CN1569779A - Alkylation process - Google Patents

Alkylation process Download PDF

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Publication number
CN1569779A
CN1569779A CN 03146474 CN03146474A CN1569779A CN 1569779 A CN1569779 A CN 1569779A CN 03146474 CN03146474 CN 03146474 CN 03146474 A CN03146474 A CN 03146474A CN 1569779 A CN1569779 A CN 1569779A
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molecular sieve
reaction
alkene
isoparaffin
nano
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CN1234663C (en
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付强
王永睿
谢文华
慕旭宏
宗保宁
闵恩泽
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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Abstract

Disclosed is an alkylation process by subjecting reaction raw material containing isoalkane and alkene to reaction at the presence of solid acid catalyst, wherein the solid acid catalyst being a composite material consisting of SiO2 and/or Al2O3 with beta-molecular sieve, the weight ratio of SiO2 and/or Al2O3 with beta-molecular sieve in the composite material is (0.2-5) : 1.

Description

A kind of alkylation reaction method
Technical field
The invention relates to a kind of alkylation reaction method, further say so about the alkylation reaction method in the presence of solid acid catalyst.
Background technology
The alkylated reaction of isoparaffin and alkene (hereinafter to be referred as alkylation), mainly be meant isoparaffin under the strongly acidic catalyst effect with C 3-C 5Alkene reacts and generates the technology of alkylate oil, wherein with the catalytic cracking reaction product C in the petrochemical industry 4The reaction that the hydrocarbon component is converted into C8 side chain octane-iso (gasoline alkylate) is topmost.This reaction has obtained industrialization very soon since nineteen twenty-six comes out, since the fifties, the production of alkylate oil has obtained continuing significantly increasing, and alkylated reaction has become important technological process in the petrochemical industry.Gasoline alkylate is with its octane value height (RON94~96, MON92~94), susceptibility little, do not contain alkene and aromatic hydrocarbons, sulphur content is extremely low, the Reid steam forces down, the characteristics of combustion cleaning, become the ideal composition of reformulated gasoline (Reformulated Gasoline), be a kind of eco-friendly petrochemicals, and alkylation process also is acknowledged as one of the preferred plan that refinery olefins changes into the gasoline blend component of valuable, cleaning for a long time.
Though alkylation process has passed through 50 years of development, in petrochemical industry, still adopt traditional liquid acid alkylation process, i.e. sulfuric acid process and hydrofluoric acid method, and be found everywhere through the world, and with North America for.Liquid acid alkylation production can cause serious environmental to be polluted, and for example, hydrofluoric acid is volatile hypertoxic chemical, can produce acid mist in case leak in atmosphere, and human body and ecotope are had an immense impact on; Though it is littler than hydrofluoric acid that sulfuric acid is considered to danger, need to handle a large amount of spent acid.
The challenge that gasoline alkylate production faces makes people's active development alternative techniques, contains the catalyzer of halogen as use, but this can not fundamentally solve the uneasy congruent problem of pollution of ecological environment in the production, etching apparatus and production operation.From the angle of technical development, real solid acid catalyst not halogen-containing and other hazardous and noxious substances is only the target that people pursue.
The broad research of possible heterogeneous catalyst the metal oxide of molecular sieve, sulfur-bearing, sulfonate resin, solid super-strong acid/inorganics etc. have been comprised.Molecular sieve has had the history in more than 30 year as the research of hydrocarbon reaction catalyzer, it is because have real environmental friendliness characteristic, favorable industrialization basis and be easy to advantage such as regeneration receives increasing concern, is the solid acid catalyst that is considered to be hopeful most alternative liquid acid.In various molecular sieves, a cube zeolite, BETA, MCM-46, MCM-22, ZSM-4, USY, six euthalites, H-EMT, FAU, CEY-98 etc. have been comprised.
USP4,300,015 disclose a kind of catalyzer that is used for alkylated reaction, promptly with polyvalent metal ion large pore molecular sieve are carried out modification, thereby improve activity of such catalysts and selectivity.
USP4,384,161 disclose a kind of catalyzer of alkylated reaction, and this catalyzer comprises a kind of large pore zeolite (ZSM-4, ZSM-20, ZSM-3, ZSM-18, BETA, mordenite, FAU, Y, REY etc.) and Lewis acid.
USP4, disclosing MCM-22 in 992,615 is the alkylation of catalyzer.
USP5,258,569,5,254,792 disclose the method that adopts MCM-36 and MCM-49 catalytic alkylation reaction.
USP5,012,033 discloses a kind of isoparaffin-olefin alkylation catalyzer and technology.This technology is used with the acid-treated molecular sieve of Lewis and is catalyzer, makes under the condition that is reflected at higher space velocity and low alkane alkene ratio to carry out, and active and selectivity all increases.
