the linear chain olefin is 9:1, and the molar ratio of benzene to the linear chain olefin is 20: 1. In thatThe two reactors connected in series are carried out at the temperature of 250 ℃, the pressure of 4.0MPa and the mass space velocity of 2.0h -1 And collecting the reactor effluent. The effluent is subjected to reduced pressure distillation separation to obtain C 10 ～C 13 A linear alkylbenzene product. According to the national standard of the people's republic of China GBT 5177- 10 ～C 13 Linear alkyl benzene products, and hydrofluoric acid catalyzed process for industrial production of C 10 ～C 13 Bromine index, refractive index n of linear alkylbenzenes D 20 Mass fraction of the sulfonatable compound, and the measurement results are shown in Table 8.
TABLE 8 Properties and compositions of the experimentally synthesized and commercial hydrofluoric acid catalyzed Linear alkylbenzenes
| Properties and composition | Experimental Synthesis of Linear alkylbenzenes | Industrial HF process for linear alkylbenzenes |
| Bromine index, mgBr/100g | 9.26 | 14.65 |
| Refractive index n D 20 | 1.4824 | 1.4825 |
| Mass fraction of sulfonatable substance,% | 97.57 | 97.56 |
As can be seen from Table 8, the mesoporous WO is used 3 /ZrO 2 The bromine index of the linear alkylbenzene synthesized by the composite oxide catalyst is obviously less than that of the linear alkylbenzene industrially produced by a hydrofluoric acid catalytic method, and reaches below 10.0mgBr/100g, and the refractive index and the mass fraction of the sulfonated substance of the linear alkylbenzene are equivalent to those of the linear alkylbenzene synthesized by an industrial hydrofluoric acid method. This shows that mesoporous WO is used 3 /ZrO 2 The stability and subsequent processing performance of the linear alkyl benzene synthesized by the composite oxide catalyst are superior to those of linear alkyl benzene synthesized by an industrial hydrofluoric acid method. In addition, the hydrofluoric acid catalytic industrial device is used for producing the linear alkylbenzene through the processes of hydrofluoric acid catalytic reaction, distillation separation and activated clay adsorption refining. The catalyst used in the invention has the double functions of alkylation catalysis and product refining, and can omit the activated clay adsorption refining operation of linear alkyl aromatic hydrocarbon products, or reduce the clay refining load, and avoid or reduce the environmental pollution caused by the disposal of waste clay.
The above experimental results show that the invention utilizes WO with mesoporous structure 3 /ZrO 2 The method for synthesizing the linear alkyl aromatic hydrocarbon by using the composite oxide solid acid catalyst has the advantages of high catalyst activity, good activity stability, high selectivity, good regeneration performance, good product quality, environment-friendly process method and good application prospect.
Claims (6)
1. A method for synthesizing a linear alkyl aromatic hydrocarbon, the method comprising:
firstly, inputting raw material aromatic hydrocarbon into a fixed bed alkylation reactor, and filling the fixed bed alkylation reactor with the raw material aromatic hydrocarbon; then raw material aromatic hydrocarbon and raw material C are mixed 6 ～C 24 The mixture of the linear olefin and the additive is input into a fixed bed reactor and is mixed with the mesoporous WO 3 /ZrO 2 The composite oxide solid acid catalyst is contacted with the mixture at the temperature of 100-300 ℃, the pressure of 0.2-10.0 MPa and the total mass airspeed of the feeding of 0.1-20.0 h -1 Carrying out a liquid phase reaction under the conditions of the amount ratio of aromatic hydrocarbon to linear olefin substance of 2-50: 1 and the amount ratio of additive to linear olefin substance of 0-20: 1Performing olefin alkylation reaction to generate a product, namely linear alkyl aromatic hydrocarbon;
taking one part of the effluent of the alkylation reactor as a circulating fluid which is circulated to the reactor, taking the other part of the effluent as an effluent fluid which is used for separating excessive raw materials and products by a distillation separation system, wherein the circulating ratio of the circulating fluid to the effluent fluid volume flow is 0-80;
after the catalyst is deactivated, the catalyst is burnt and regenerated for recycling;
the method comprises the following steps:
the raw material aromatic hydrocarbon is one or a mixture of more than two of benzene, toluene, ethylbenzene, xylene, methyl ethyl benzene, propyl benzene and diethyl benzene in any proportion;
the additive is a straight-chain alkyl aromatic hydrocarbon solvent or a straight-chain alkane solvent; the linear alkyl aromatic hydrocarbon solvent is selected from C 6 ～C 24 One or a mixture of more than two of linear alkyl benzene, toluene, ethylbenzene, xylene, methyl ethyl benzene, propyl benzene and diethyl benzene in any proportion; the straight-chain alkane solvent is selected from C 6 ～C 24 One or a mixture of more than two of straight-chain alkanes in any proportion.
2. The method for synthesizing linear alkyl aromatic hydrocarbons according to claim 1, wherein the mesopores of WO 3 /ZrO 2 After the composite oxide solid acid catalyst is loaded into a reactor, the composite oxide solid acid catalyst is firstly treated at the temperature of 100-500 ℃, the pressure of 0.1-5.0 MPa and the mass ratio of nitrogen flow to the catalyst of 0.01-0.1 m 3 /(h.g) pretreatment with nitrogen purge for 0.5-24 h, then used for alkylation reaction.
