CN103964994A - Alkylation reaction method - Google Patents
Alkylation reaction method Download PDFInfo
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- CN103964994A CN103964994A CN201310038433.1A CN201310038433A CN103964994A CN 103964994 A CN103964994 A CN 103964994A CN 201310038433 A CN201310038433 A CN 201310038433A CN 103964994 A CN103964994 A CN 103964994A
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Abstract
The present invention provides an alkylation reaction method, which is characterized in that an alkylation reaction of isobutane and butene is performed in the presence of a catalyst under alkylation reaction conditions, wherein the catalyst is prepared through a molecular sieve modification step and a matrix introduction step, and the molecular sieve modification step comprises: uniformly mixing a molecular sieve, one or a plurality of substances selected from water, an alcohol and an ester, and an organic alkali, treating at a temperature of 100-250 DEG C under autogenous pressure in a sealed reaction kettle, recovering the product obtained from the treating, and carrying out rare earth ion salt exchange.
Description
Technical field
The present invention relates to a kind of alkylation reaction method, relate to furtherly the method for Trimethylmethane/butene alkylation.
Background technology
The alkylated reaction of isobutane and butene is the significant process of a production high octane gasoline component.The alkylation production technique of industrial application has sulfuric acid process and hydrofluoric acid method at present, and in the alkylation throughput of nearly 9,000 ten thousand t/a in the whole world, two kinds of methods approximately respectively account for half.From alkylate oil proportion total gasoline composition, the U.S. accounts for 12.5%, and Europe accounts for 4%, and China only accounts for approximately 0.4%.
Because the spent acid of corrodibility, toxicity and the technological process of sulfuric acid and hydrofluoric acid itself discharges the harm to environment, the safety and environmental protection pressure that alkylate oil manufacturing enterprise faces is increased day by day.In order to address these problems, since last century the eighties, the world is permitted great oil company and scientific research institution and is devoted to always the research and development of solid acid alkylation processes, to substituting liquid acid technique by eco-friendly solid acid technique.Due to solid acid catalyst rapid deactivation in alkylation process of exploitation, solid acid alkylation processes technology not yet realizes industrialization so far.
Utilize the difference in the specific pore passage structure of zeolite and aperture size, can realize to a certain extent molecule screening and do.Owing to needing the molecular dynamics diameter difference of identification much smaller than 0.1nm in research and production reality, and the varying aperture of zeolite is great-jump-forward, and rangeability exceedes 0.1nm, is difficult to realize meticulous modulation is carried out in its aperture by traditional single sintering method.On the other hand, in order to improve absorption and the catalytic selectivity of zeolite molecular sieve, also need zeolite surface structure and acidity can carry out study on the modification.Method of modifying mainly contains: (1) zeolite molecular sieve cationic exchange; (2) the heteroatoms isomorphous substitution of zeolite molecular sieve skeleton; (3) Dealumination of zeolite molecular sieve skeleton and Dealumination; (4) molecular sieve pore passage and finishing.
The method of acid treatment Dealumination zeolite relatively, processing zeolite with alkali lye is a kind of method of modifying of desiliconization.It also can change the SiO of zeolite
2/ M
2o
2(M=Al or Fe, B, Ca etc.).Thereby reach the object that changes zeolite acidity, the specific surface area on catalyzer and micro pore volume also have impact simultaneously.Alkali lye is processed limited to the modifying function of zeolite pore structure and Acidity, the structure that concentration of lye is too high or the harsh meeting of modified condition saboteur sieves.
Molecular sieve is carried out to the adjustable change acidic zeolite of rare earth ion modification.Rare earth ion, by polarization and inducing action, makes its water molecules polarization around, is effectively attracting OH
-, make H
+in unbound state, produce B acid site, thereby improved the cracking activity of catalyzer.Another vital role of rare earth ion is the stability that increases skeleton Al.Rare earth ion enters molecular sieve crystal inside by finishing, moves to β cage by supercage, interacts with skeleton Sauerstoffatom, has suppressed the de-Al of the skeleton of molecular sieve under hydrothermal condition, thereby has strengthened the stability of framework of molecular sieve structure.Rare earth modified degree is subject to the impact of rare earth loaded amount, and the too high meeting of rare earth loaded amount causes duct to stop up.
CN1775360A discloses a kind of for improving the method for ketone compound ammonia oxidation catalyst stability.Nano-titanium si molecular sieves process acidic cpd processing in this method, then use organic bases processing, or directly use organic bases processing.Molecular sieve after treatment has formed micropore that a large amount of apertures are about 0.1-10nm and a large amount of cavity and pits.This method modification obtains molecular sieve and has excellent catalytic oxidation activity and activity stability.