WO9720787 discloses the method that adopts REUSY, REUSX catalytic alkylation reaction.
USP3,549,557 disclose a kind of method of alkylated reaction.It is catalyzer that this method adopts molecular sieve, catalyzing iso-butane alkane and C in fixed bed, moving-bed and fluidized-bed 2~C 3The alkylated reaction of alkene.
USP5,824,835 to disclose a kind of be the isoparaffin of catalyzer and the alkylation of alkene with the BETA molecular sieve, the silica alumina ratio of this molecular sieve is less than 18, and the metal constituent element of at least a divalence of load.
The disclosed alkylation of CN1059192C, comprise and use a kind of molecular sieve to be catalyzer with the polyvalent metal ion modification, and to introduce the lower material of a kind of critical temperature in reaction process be reaction medium, thereby improve the alkylated reaction selectivity and prolong the cycle lie of catalyzer.
Trimethylmethane that CN1230463A provides and iso-butylene alkylated solid super acidic catalyst are by the column IV element oxide compound TiO as carrier 2, ZrO 2, HfO 2With the six element oxide Cr of family as first promotor 2O 3, MoO 3And WO 3Form, by adding the yield that second kind of promotor, eight family's elements further improve strength of acid and improve alkylate.
CN1277893A is disclosed to be used for Trimethylmethane, butene alkylation to produce the modified zeolite catalyst of stop bracket gasoline is to be parent with the BETA zeolite, leach with metal-salt behind the conventional dealuminzation, promote that with vitriol perhaps use the titanium chloride load, roasting obtains then again.
At present, general viewpoint thinks that the structure of BETA molecular sieve is the most desirable concerning alkylated reaction.
Summary of the invention
The purpose of this invention is to provide a kind of solid acid catalyst and be difficult for alkylation inactivation, that running period is longer.
Alkylation provided by the invention is that the reaction raw materials that will contain isoparaffin and alkene reacts in the presence of solid acid catalyst, and said solid acid catalyst is a kind of by SiO 2And/or Al 2O 3With the matrix material that nano-beta molecular sieve is formed, SiO in this matrix material 2And/or Al 2O 3With the weight ratio of nano-beta molecular sieve be (0.2~5): 1.
In the method provided by the invention, in the preferred C4 of said isoparaffin~C7 isoparaffin one or more are considered industrial needs, and this isoparaffin is one or more in C4~C6 isoparaffin more preferably, as Trimethylmethane, iso-pentane or its mixture, Trimethylmethane most preferably wherein.
The various monoene that the preferred C3 of said alkene is above do not require the position of two keys in the described alkene, consider industrial needs, and this alkene is one or more in C3~C6 monoene more preferably, for example propylene, butylene or its mixture, wherein butylene most preferably.
In the alkylation provided by the invention, said solid acid catalyst can adopt the matrix material through prepared in various methods.For example people such as Landau is at Chem.Mater 1999, Vol.11, what describe in P2030~2037 is the matrix material that the beta-molecular sieve of 10-15nm is stable at method preparation in the alumina gel with granular size, this method is that the aluminum hydroxide gel filter cake is scattered in the water, make the aluminium hydroxide suspension of pH=9.05, under the room temperature with the beta-molecular sieve slurries of pH=12.7 according to Al 2O 3The weight ratio of/molecular sieve=1: 1 is mixed to pH=11.8, stirs after 2 hours under the room temperature aging 24 hours; Isolate precipitation by decant, and be 70 weight %, extruder grain and 120 ℃ of dryings 5 hours at 50 ℃ of vacuum-dryings to water-content.
In alkylation provided by the invention, said solid acid catalyst preferably adopt at application number be 02100379.3, the SiO of disclosed method preparation in the Chinese patent application that the applying date is on January 17th, 2002 2And/or Al 2O 3Matrix material with the nano-beta molecular sieve composition.Specifically, this matrix material be with pH be 1~4, SiO 2And/or Al 2O 3Content be the acidic silicasol of 10~50 weight % or acidic aluminum sol or acidic silicasol and aluminium colloidal sol mixture with contain 10~50 weight % nano-beta molecular sieves, pH is that 9~14 molecular sieve pulp is according to (SiO 2And/or Al 2O 3The weight ratio of)/molecular sieve=0.2~5 is under agitation mixed, and making the pH that mixes back gained mixture is 7~9.5, thereby forms gel, then gained gel drying and pulverizing or shaping is obtained.