3. The method of synthesizing linear alkyl aromatic hydrocarbons according to claim 1, wherein the alkylation reaction conditions are: the temperature is 150-280 ℃, the pressure is 0.5-8.0 MPa, and the total mass airspeed of the feed is 0.2-5.0 h -1 The ratio of the amount of aromatic hydrocarbon to linear olefin material is 5 to 30:1, the ratio of the amount of additive to linear olefin material is 1 to 10:1, and the circulation of the ratio of the volume flow rate of the circulating fluid of the alkylation reactor to the volume flow rate of the effluent fluid of the de-distillation separation systemThe ratio is 1 to 50.
4. The method for synthesizing linear alkyl aromatic hydrocarbons according to claim 1, wherein the method for coke regeneration after catalyst deactivation comprises:
after the alkylation reaction raw material is stopped, firstly, nitrogen is input into the reactor, and the ratio of the nitrogen flow to the catalyst mass is 0.01-0.5 m 3 H, purging with nitrogen for 1-24 h, and completing the nitrogen purging operation; then, the ratio of the air flow to the catalyst mass is 0.05-0.25 m 3 /(h &), raising the temperature of air scorching regeneration from the initial temperature of 100-400 ℃ to the final temperature of 450-650 ℃ at the heating rate of 0.2-5.0 ℃/min, and scorching at the constant temperature of the final temperature for 1.0-24.0 h; finally, nitrogen is input, the ratio of the nitrogen flow to the catalyst mass is 0.01-0.5 m 3 And (h &), reducing the temperature of the catalyst bed layer of the reactor from the final scorching temperature to the alkylation reaction temperature, and continuing nitrogen purging for 1-24 h to finish the scorching regeneration operation of the catalyst.
5. The process for the synthesis of linear alkyl aromatic hydrocarbons according to claim 1, wherein the alkylation reaction unit is operated by a plurality of reactors in parallel or in series, each reactor being filled with the same or different alkylation catalyst; the reaction conditions in each reactor are the same or different.
6. The method for synthesizing linear alkyl aromatic hydrocarbons according to claim 1, wherein the mesopores of WO 3 /ZrO 2 The composite oxide solid acid catalyst is prepared by the following method:
(1) preparation of mesoporous WO by coprecipitation method 3 /ZrO 2 Composite oxide:
respectively preparing a zirconium source aqueous solution and an ammonium metatungstate aqueous solution with the concentrations of 0.1-0.5 mol/L and 0.02-0.2 mol/L, slowly adding the ammonium metatungstate aqueous solution into the zirconium source aqueous solution while stirring according to the composition requirements of the composite oxide, and continuously stirring for 5-30 min after the ammonium metatungstate aqueous solution is added, so that the zirconium source aqueous solution and the ammonium metatungstate aqueous solution are uniformly mixed to obtain a mixed solution; then adding ammonia water with the mass fraction of 25-28% into the mixture dropwiseMixing the solution until the pH value of the final solution is 9-10, continuously stirring for 30-60 min after the dropwise adding is finished, and then aging for 8-48 h at the temperature of 10-100 ℃; filtering after the aging is finished, washing with deionized water, filtering for 0-5 times, and drying for 8-48 h at the temperature of 80-120 ℃; finally, the temperature is programmed to be increased from 5-40 ℃ to 600-850 ℃ at the heating rate of 0.5-10 ℃/min, the mixture is roasted for 1-8 hours at constant temperature, and the WO is obtained after crushing 3 ：ZrO 2 The molar ratio is 0.05-0.2: 1 mesoporous WO 3 /ZrO 2 A composite oxide powder;
the zirconium source is one or a mixture of more than two of the following materials in any proportion: zirconyl nitrate, zirconyl chloride, zirconium hydroxide;
(2) extruding and forming a catalyst strip:
mixing the composite oxide, the alumina monohydrate and the sesbania powder for 5-30 min according to the mass ratio of the composite oxide to the alumina monohydrate of 0.1-1.8: 1 and the ratio of the sesbania powder to the total mass of the composite oxide and the alumina monohydrate of 0.02-0.08: 1 to obtain a solid mixture, adding deionized water in the mass ratio of 0.2-1.0: 1 to the solid mixture, and stirring and mixing for 5-30 min; then dropwise adding a dilute nitric acid aqueous solution with the mass fraction of 5-10% while stirring, wherein the addition amount of the dilute nitric acid aqueous solution ensures that the mixture can be kneaded into a mud mass, and extruding and forming; standing the strip object at the temperature of 5-40 ℃ for 4-24 h, and drying at the temperature of 90-120 ℃ for 5-24 h; then, the temperature is programmed to be increased from 5-40 ℃ to 500-600 ℃ at a heating rate of 0.5-10 ℃/min, and the mixture is roasted at a constant temperature for 1-10 hours to obtain WO 3 /ZrO 2 Molded mesoporous WO with composite oxide mass fraction of 10-70% 3 /ZrO 2 Catalyst, balance Al 2 O 3 。
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