CN1245090A mixes gained through acid-treated TS-1 molecular sieve, organic bases and water, and under the temperature of 120～200 DEG C and autogenous pressure, react 2 hours to 8 day time in sealed reactor, wherein said organic bases is fatty amines, alcamines or quaternary ammonium hydroxide compounds; Products therefrom is filtered, washs and be dried.
USP6475465 discloses a kind of method of HTS directly being used to the processing of organic bases compounds such as fatty amines, alcamines, quaternary ammonium bases.
USP4497969 discloses a kind of method of processing crystalline silico-alumino molecular sieve with organic bases, organic acid, ethanol, glycerine, phenol, ester.
A kind of method that USP5705729 discloses USY molecular sieve partly or entirely carries out rare earth exchanged modification.This method modification obtains molecular sieve and in Trimethylmethane/butene alkylation, has good alkylation activity and activity stability.
USP7550405 and USP7470645 disclose a kind of catalyzer for catalyzing iso-butane alkane/butene alkylation.The preparation method of this catalyzer for by β, Y, mordenite, L for zeolite the metal such as Al, Ti, Mo, Ni, Co, Fe, Pa, Pt carry out modification.
Above-mentioned method of modifying is single organo-metallic modification or rare earth modified, therefore can not avoid alkali metals modified and the rare earth modified shortcoming of bringing.Can not meet the requirement of alkylated reaction to catalyzer, to realize best selectivity, transformation efficiency and life-span.
Summary of the invention
The inventor finds by a large amount of tests, when organic bases and the common modification of rare earth for molecular sieve, unexpectedly can be in ensureing that molecular sieve pore passage is unimpeded, significantly increase the charge capacity of the rare earth atom of the molecular sieve after modification, the catalyzer obtaining in conjunction with introducing matrix thus has better catalytic performance during for Trimethylmethane/butene alkylation.Based on this, form the present invention.
Therefore, the object of this invention is to provide the method for the better Trimethylmethane/butene alkylation of a kind of catalytic performance.
The method of alkylated reaction provided by the invention, it is characterized in that carrying out the alkylated reaction of Trimethylmethane and butylene under the condition of a kind of catalyzer existence and alkylated reaction, wherein said catalyzer is to be prepared with the step of introducing matrix by the step that comprises modified molecular screen, the step of said modified molecular screen be by molecular sieve, be selected from water, alcohol, ester one or more material and after organic bases mixes, in sealed reactor, under 100～250 DEG C and autogenous pressure, process, to process again after products therefrom recovery, then exchange through rare earth ion salt.
Alkylation provided by the invention, under identical introducing matrix condition and identical alkylation reaction condition, significantly improves selectivity and the catalyst life of object product trimethylpentane (TMP).
Embodiment
The method of alkylated reaction provided by the invention, it is characterized in that carrying out the alkylated reaction of Trimethylmethane and butylene under the condition of a kind of catalyzer existence and alkylated reaction, wherein said catalyzer is to be prepared with the step of introducing matrix by the step that comprises modified molecular screen, the step of said modified molecular screen be by molecular sieve, be selected from water, alcohol, ester one or more material and after organic bases mixes, in sealed reactor, under 100～250 DEG C and autogenous pressure, process, to process again after products therefrom recovery, then exchange through rare earth ion salt.
In method provided by the invention, the step of said modified molecular screen, this step comprise by molecular sieve, be selected from water, alcohol, ester one or more material and after organic bases mixes, in sealed reactor, under 100～250 DEG C and autogenous pressure, process, to process again after products therefrom recovery, then exchange through rare earth ion salt.
Said molecular sieve is Si-Al molecular sieve or aluminium silicophosphate molecular sieve, through hydrothermal crystallizing synthetic obtain, through ammonium exchange by sodium ion wherein in sodium oxide≤0.2 % by weight, roasting removes the molecular sieve of organic formwork agent wherein.Further, can be also at a certain temperature, organic acid or mineral acid or water vapour are contacted to the Si-Al molecular sieve or the aluminium silicophosphate molecular sieve that obtain with molecular sieve.Said Si-Al molecular sieve or aluminium silicophosphate molecular sieve can be selected from one or more in FAU structural zeolite, BETA structural zeolite, MFI structural zeolite, CHA structural zeolite, mordenite, ZSM-11 zeolite, ZSM-22 zeolite and ZSM-48 zeolite.