In the preparation method of this matrix material, said acidic silicasol can be commercially available acid inorganic silicon colloidal sol, also can be the acidic hydrolysis solution of the silicon that makes of the hydrolysis by the organosilicon acid esters.Described organosilicon acid esters is methyl silicate, tetraethoxy, positive silicic acid propyl ester etc.; The hydrolysising condition of described organosilicon acid esters is that the technician in Preparation of Catalyst field is known; For example, the method that hydrolysis by the organosilicon acid esters prepares the acidic hydrolysis solution of silicon can be: a kind of organosilicon acid esters is mixed with the alcohols with 1~6 carbon atom make solution, and add entry, make that the weight ratio of organosilicon acid esters and said alcohol and water is an ester in the gained mixture: alcohol: water=1: (0.1~4.0): (0.1~4), preferred ester: alcohol: water=1: (0.1~2.0): (0.1~3), the gained mixture was at room temperature stirred 0.5~3 hour, then with pH regulator to 1~4 of diluted mineral acid gained solution.
Alkylation reaction method provided by the invention, the type of defined reaction device can not carried out in various reactors, as fixed-bed reactor, tank reactor, moving-burden bed reactor, fluidized-bed reactor or three-phase slurry bed reactor etc.
In the method provided by the invention, said raw material feeding manner can adopt alkane and alkene respectively charging or the mixture of alkane and alkene and the mode that alkane is distinguished independent charging after charging, alkane and the olefin separately.Any one or a few alkane or alkene or any one or a few alkane in the raw material or/and the mixture of alkene can add in the reaction system at any position of reactive system, and can adopt respectively intermittently, semicontinuous or successive feeding manner.
Said alkylation reaction condition has no particular limits, existing alkylation reaction condition in the preferred employing prior art, as temperature is 10~350 ℃, and pressure is 0.5~10.0MPa, and the weight ratio scope of isoparaffin and alkene is reaction conditionss well known to those skilled in the art such as 2~100.
The alkylation of isoparaffin provided by the invention and alkene is with SiO 2And/or Al 2O 3The matrix material of forming with nano-beta molecular sieve is as alkylation catalyst, adopt this matrix material, compare with the art methods that adopts beta-molecular sieve, can effectively prolong butene conversion and reduce to runtime of 90% by 100%, for example, under the nanometer β zeolite existence condition of same operation parameter and same amount, it is 390 minutes that embodiment 36 transformation efficiencys are reduced to runtime of 90% by 100%, TMP/DMH is 6.82, and Comparative Examples has only 227 minutes, and TMP/DMH is 4.12.
Embodiment
The present invention is further illustrated below by embodiment, but content not thereby limiting the invention.
The preparation process of the matrix material that adopts in embodiment 1~5 explanation the inventive method.
In embodiment 1~5, said nano-beta molecular sieve is the method synthetic of describing according to the embodiment in the Chinese patent application 00107486.5 7.Detailed process is as follows:
Pseudo-boehmite (is contained Al 2O 356.6 weight %, Qilu Petrochemical company catalyst plant product), sodium hydroxide (chemical pure, Beijing Chemical Plant's product), tetraethyl ammonium hydroxide solution (2.633N, go in in a big way emerging good fortune fine chemistry industry institute) add deionized water, heating for dissolving stirs, and makes working solution, with silochrom (80-120 order, igloss 3.7%, Haiyang Chemical Plant, Qingdao) mix with above-mentioned working solution, make the silica gel surface wetting by working solution, obtain reaction mixture, wherein the mol ratio of each component is SiO 2/ Al 2O 3=30, Na 2O/SiO 2=0.075, TEAOH/SiO 2=0.09, H 2O/SiO 2=6.5, add then that additive SY1634-70 (50 weight %)+(wherein SY1634-70 is a kind of commercially available vacuum pump oil to Tween-65 (50 weight %), seven factories of Dalian Petrochemical Industry Company produce, molecular weight 800-1000, and polyoxyethylene groups shared weight ratio in said polyalkylene ether is 25%; Tween-65 is Farco company commodity, molecular weight 800-1000, HLB=10.5) and stir additive/SiO 2Weight ratio is 2.5.With this reaction mixture 120 ℃ of crystallization 24 hours in autoclave, again 140 ℃ of crystallization 48 hours, promptly get molecular sieve pulp (containing molecular sieve 38 weight %) after being cooled to room temperature, this molecular sieve pulp is directly used in the preparation of the catalytic composite materials of back without filtration.
Above-mentioned molecular sieve pulp takes a morsel, the slurries of each part weight add the flocculation agent ammonium chloride (promoting to filter) of a weight, filter to isolate solid product, with carrying out ammonium exchange 4 times among the 1N ammonium chloride solution 400ml, each 2 hours, exchange after-filtration, washing, 110 ℃ of dryings 2 hours at every turn, obtain ammonium type β zeolite powder, be designated as A, the granularity that transmission electron microscope records this zeolite powder is 50~60 nanometers.
Embodiment 1
Present embodiment explanation nano-beta molecular sieve/SiO 2Preparation.
