CN1569778A - Process for alkylation of isoalkane and olefin - Google Patents
Process for alkylation of isoalkane and olefin Download PDFInfo
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- CN1569778A CN1569778A CN 03146473 CN03146473A CN1569778A CN 1569778 A CN1569778 A CN 1569778A CN 03146473 CN03146473 CN 03146473 CN 03146473 A CN03146473 A CN 03146473A CN 1569778 A CN1569778 A CN 1569778A
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Abstract
The invention discloses a process for alkylation of isoalkane and olefin, which comprises subjecting reaction raw material containing isoalkane and alkene to alkylation reaction at the presence of solid acid catalyst and a dielectric, wherein the solid acid catalyst is a composite material consisting of SiO2 and/or Al2O3 with nano beta molecular sieve, said dielectric being mixture of one or more selected from, C2-C6 oxygen-containing organic compound, C2-C6 halogen-containing organic compound, C3-C16 saturated aliphatic hydrocarbon.
Description
Technical field
The invention relates to the addition method of a kind of stable hydrocarbon and unsaturated hydrocarbons, further say so about the alkylation reaction method of isoparaffin and alkene.
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, comprised a cube zeolite, BETA, MCM-46, MCM-22, ZSM-4, USY, six euthalites, H-EMT, FAU, CEY-98 etc., at present, general viewpoint thinks that the structure of BETA molecular sieve is the most desirable concerning alkylated reaction.
CN 1277893A is disclosed to be used for Trimethylmethane, butene alkylation to produce the modification BETA 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.
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.
Summary of the invention
The objective of the invention is to overcome solid acid catalyst very easily inactivation, shortcoming that the conversion of olefines rate is lower in alkylated reaction, a kind of yield that can either effectively improve olefin conversion and alkylate oil is provided, can keeps the method for higher catalyst activity stability again.
The alkylation reaction method of isoparaffin provided by the invention and alkene, be that the reaction raw materials that will contain isoparaffin in the presence of solid acid catalyst and a kind of medium alkylated reaction takes place with the reaction raw materials that contains alkene, it is characterized in that 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, said medium be selected from oxygen-containing organic compound, the C1～C6 of one or more in the following substances: C2～C6 organic halogen compound, have the aliphatic saturated hydrocarbon of C3～C16.
In the method provided by the invention, in the preferred C4 of said isoparaffin～C7 isoparaffin one or more, consider industrial needs, this isoparaffin is one or more in C4～C6 isoparaffin more preferably, for example Trimethylmethane, iso-pentane or its mixture, wherein Trimethylmethane most preferably.
The various monoene that the preferred C3 of said alkene is above, position to two keys in the described alkene does not require, and considers industrial needs, and this alkene is one or more in C3～C6 monoene more preferably, for example propylene, butylene or its mixture, wherein most preferred 1-butylene.
Method provided by the invention is the alkylated reaction that takes place in the presence of a kind of medium, and said medium is selected from a kind of in the following substances: C2～C6 oxygen-containing organic compound, C1～C6 organic halogen compound, have the aliphatic saturated hydrocarbon of C3～C16.
Wherein said oxygen-containing organic compound is selected from Fatty Alcohol(C12-C14 and C12-C18), alicyclic ring alcohol, ketone, ether, alicyclic ether, alicyclic ring thioether, wherein preferred alcohol, propyl alcohol, isopropylcarbinol or tetrahydrofuran (THF).
Wherein said organic halogen compound is selected from alkane or the naphthenic hydrocarbon that is replaced by one or more halogen atoms, wherein preferred methylene dichloride, 1-chlorobutane or 1-fluorine hexanaphthene.
The aliphatic saturated hydrocarbon of said said C3～C16 can be selected from iso-pentane, pure isooctane or 2,2,5-trimethylammonium heptane etc., wherein preferred iso-pentane, pure isooctane.