In said one or more the material being selected from water, alcohol, ester, alcohol is selected from the one comprising in saturated monohydroxy alcohol, unsaturated monohydroxy-alcohol, saturated dibasic alcohol, unsaturated dibasic alcohol, saturated trivalent alcohol and unsaturated trivalent alcohol; Ester is selected from the one in unsaturated organic acid ester, unsaturated organic acid ester, saturated inorganic acid ester and unsaturated inorganic acid ester; In specific embodiments more of the present invention, can be water, methyl alcohol, ethanol, one or more in methyl-formiate.
Said organic bases is the organic basic compound that contains amino (NH2) in molecule.Organic bases is fatty amines, alcamines, quaternary ammonium bases, nitrogen heterocyclic ring organic bases, aromatic amine compound, for example, be diethylamine, triethylamine, tetraethyl ammonium hydroxide, arsenic pyridine etc.
Said organic bases also can substitute with the alkoxide that is selected from I A, II A family metal, and preferred alkoxide is sodium ethylate.
Said molecular sieve, be selected from water, alcohol, ester one or more material and the weight ingredient proportion of organic bases be preferably 1:2～10:0.5～3.Said processing, preferably in sealed reactor, temperature of reaction is 120～200 DEG C, reacts 1 hour to 8 day time under autogenous pressure.The said process that processing products therefrom is reclaimed typically refers to washing and dry, for example process of 110 DEG C of oven dry.
In the step of said modified molecular screen, said rare earth ion salt exchange, is the process that molecular sieve is contacted to exchange with rare earth ion.Said rare earth ion salt is one or more salt that are selected from the rare earth metal of La system and Ac system, is wherein preferably the soluble metallic salt of lanthanum and/or cerium, as lanthanum nitrate, cerous nitrate etc.Said exchange, is to be 50～200 DEG C, preferably 50～100 DEG C in temperature, and said exchange, can carry out 1-5 time; After each exchange, wash, suction filtration, dry and in the step of 350～650 DEG C of roastings.
In method provided by the invention, also comprise the step of said introducing matrix.Described matrix plays binding agent, thinner and carrier in catalyzer.Optionally one or more in the various heat-resistant inorganic oxides that are commonly used for support of the catalyst and/or matrix of described matrix.For example, be selected from one or more in aluminum oxide, silicon oxide, titanium oxide, magnesium oxide, aluminum oxide-magnesium oxide, silica-alumina, silicon oxide-magnesium oxide, silicon oxide-zirconium white, silicon oxide-Thorotrast, silicon oxide-beryllium oxide, silicon oxide-titanium oxide, silicon oxide-zirconium white, oxidation titania-zirconia, silica-alumina-Thorotrast, silica-alumina-titanium oxide, silica-alumina-magnesium oxide, silica-alumina-zirconium white, natural zeolite, synthesis zeolite, non-zeolitic molecular sieves and clay.Preferably a kind of in synthesis zeolite, non-zeolitic molecular sieves, silicon oxide, aluminum oxide, silica-alumina or their mixture; More preferably one or more in aluminum oxide, silicon oxide, silica-alumina.Taking catalyzer total amount as benchmark, the content of described matrix components is no more than 95 % by weight, more preferably 10 % by weight～90 % by weight.
The introducing method of described matrix is this area conventional process, in a preferred embodiment, described matrix is under the condition of the molecular sieve that is enough to described modification procedure to obtain and matrix pulp, and the molecular sieve that described matrix is obtained with described modification mixes with water and pulls an oar, afterwards dry and roasting.And said method and condition dry and roasting are this area customary way and condition, for example described maturing temperature can be 400～1000 DEG C, is preferably 450～800 DEG C.Molecular sieve in said catalyzer, can sieve for different kinds of molecules the mixture of the molecular sieve obtaining through modification procedure, for example, two kinds and two or more mixtures in mordenite, beta-molecular sieve, Y molecular sieve, ZSM-5 molecular sieve, ZSM-22 molecular sieve, SAPO-34 molecular sieve.Of the present invention preferred embodiment in, can be the mixture of mordenite, beta-molecular sieve and Y molecular sieve, can be the mixture of SAPO-34 and ZSM-5 molecular sieve, can be also the mixture of Y molecular sieve and ZSM-22 molecular sieve.
Method provided by the invention, depending on different objects or require also can comprise the step of the forming composition of making various easy handlings, for example, forms the forming step of microballoon, spherical, tablet or bar shaped etc.Forming step can carry out according to a conventional method, as the methods such as spray drying forming, compression molding, roller forming, extruded moulding all can.
In method provided by the invention, the method for said alkylated reaction, its reaction conditions is that temperature of reaction is that 30-200 DEG C, pressure are 0.5-6.0MPa, and charging air speed is 10-3000mL/g.h, and alkane alkene is than being 1.0-1000.