(Beijing chemical reagents corporation produces with the 20.8g tetraethoxy, analytical pure) is dissolved in 5.76g dehydrated alcohol (Beijing Chemical Plant, analytical pure) in, stir down it is added dropwise among the 0.01MHCl of 100ml, obtain the clear sol (pH=2) after the silicon hydrolysis, (molecular sieve concentration is 38 heavy % in the slurries with nano-beta molecular sieve slurries 28.8g then, adjust its pH=14 with 0.8M NaOH) under agitation join in the above-mentioned silicon sol, colloidal sol forms gel (recording the pH=9 of this gel with accurate pH test paper) at 10-20 in second.With gained gel drying under 40 ℃, obtain containing the mixture xerogel of 65% molecular sieve.Product is ground, and sieve is got 40-60 purpose particle, with 60 ℃ hot water making beating washing secondary, exchange 4 times with carrying out ammonium among the 1N ammonium chloride solution 400ml more earlier, and each 2 hours, exchange after-filtration, washing, 110 ℃ of dryings 2 hours at every turn, obtain ammonium type product.Be designated as B1, SiO 2With the weight ratio of beta-molecular sieve be 0.54.
According to document Chem.Mater 1999, Vol.11, the method of describing in P2030~2037 is promptly judged the dispersity of nano molecular sieve on carrier in β/carrier complexes by the sudden change that changes electronic probe beam diameter mensuration catalytic material silica alumina ratio with the particle diameter (down together) of molecular sieve in the determination of transmission electron microscopy catalytic material of being with the microcell ultimate analysis.When electronic probe beam diameter during greater than the nano molecular sieve particle diameter, show as the average silica alumina ratio of system, reduce the probe beam diameter until with the nano molecular sieve particle diameter near the time, the silica alumina ratio that shows as system produces sudden change.The result shows that beta-molecular sieve is scattered in SiO with 50nm among the B1 2In.
Embodiment 2
Present embodiment explanation nano-beta molecular sieve/SiO 2Preparation.
Nano-beta molecular sieve slurries 3.84g (molecular sieve concentration is 38 heavy % in the slurries, adjusts its pH=13 with 0.8M NaOH) is under agitation joined the acid inorganic silicon colloidal sol of 22.5g (Changhong chemical plant, Beijing commodity, SiO 2Content is 25.9 weight %, pH=1.6) in, colloidal sol forms gel (recording the pH=7.5 of this gel with accurate pH test paper) at 10-20 in second.With gained gel drying under 40 ℃, obtain containing the mixture xerogel of 20% molecular sieve.Product is ground, and sieve is got 40-60 purpose particle, with 60 ℃ hot water making beating washing secondary, exchange 4 times with carrying out ammonium among the 1N ammonium chloride solution 400ml more earlier, and each 2 hours, exchange after-filtration, washing, 110 ℃ of dryings 2 hours at every turn, obtain ammonium type product.Be designated as B2, SiO 2With the weight ratio of beta-molecular sieve be 4.
Record according to the method for embodiment 1 that beta-molecular sieve is scattered in SiO with 50nm among the B2 2In.
Embodiment 3
Nano-beta molecular sieve/Al is described 2O 3Preparation.
(Qilu Petrochemical company catalyst plant commodity are made Al by metallic aluminium and hydrochloric acid reaction under agitation to join the 7.3g acidic aluminum sol with nano-beta molecular sieve slurries 1.68g (molecular sieve concentration is 38 heavy % in the slurries, its pH=13) 2O 3Content is 35 weight %, pH=1.5) in, colloidal sol forms gel (recording the pH=8 of this gel with accurate pH test paper) rapidly in 5-10s.With gained gel drying under 70 ℃, obtain containing the mixture xerogel of 65% molecular sieve.Product is ground, and sieve is got 40-60 purpose particle, with 60 ℃ hot water making beating washing secondary, exchange 4 times with carrying out ammonium among the 1N ammonium chloride solution 400ml more earlier, and each 2 hours, exchange after-filtration, washing, 110 ℃ of dryings 2 hours at every turn, obtain ammonium type product.Be designated as B3, Al 2O 3With the weight ratio of beta-molecular sieve be 0.54.
Record according to the method for embodiment 1 that beta-molecular sieve is scattered in Al with 5nm among the B3 2O 3In.
Embodiment 4
Nano-beta molecular sieve/Al is described 2O 3Preparation.