In the method provided by the invention, alkane alkene mol ratio is (1～100): 1, preferred (2～20): 1, and the mol ratio of medium and alkene is (1～300): 1, preferred (2～30): 1.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 molar ratio range of isoparaffin and alkene is reaction conditionss well known to those skilled in the art such as 2～100.
In the method 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 the method preparation in the alumina gel with granular size, this method is that the aluminum hydroxide gel filter cake is scattered in the water, makes the aluminium hydroxide suspension of pH=9.05; With its at 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 (add rare nitric acid and make the pH that mixes rear slurry be respectively 11.0 and 10.0 in the said back of mixing) in the preparation of other two batch samples; Stir after 2 hours, wore out 24 hours under the room temperature; 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 nanometer β zeolite 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 provided by the invention does not limit the reactor types that reacts, and can finish in high pressure tank reactor or fixed-bed reactor.Alkylated reaction in the wherein said high pressure tank reactor can adopt periodical operation, semi-batch operation or operate continuously; Alkylated reaction in the said fixed-bed reactor, any one or a few alkane or alkene or any one or a few alkane in its raw material are or/and the mixture of alkene can be in any position adding reaction system of reactive system.
Alkylation provided by the invention is to be catalyzer with a kind of matrix material that contains nano-beta molecular sieve, and its C8 selectivity is better than the method for prior art; The medium that adds in reaction system gets off the timely dissolved flushing of the coke precursor that generates in the reaction process, reduces to runtime of 90% thereby prolonged olefin conversion by 100%.
Embodiment
The present invention is further illustrated below by embodiment, but content not thereby limiting the invention.
That adopts in embodiment 1～5 explanation the inventive method contains nanometer β prepare zeolite process.
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 JY 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 50nm 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 JY 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.
Following examples illustrate the result of alkylation provided by the invention in fixed-bed reactor.
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 for describing among the P2030-2037 prepares, wherein Al
2O
3With the weight ratio of nano-beta molecular sieve be 0.56.
Embodiment 6
Adopt autoclave reactor, in reactor, add the matrix material B1 and the 5 gram tetrahydrofuran (THF)s of 10.0 gram embodiment, 1 preparation earlier, sealed reactor.Squeeze into 100 gram Trimethylmethanes with pump then, reactor is warming up to 80 ℃, when pressure reaches 2MPa, squeezes into 1-butylene with pump in reactor again and react (the little hourly space velocity of weight (WHSV) 0.2g/g.h that with alkene is standard), and the collection product also detects.The time that product is formed and butene conversion was reduced to 90% o'clock sees Table 1.
Embodiment 7
With embodiment 6, difference is that the medium that adds is a methylene dichloride.The time that product is formed and butene conversion was reduced to 9 0% o'clock sees Table 1.
Embodiment 8
With embodiment 6, difference is that the medium that adds is a pure isooctane.The time that product is formed and butene conversion was reduced to 90% o'clock sees Table 1.
Embodiment 9
With embodiment 6, difference is that the medium that adds is the mixture (mol ratio is 1: 3) of methylene dichloride and pure isooctane).The time that product is formed and butene conversion was reduced to 90% o'clock sees Table 1.
Comparative Examples 1
Catalyst system therefor is commercially available beta-molecular sieve product (Si/Al=25, Qilu Petrochemical company catalyst plant is produced), gets 6.5 gram catalyzer and adds in the reactor (suitable with the 'beta ' activity component concentration of B1), and sealed reactor is squeezed into 100 gram Trimethylmethanes with pump then.Reactor is warming up to 80 ℃, when pressure reaches 2MPa, squeezes into 1-butylene with pump in reactor again and react (the little hourly space velocity of weight (WHSV) 0.2g/g.h that with alkene is standard), and the collection product also detects.The time that product is formed and butene conversion was reduced to 90% o'clock sees Table 1.