(Qilu Petrochemical company catalyst plant commodity are made Al by metallic aluminium and hydrochloric acid reaction under agitation to join the 1.8g acidic aluminum sol with nano-beta molecular sieve slurries 1.68g (molecular sieve concentration is 38 heavy % in the slurries, its pH=13) 2O 3Content is 35 weight %, pH=1.5) in, colloidal sol forms gel (recording the pH=8 of this gel with accurate pH test paper) rapidly in 5-10s.With gained gel drying under 70 ℃, obtain containing the mixture xerogel of 50% molecular sieve.Product is ground, and sieve is got 40-60 purpose particle, with 60 ℃ hot water making beating washing secondary, exchange 4 times with carrying out ammonium among the 1N ammonium chloride solution 400ml more earlier, and each 2 hours, exchange after-filtration, washing, 110 ℃ of dryings 2 hours at every turn, obtain ammonium type product.Be designated as B4, Al 2O 3With the weight ratio of beta-molecular sieve be 1.
Record according to the method for embodiment 1 that beta-molecular sieve is scattered in Al with 50nm among the B4 2O 3In.
Embodiment 5
Nano-beta molecular sieve/SiO is described 2-Al 2O 3The preparation of mixture.
1.53g embodiment 1 described silicon sol and 5.8g embodiment 3 described aluminium colloidal sols are at room temperature mixed obtain combination of acidic silicon-aluminum sol (pH=3.7).Then nano-beta molecular sieve slurries 9.6g (molecular sieve concentration is 38 heavy % in the slurries, its pH=13) is under agitation joined in the described complex sol, colloidal sol forms gel (recording the pH=9.5 of this gel with accurate pH test paper) rapidly in 5-10s.With gained gel drying under 70 ℃, obtain containing the mixture xerogel of 65% molecular sieve.Product is ground, and sieve is got 40-60 purpose particle, with 60 ℃ hot water making beating washing secondary, exchange 4 times with carrying out ammonium among the 1N ammonium chloride solution 400ml more earlier, and each 2 hours, exchange after-filtration, washing, 110 ℃ of dryings 2 hours at every turn, obtain ammonium type product.Note is made B5, (SiO 2+ Al 2O 3) with the weight ratio of beta-molecular sieve be 0.54.
Record according to the method for embodiment 1 that beta-molecular sieve is scattered in SiO with 50nm among the B5 2-Al 2O 3In.
Embodiment 6~36 explanations alkylation provided by the invention.
In following examples, used matrix material B1~B5 is respectively by the preparation of the process of embodiment 1~5, used matrix material B6 be according to people such as Landau at Chem.Mater 1999, Vol.11, the method of describing among the P2030-2037 prepares, wherein nano-beta molecular sieve and Al 2O 3Weight ratio be 0.54.
Embodiment 6~29 alkylated reaction results of explanation in fixed-bed reactor.
B1~B6 and commercially available beta-molecular sieve as a comparison all, use after being 20~40 orders through compressing tablet, pulverizing after 3.0 hours at 550 ℃ of roasts.
Embodiment 6
Adopt fixed-bed reactor, add 1.0 gram B1 in reactor, reactor is warming up to 80 ℃, when pressure reaches 2MPa, with 2.0h -1Weight space velocity add raw material 100 grams (weight ratio of Trimethylmethane and n-butene is 10: 1 in the raw material, down with) of Trimethylmethane and n-butene, with the reaction end gas on-line analysis, collect product at last and detect, reaction result sees Table 1.
Comparative Examples 1
With the operational condition of embodiment 6, difference is that catalyst system therefor is that (its active component content is identical with B1 for commercially available beta-molecular sieve 0.65 gram.Reaction result sees Table 1.
Embodiment 7
With embodiment 6 operational conditions, difference is that temperature of reaction is 90 ℃.Reaction result sees Table 1.
Embodiment 8
With embodiment 6 operational conditions, difference is that temperature of reaction is 100 ℃.Reaction result sees Table 1.
Embodiment 9
With embodiment 6 operational conditions, difference is that raw material is raw material 100 gram (weight ratio of iso-pentane and propylene is 10: 1 in the raw material) of iso-pentane, propylene, with the reaction end gas on-line analysis, collects product at last and detects, and reaction result sees Table 1.
Table 1
The embodiment numbering ??6 Comparative Examples 1 ??7 ??8 ??9
Product is formed ????C5-C7 ??8.81 ??29.30 ??21.4 ??4.60 ??13.27
????C8 ??68.63 ??40.95 ??56.18 ??58.84 ??56.70
????C9+ ??22.56 ??29.75 ??22.42 ??36.56 ??30.03
????TMP/DMH ??5.08 ??3.06 ??4.98 ??4.31 ??3.24
Butene conversion reduce to 90% o'clock time (minute) ??300 ??170 ??269 ??184 ??271
The C8 component mainly is made up of isoparaffin dimethylhexane (DMH) and trimethylpentane (TMP) in the alkylated reaction, and wherein TMP is the purpose product, so product is bigger as if the ratio of C8 content height and TMP/DMH, then the excellent catalytic effect of catalyzer.
Olefin conversion reduced to for 90% required time, can be used as the whether standard of inactivation of catalyzer of weighing.
As can be seen from Table 1, embodiment 6 can obtain better reaction result than Comparative Examples 1.
Embodiment 10~13
The matrix material that adopts is B2, the reaction parameter of the corresponding embodiment 6~9 of embodiment 10~13 orders, and gained the results are shown in table 2.
Comparative Examples 2
With the operational condition of embodiment 10, difference is that catalyst system therefor is that (its active component content is identical with B2 for commercially available beta-molecular sieve 0.2 gram.Reaction result sees Table 2.
Table 2
The embodiment numbering ??10 Comparative Examples 2 ??11 ??12 ??13
Product is formed ????C5-C7 ??18.65 ??28.14 ??23.60 ??14.60 ??23.66
????C8 ??58.61 ??32.77 ??42.21 ??44.84 ??48.62
????C9+ ??22.74 ??39.09 ??34.19 ??40.56 ??27.72
????TMP/DMH ??5.89 ??3.03 ??4.26 ??4.02 ??2.96
Butene conversion reduce to 90% o'clock time (minute) ??275 ??209 ??223 ??193 ??218
As can be seen from Table 2, embodiment 10 can obtain better reaction result than Comparative Examples 2.
Embodiment 14~17
The matrix material that adopts is B3, the reaction parameter of the corresponding embodiment 6~9 of embodiment 14~17 orders, and gained the results are shown in table 3.
Table 3
The embodiment numbering ??14 Comparative Examples 1 ??15 ??16 ??17
Product is formed ????C5-C7 ??14.44 ??29.30 ??15.41 ??18.60 ??19.97
????C8 ??72.18 ??40.95 ??64.63 ??53.84 ??46.88
????C9+ ??13.38 ??29.75 ??19.96 ??27.56 ??33.15
????TMP/DMH ??6.51 ??3.06 ??5.22 ??4.79 ??4.34
Butene conversion reduce to 90% o'clock time (minute) ??376 ??170 ??243 ??281 ??296
List file names with the data of Comparative Examples 1 in the table 3.As can be seen from Table 3, embodiment 14 can obtain better reaction result than Comparative Examples 1.
Embodiment 18~21
The matrix material that adopts is B4, the reaction parameter of the corresponding embodiment 6~9 of embodiment 18~21 orders, and gained the results are shown in table 4.
Comparative Examples 3
With the operational condition of embodiment 18, difference is that catalyst system therefor is commercially available beta-molecular sieve 0.5 gram (its active component content is identical with B4).Reaction result sees Table 4.
Table 4
The embodiment numbering ??18 Comparative Examples 3 ??19 ??20 ??21
Product is formed ????C5-C7 ??10.94 ??27.55 ??15.82 ??20.01 ??21.74
????C8 ??70.99 ??48.34 ??64.57 ??60.84 ??55.79
????C9+ ??18.07 ??24.11 ??19.61 ??19.15 ??22.47
????TMP/DMH ??5.61 ??4.39 ??4.28 ??3.99 ??4.73
Butene conversion reduce to 90% o'clock time (minute) ??301 ??210 ??284 ??227 ??256
As can be seen from Table 4, embodiment 18 can obtain better reaction result than Comparative Examples 3.
Embodiment 22~25
The matrix material that adopts is B5, the reaction parameter of the corresponding embodiment 6~9 of embodiment 22~25 orders, and gained the results are shown in table 5.
Table 5
The embodiment numbering ??22 Comparative Examples 1 ??23 ??24 ??25
Product is formed ????C5-C7 ??11.88 ??29.30 ??18.81 ??20.50 ??19.22
????C8 ??78.86 ??40.95 ??69.93 ??60.48 ??57.19
????C9+ ??9.26 ??29.75 ??11.26 ??19.02 ??23.59
????TMP/DMH ??6.41 ??3.06 ??5.69 ??4.82 ??4.53
Butene conversion reduce to 90% o'clock time (minute) ??357 ??170 ??311 ??282 ??266
The data of Comparative Examples 1 have been listed file names with in the table 5.As can be seen from Table 5, embodiment 22 can obtain better reaction result than Comparative Examples 1.
Embodiment 26~29
The matrix material that adopts is B6, the reaction parameter of the corresponding embodiment 6~9 of embodiment 26~29 orders, and gained the results are shown in table 6.
Table 6
Numbering Embodiment 26 Embodiment 27 Embodiment 28 Embodiment 29
Product is formed ????C5-C7 ??21.40 ??26.01 ??28.03 ??26.55
????C8 ??64.23 ??60.59 ??57.62 ??55.98
????C9+ ??14.37 ??13.40 ??14.35 ??17.47
????TMP/DMH ??4.98 ??5.98 ??4.31 ??3.24
Butene conversion reduce to 90% o'clock time (minute) ??265 ??241 ??209 ??213
As can be seen from Table 6, embodiment 26 can obtain reaction result preferably.