Table 1
| Numbering | Comparative Examples 1 | Embodiment 6 | Embodiment 7 | Embodiment 8 | Embodiment 9 | |
| Add the medium kind | ? ? ??- | Tetrahydrofuran (THF) | Methylene dichloride | Pure isooctane | Methylene dichloride and 2,2, the mixture of 4-trimethylpentane | |
| Product is formed | ??C5-C7 | ??22.69 | ??18.81 | ??21.47 | ??14.60 | ??13.27 |
| ??C8 | ??40.41 | ??48.63 | ??46.18 | ??52.84 | ??56.70 | |
| ??C9+ | ??36.90 | ??32.56 | ??32.35 | ??32.56 | ??30.03 | |
| ??TMP/DMH | ??3.66 | ??4.08 | ??3.98 | ??4.01 | ??4.24 | |
| Butene conversion reduce to 90% o'clock time (minute) | ? ??260 | ? ??355 | ? ??369 | ? ??414 | ? ??471 | |
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.Butene conversion reduce to 90% o'clock time (minute) be the method for a kind of expression catalyst life commonly used in the alkylated reaction, the time is long more, life of catalyst is long more.
As can be seen from the above table, adopt matrix material, carry out alkylated reaction in the presence of medium, selectivity obviously is better than commercially available industrialization beta-molecular sieve catalyzer reaction result under the same conditions.
Embodiment 10
Adopt autoclave reactor, in reactor, add the matrix material B2 and the 1 gram methylene dichloride of 10.0 gram embodiment, 2 preparations earlier, sealed reactor.Squeeze into 100 gram Trimethylmethanes with pump then, reactor is warming up to 80 ℃, when pressure reaches 2MPa, squeezes into 1-butylene with pump in reactor again and react (the little hourly space velocity of weight (WHSV) 2.0g/g.h that with alkene is standard), and the collection product also detects.The time that product is formed and butene conversion was reduced to 90% o'clock sees Table 2.
Embodiment 11
With embodiment 10, difference is that the medium that adds is an iso-pentane.The time that product is formed and butene conversion was reduced to 90% o'clock sees Table 2.
Comparative Examples 2
Catalyst system therefor is commercially available beta-molecular sieve product (Si/Al=25, Qilu Petrochemical company catalyst plant is produced), adopt autoclave reactor, get 2.0 gram catalyzer and add in the reactor (suitable) with the 'beta ' activity component concentration of B2, sealed reactor is squeezed into 100 gram Trimethylmethanes with pump then.Reactor is warming up to 80 ℃, when pressure reaches 2MPa, squeezes into 1-butylene with pump in reactor again and react (the little hourly space velocity of weight (WHSV) 2.0g/g.h that with alkene is standard), and the collection product also detects.The time that product is formed and butene conversion was reduced to 90% o'clock sees Table 2.
Table 2
| Numbering | Comparative Examples 2 | Embodiment 10 | Embodiment 11 | |
| Add the medium kind | ??- | Methylene dichloride | Iso-pentane | |
| Product is formed | ????C5-C7 | ??37.51 | ??28.81 | ??22.78 |
| ????C8 | ??35.99 | ??38.63 | ??42.56 | |
| ????C9+ | ??26.50 | ??32.56 | ??34.66 | |
| ????TMP/DMH | ??3.03 | ??4.08 | ??4.23 | |
| Butene conversion reduce to 90% o'clock time (minute) | ??378 | ??424 | ??489 | |
As can be seen from the above table, adopt matrix material, carry out alkylated reaction in the presence of medium, selectivity of catalyst obviously is better than commercially available industrialization beta-molecular sieve catalyzer reaction result under the same conditions.
Embodiment 12
The employing fixed-bed reactor add the matrix material B3 (after 3.0 hours, using after being 20～40 orders through compressing tablet, pulverizing at 550 ℃ of roasts) that 2.0 gram embodiment 3 prepare earlier in reactor.
Squeeze into 5 grams 2 with pump, 2, the 4-trimethylpentane, reactor is warming up to 80 ℃, when pressure reaches 2MPa, the mixing raw material of squeezing into Trimethylmethane and 1-butylene with pump in reactor reacts (the little hourly space velocity of weight (WHSV) 2.0g/g.h that with alkene is standard) again, and the mol ratio of Trimethylmethane and 1-butylene is 1: 3.The collection product also detects, and the time that product is formed and butene conversion was reduced to 90% o'clock sees Table 3.
Embodiment 13
With embodiment 12, difference is that used medium is the mixed solution (mol ratio is 1: 3) of 5 gram methylene dichloride and trimethylpentane, and the time that product is formed and butene conversion was reduced to 90% o'clock sees Table 3.
Comparative Examples 3
Catalyst system therefor is commercially available beta-molecular sieve product.Adopt fixed-bed reactor, in reactor, add 1.3 gram beta-molecular sieves (active component content and B3 are suitable) earlier.Reactor is warming up to 80 ℃, when pressure reaches 2MPa, the mixing raw material of squeezing into Trimethylmethane and 1-butylene with pump in reactor reacts (the little hourly space velocity of weight (WHSV) 2.0g/g.h that with alkene is standard), the mol ratio of Trimethylmethane and 1-butylene is 1: 3.The collection product also detects, and the time that product is formed and butene conversion was reduced to 90% o'clock sees Table 3.
Table 3
| Numbering | Comparative Examples 3 | Embodiment 12 | Embodiment 13 | |
| Add the medium kind | ? ? ??- | Pure isooctane | Methylene dichloride and 2, the mixture of 2,4 trimethylpentanes | |
| Product is formed | ????C5-C7 | ??30.34 | 25.60 | 28.81 |
| ????C8 | ??41.39 | 51.46 | 52.47 | |
| ????C9+ | ??28.27 | 22.94 | 18.72 | |
| ????TMP/DMH | ??4.88 | 4.35 | 5.08 | |
| Butene conversion reduce to 90% o'clock time (minute) | ??409 | 482 | 510 | |
As can be seen from Table 3, adopt matrix material provided by the invention, carry out alkylated reaction in the presence of medium, selectivity of catalyst obviously is better than commercially available industrialization beta-molecular sieve catalyzer reaction result under the same conditions.
Embodiment 14
Adopt autoclave reactor, add the B4 of 10.0 gram embodiment, 4 preparations and the mixed solution (mol ratio is 1: 3) that 100 gram Trimethylmethanes and 5 restrain methylene dichloride and pure isooctane earlier in reactor, reactor is warming up to 80 ℃, when pressure reaches 2MPa, with 2.0h
-1Weight space velocity add 1-butylene and react, collect product and also detect.The time that product is formed and butene conversion was reduced to 90% o'clock sees Table 4.
Comparative Examples 4
With embodiment 14, difference is that catalyst system therefor is commercially available beta-molecular sieve product 5.0 grams (active component content and B4 are suitable).The collection product also detects, and the time that product is formed and butene conversion was reduced to 90% o'clock sees Table 4.
Table 4
| Numbering | Comparative Examples 4 | Embodiment 14 | |
| Add the medium kind | ????- | Pure isooctane | |
| Product is formed | ????C5-C7 | ????26.64 | 20.95 |
| ????C8 | ????45.63 | 58.63 | |
| ????C9+ | ????27.73 | 20.42 | |
| ????TMP/DMH | ????3.95 | 4.77 | |
| Butene conversion reduce to 90% o'clock time (minute) | ????421 | 522 | |
Last table as can be seen, adopt described in the embodiment 14 in the presence of the pure isooctane medium, the compound catalyze material that employing contains nano-beta molecular sieve carries out alkylated reaction, and selectivity obviously is better than commercially available industrialization beta-molecular sieve catalyzer reaction result under the same conditions.