Embodiment 30~36 alkylated reaction results of explanation in tank reactor.
Used B1~B6 all uses after 3.0 hours at 550 ℃ of roasts.
Embodiment 30
10 gram B1 are added autoclave, be warming up to 80 ℃, when pressure reaches 2MPa, add the 100g Trimethylmethane earlier, again with 0.2h -1Weight space velocity add the mixing raw material (Trimethylmethane and butylene weight ratio are 10: 1, down with) of Trimethylmethane, butylene, online collection product also detects, time and final product composition that butene conversion was reduced to 90% o'clock see Table 7.
Embodiment 31
With embodiment 30, difference is that matrix material is 10 gram B2, and time and final product composition that butene conversion was reduced to 90% o'clock see Table 7.
Embodiment 32
With embodiment 30, difference is that matrix material is 10 gram B3, and time and final product composition that butene conversion was reduced to 90% o'clock see Table 7.
Embodiment 33
With embodiment 32, difference is that temperature of reaction is 90 ℃, and time and final product composition that butene conversion was reduced to 90% o'clock see Table 7.
Embodiment 34
With embodiment 30, difference is that matrix material is 10 gram B4, and temperature of reaction is 100 ℃, and time and final product composition that butene conversion was reduced to 90% o'clock see Table 7.
Embodiment 35
With embodiment 30, difference is that matrix material is 10 gram B6, and time and final product composition that butene conversion was reduced to 90% o'clock see Table 7.
Table 7
The embodiment numbering Butene conversion reduce to 90% o'clock time (minute) Product is formed
??C5-C7 ??C8 ??C9+ ????TMP/DMH
??30 ??358 ??16.38 ??69.20 ??14.42 ????5.64
??31 ??324 ??19.09 ??62.33 ??18.58 ????5.03
??32 ??371 ??13.30 ??74.05 ??12.65 ????6.47
??33 ??362 ??15.48 ??70.69 ??13.83 ????6.05
??34 ??336 ??12.96 ??70.37 ??16.67 ????5.67
??35 ??294 ??9.57 ??68.55 ??21.88 ????4.97
By last table embodiment 32,33 as can be known, in the experimental temperature scope, when using identical catalyzer, temperature of reaction is low more, and it is long more that olefin conversion is reduced to 90% required time.Embodiment 32 can obtain more excellent reaction result.
Embodiment 36
10 gram B5 are added autoclave, be warming up to 80 ℃, when pressure reaches 2MPa, add the 100g Trimethylmethane earlier, again with 0.2h -1Weight space velocity add the mixing raw material of Trimethylmethane, butylene, online collection product also detects, butene conversion is reduced to time of 90% o'clock and final product and is formed and see Table 8.
Comparative Examples 4
With embodiment 36, difference is that catalyst system therefor is commercially available beta-molecular sieve product 6.5 gram (Si/Al=25, Qilu Petrochemical company catalyst plant is produced, and is identical with the content of beta-molecular sieve active ingredient among the B5), time and final product composition that butene conversion was reduced to 90% o'clock see Table 8.
Table 8
The embodiment numbering Butene conversion reduce to 90% o'clock time (minute) Product is formed
??C5-C7 ??C8 ??C9+ ??TMP/DMH
??36 ??390 ??9.53 ??80.36 ??10.11 ??6.82
Comparative Examples 4 ??227 ??24.34 ??45.52 ??30.14 ??4.12
As can be seen from Table 8, the butene conversion of the embodiment time and the selectivity of reducing to 90% o'clock obviously is better than Comparative Examples 4.

Claims (19)

1, a kind of alkylation reaction method is that the reaction raw materials that will contain isoparaffin and alkene reacts in the presence of solid acid catalyst, it is characterized in that used solid acid catalyst is a kind of by SiO 2And/or Al 2O 3With the matrix material that nano-beta molecular sieve is formed, SiO in this matrix material 2And/or Al 2O 3With the weight ratio of nano-beta molecular sieve be (0.2~5): 1.
2, according to the method for claim 1, said matrix material be by pH be 1~4, SiO 2And/or Al 2O 3Content be the acidic silicasol of 10~50 weight % or acidic aluminum sol or acidic silicasol and aluminium colloidal sol mixture with contain 10~50 weight % nano-beta molecular sieves, pH is that 9~14 molecular sieve pulp is according to (SiO 2And/or Al 2O 3The weight ratio of)/molecular sieve=0.2~5 is under agitation mixed, and making the pH that mixes back gained mixture is 7~9.5, thereby forms gel, then gained gel drying and pulverizing or shaping is obtained.