Embodiment 15
Adopt autoclave reactor, in reactor, add the B5 of 10.0 gram embodiment, 5 preparations and the mixed solution (mol ratio is 1: 3) of 5 gram methylene dichloride and pure isooctane earlier, sealed reactor.Squeeze into 100 gram Trimethylmethanes with pump then, reactor is warming up to 80 ℃, when pressure reaches 2MPa, squeezes into 1-butylene with pump in reactor again and react (the little hourly space velocity of weight (WHSV) 2.0g/g.h that with alkene is standard), instead collects product and detects.The time that product is formed and butene conversion was reduced to 90% o'clock sees Table 5.
Embodiment 16
With embodiment 15, difference is that medium is a tetrahydrofuran (THF), the ratio of alkane and medium 2: 1.The time that product is formed and butene conversion was reduced to 90% o'clock sees Table 5.
Embodiment 17
With embodiment 15, difference is the ratio 20: 1 of medium pure isooctane, medium and alkene.The time that product is formed and butene conversion was reduced to 90% o'clock sees Table 5.
Embodiment 18
With embodiment 15, difference is that medium is a 1-fluorine hexanaphthene.The time that product is formed and butene conversion was reduced to 90% o'clock sees Table 5.
Embodiment 19
With embodiment 15, difference is that medium is 2,2,5-trimethylammonium heptane.The time that product is formed and butene conversion was reduced to 90% o'clock sees Table 5.
Table 5
| Numbering | Comparative Examples 1 | Embodiment 15 | Embodiment 16 | Embodiment 17 | Embodiment 18 | Embodiment 19 | |
| Add the medium kind | ? ? ??- | Methylene dichloride and 2,2, the mixture of 4-trimethylpentane | Tetrahydrofuran (THF) | Pure isooctane | 1-fluorine hexanaphthene | 2,2,5-trimethylammonium heptane | |
| Product is formed | ??C5-C7 | ??22.69 | 8.81 | 21.4 | 13.21 | 13.27 | 15.45 |
| ??C8 | ??40.41 | 68.63 | 56.18 | 58.84 | 56.70 | 60.57 | |
| ??C9+ | ??36.90 | 22.56 | 22.42 | 27.95 | 30.03 | 23.98 | |
| ??TMP/DMH | ??3.66 | 5.11 | 4.98 | 4.31 | 3.24 | 4.79 | |
| Butene conversion reduce to 90% o'clock time (minute) | ? ??260 | ? 528 | ? 500 | ? 509 | ? 349 | ? 471 | |
Listed file names with the reaction result of Comparative Examples 1 in the table, it can be seen from the table, adopt the alkylated reaction that carries out in the presence of matrix material and medium provided by the invention, selectivity of catalyst obviously is better than commercially available industrialization beta-molecular sieve catalyzer reaction result under the same conditions.
Embodiment 21
Adopt autoclave reactor, in reactor, add the B6 of 10.0 gram embodiment, 6 preparations and the mixed solution (mol ratio is 1: 3) of 5 gram methylene dichloride and pure isooctane earlier, sealed reactor.Squeeze into 100 gram Trimethylmethanes with pump then, reactor is warming up to 80 ℃, when pressure reaches 2MPa, squeezes into 1-butylene with pump in reactor again and react (the little hourly space velocity of weight (WHSV) 2.0g/g.h that with alkene is standard), and the collection product also detects.The time that product is formed and butene conversion was reduced to 90% o'clock sees Table 6.
Table 6
| Numbering | Comparative Examples 1 | Embodiment 21 | |
| Add the medium kind | ? ? ????- | The mixed solution of methylene dichloride and pure isooctane | |
| Product is formed | ????C5-C7 | ????22.69 | 28.81 |
| ????C8 | ????40.41 | 49.90 | |
| ????C9+ | ????36.90 | 22.56 | |
| ????TMP/DMH | ????3.66 | 5.76 | |
| Butene conversion reduce to 90% o'clock time (minute) | ????260 | 428 | |
Listed file names with the result of Comparative Examples 1 in the table 6, as can be seen from the above table, adopt described in the embodiment 21 in matrix material and methylene dichloride and 2,2, the mixed solution medium of 4-trimethylpentane carries out alkylated reaction under existing, and selectivity of catalyst obviously is better than the commercially available result of industrialization beta-molecular sieve catalyzer under same reaction conditions.
Claims (24)
1, the alkylation reaction method of a kind of isoparaffin and alkene, be that the reaction raw materials that will contain isoparaffin in the presence of solid acid catalyst and a kind of medium alkylated reaction takes place with the reaction raw materials that contains alkene, it is characterized in that 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, said medium is selected from one or more the mixture in the following substances: the aliphatic saturated hydrocarbon of the oxygen-containing organic compound of C2～C6, C1～C6 organic halogen compound, C3～C16.
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 claim 1, the oxygen-containing organic compound of said C2～C6 is selected from Fatty Alcohol(C12-C14 and C12-C18), alicyclic ring alcohol, ketone, ether, alicyclic ether or alicyclic ring thioether in the medium.
17, according to the method for claim 16, said oxygen-containing organic compound is ethanol, propyl alcohol, isopropylcarbinol or tetrahydrofuran (THF).
18, according to the method for claim 1, the organic halogen compound of said C1～C6 is selected from and has alkane or the naphthenic hydrocarbon that is replaced by one or more halogen atoms in the medium.
19, according to the method for claim 18, said organic halogen compound is methylene dichloride, 1-chlorobutane or 1-fluorine hexanaphthene.
20, according to the method for claim 1, said aliphatic saturated hydrocarbon with 3～16 carbon atoms is selected from iso-pentane, pure isooctane or 2,2 in the medium, 5-trimethylammonium heptane.
21, according to the method for claim 1, alkane alkene mol ratio is (1～100): 1, and the mol ratio of medium and alkene is (1～300): 1.
22, according to the method for claim 21, alkane alkene mol ratio is (2～20): 1, and the mol ratio of medium and alkene is (2～30): 1.
23, according to the method for claim 1, alkylated reaction carries out in autoclave or fixed-bed reactor.
24, according to the method for claim 23, the alkylated reaction that carries out in the said autoclave reactor adopts periodical operation, semi-batch operation or operate continuously.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107163980A (en) * | 2017-06-26 | 2017-09-15 | 南京工业大学 | A kind of C3And C5The method that hydro carbons prepares alkylate oil |
| WO2020151646A1 (en) * | 2019-01-25 | 2020-07-30 | 中国石油化工股份有限公司 | Solid acid catalyst, preparation therefor and use thereof |
| 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 |
| 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 |
| 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 |
| CN111482195A (en) * | 2019-01-25 | 2020-08-04 | 中国石油化工股份有限公司 | Solid acid catalyst |
| RU2806559C2 (en) * | 2019-01-25 | 2023-11-01 | Чайна Петролеум Энд Кемикал Корпорейшн | Solid acid catalyst, its preparation and application |
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107163980A (en) * | 2017-06-26 | 2017-09-15 | 南京工业大学 | A kind of C3And C5The method that hydro carbons prepares alkylate oil |
| WO2020151646A1 (en) * | 2019-01-25 | 2020-07-30 | 中国石油化工股份有限公司 | Solid acid catalyst, preparation therefor and use thereof |
| 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 |
| 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 |
| 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 |
| CN111482195A (en) * | 2019-01-25 | 2020-08-04 | 中国石油化工股份有限公司 | 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 |
| RU2806559C2 (en) * | 2019-01-25 | 2023-11-01 | Чайна Петролеум Энд Кемикал Корпорейшн | Solid acid catalyst, its preparation and application |
| US11951461B2 (en) | 2019-01-25 | 2024-04-09 | China Petroleum & Chemical Corporation | Solid acid catalyst, preparation therefor and use thereof |
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