3, according to the method for claim 2, wherein said acidic silicasol is acid inorganic silicon colloidal sol.
4, according to the method for claim 2, the hydrating solution of the tart silicon that wherein said acidic silicasol makes for the hydrolysis by the organosilicon acid esters.
5, according to the method for claim 2, the metallic aluminium colloidal sol of wherein said acidic aluminum sol for making by metallic aluminium and hydrochloric acid reaction.
6, according to the method for claim 2, wherein said acidic aluminum sol is colloidal sol or the soliquid that hydrated aluminum oxide obtains after with sour peptization.
7, according to the method for claim 2, wherein said nano-beta molecular sieve is that granular size is the molecular sieve of 1~100nm.
8, according to the method for claim 2, wherein said molecular sieve pulp is not through filtering the molecular sieve pulp that directly obtains behind the synthesis of nano molecular sieve.
9, according to the method for claim 1, said isoparaffin is selected from one or more in C3~C7 isoparaffin.
10, according to the method for claim 9, said isoparaffin is selected from one or more in C4~C6 isoparaffin,
11, according to the method for claim 10, said isoparaffin is Trimethylmethane, iso-pentane or its mixture.
12, according to the method for claim 1, said alkene is the above various monoene of C3.
13, according to the method for claim 12, said alkene is selected from one or more in C3~C6 monoene.
14, according to the method for claim 13, said alkene is propylene, butylene or its mixture.
15, according to the method for claim 1, said alkylated reaction is the reaction of Trimethylmethane and butylene.
16, according to the method for arbitrary claim in claim 1 or 9~15, can in fixed-bed reactor, tank reactor, moving-burden bed reactor, fluidized-bed reactor or three-phase slurry bed reactor, carry out.
17,, it is characterized in that alkane and alkene respectively charging or the mixture of alkane and alkene and the mode that alkane is distinguished independent charging after charging, alkane and the olefin separately according to the said method of claim 16.
18, the said method of claim 17, it is characterized in that any one or a few alkane in the raw material or alkene or any one or a few alkane or/and the mixture of alkene can add in the reaction system at any position of reactive system, adopt intermittently, semicontinuous or successive feeding manner.
19, according to the method for claim 1, said reaction conditions is 10~350 ℃ of temperature, pressure 0.5~10.0MPa, and the weight ratio scope of isoparaffin and alkene is 2~100.
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Cited By (7)

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CN102631878A (en) * 2012-05-02 2012-08-15 浙江华亿工程设计有限公司 Intelligent reaction kettle
CN107597179A (en) * 2017-09-29 2018-01-19 钦州学院 A kind of MCM 49 molecular sieve catalysts of isooctane and preparation method thereof
CN111482195A (en) * 2019-01-25 2020-08-04 中国石油化工股份有限公司 Solid acid catalyst
CN111482194A (en) * 2019-01-25 2020-08-04 中国石油化工股份有限公司 Alkylation catalyst and application thereof
CN111482196A (en) * 2019-01-25 2020-08-04 中国石油化工股份有限公司 Preparation method of solid acid alkylation catalyst
CN111482193A (en) * 2019-01-25 2020-08-04 中国石油化工股份有限公司 Preparation method of solid acid catalyst
CN111482196B (en) * 2019-01-25 2021-11-16 中国石油化工股份有限公司 Preparation method of solid acid alkylation catalyst

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102631878A (en) * 2012-05-02 2012-08-15 浙江华亿工程设计有限公司 Intelligent reaction kettle
CN107597179A (en) * 2017-09-29 2018-01-19 钦州学院 A kind of MCM 49 molecular sieve catalysts of isooctane and preparation method thereof
CN111482195A (en) * 2019-01-25 2020-08-04 中国石油化工股份有限公司 Solid acid catalyst
CN111482194A (en) * 2019-01-25 2020-08-04 中国石油化工股份有限公司 Alkylation catalyst and application thereof
CN111482196A (en) * 2019-01-25 2020-08-04 中国石油化工股份有限公司 Preparation method of solid acid alkylation catalyst
CN111482193A (en) * 2019-01-25 2020-08-04 中国石油化工股份有限公司 Preparation method of solid acid catalyst
CN111482195B (en) * 2019-01-25 2021-05-14 中国石油化工股份有限公司 Solid acid catalyst
CN111482194B (en) * 2019-01-25 2021-05-14 中国石油化工股份有限公司 Alkylation catalyst and application thereof
CN111482193B (en) * 2019-01-25 2021-08-06 中国石油化工股份有限公司 Preparation method of solid acid catalyst
CN111482196B (en) * 2019-01-25 2021-11-16 中国石油化工股份有限公司 Preparation method of solid acid alkylation catalyst

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