Below by embodiment, the present invention is described further, but content not thereby limiting the invention.
In embodiment, molecular sieve composition is measured with x ray fluorescence spectrometry (XRF), and content of rare earth is with RE
2o
3% meter.
The specific surface area of molecular sieve and pore volume are measured by static state low temperature nitrogen loading capacity method (BET), and laboratory apparatus used is the static n2 absorption apparatus of the ASAP-2405 of Micromeritics company of the U.S..Test process is: liquid nitrogen contacts with sorbent material under 77K, leaves standstill and reaches adsorption equilibrium.By the amount that remains in tolerance difference in gas phase after nitrogen air input and absorption and calculate sorbent material absorption nitrogen.Specific surface area adopts two B parameter ET Equation for Calculating, and pore distribution adopts BJH method to calculate.
Raw materials used except special instruction in embodiment, be chemically pure reagent.
Embodiment 1
The present embodiment illustrates the modification procedure of beta-molecular sieve in method provided by the invention.
(Zhou village catalyst plant provides 10g beta-molecular sieve, SiO
2/ Al
2o
3=25, Na
2o%<0.1%, 550 DEG C of roasting 2h) add 10g diethylamine and 50g ethanol, join in Pressure solution bullet 120 DEG C of heating 24h.By gained sample suction filtration, washing, after 110 DEG C of oven dry, more above-mentioned organic bases modified sample 5g is added to 300g water, add lanthanum nitrate hexahydrate 40g, 50 DEG C of exchange 5h, washing suction filtration, after 110 DEG C of oven dry, gained sample is counted A, carries out the table 1 that the results are shown in of XRD, BET sign.
Comparative example 1
The explanation of this comparative example is only carried out rare earth modified step to beta-molecular sieve.
(Zhou village catalyst plant provides 5g beta-molecular sieve, SiO
2/ Al
2o
3=25, Na
2o%<0.1%, 550 DEG C of roasting 2h) add 300g water, add lanthanum nitrate hexahydrate 40g, 50 DEG C of exchange 5h, washing suction filtration, after 110 DEG C of oven dry, gained sample is counted X, carries out the table 1 that the results are shown in of XRD, BET sign.
Embodiment 2
The present embodiment illustrates the modification procedure of Y zeolite in method provided by the invention.
(Chang Ling catalyst plant provides 10g Y molecular sieve, SiO
2/ Al
2o
3=5, Na
2o%<0.1%, 550 DEG C of roasting 2h) add 10g triethylamine and 50g methyl alcohol, join in Pressure solution bullet 120 DEG C of heating 144h.By gained sample suction filtration, washing, after 110 DEG C of oven dry, more above-mentioned organic bases modified sample 5g is added to 200g water, add six nitric hydrate cerium 30g, 60 DEG C of exchange 4h, washing suction filtration, after 110 DEG C of oven dry, gained sample is counted B, carries out the table 1 that the results are shown in of XRD, BET sign.
Embodiment 3
The present embodiment illustrates the modification procedure of mordenite in method provided by the invention.
(Zhou village catalyst plant provides 10g mordenite molecular sieve, SiO
2/ Al
2o
3=10, Na
2o%<0.1%, 550 DEG C of roasting 2h) add 10g quadrol and 50g water, join in Pressure solution bullet 150 DEG C of heating 1h.By gained sample suction filtration, washing, after 110 DEG C of oven dry, more above-mentioned organic bases modified sample is added to 200g water, add lanthanum nitrate hexahydrate 30g, 70 DEG C of exchange 3h, washing suction filtration, after 110 DEG C of oven dry, gained sample is counted C, carries out the table 1 that the results are shown in of XRD, BET sign.
Embodiment 4
The present embodiment illustrates the modification procedure of ZSM-5 molecular sieve in method provided by the invention.
10g ZSM-5 molecular sieve (Zhou village catalyst plant provides, SiO2/Al2O3=25, Na2O%<0.1%, 550 DEG C of roasting 2h) adds 20g tetraethyl-oxyammonia and 50g methyl-formiate, joins in Pressure solution bullet 150 DEG C of heating 24h.By gained sample suction filtration, washing, after 110 DEG C of oven dry, more above-mentioned organic bases modified sample is added to 100g water, add lanthanum nitrate hexahydrate 15g, 80 DEG C of exchange 2h, washing suction filtration, after 110 DEG C of oven dry, gained sample is counted D, carries out the table 1 that the results are shown in of XRD, BET sign.
Embodiment 5
The present embodiment illustrates the modification procedure of ZSM-22 molecular sieve in method provided by the invention.
(Zhou village catalyst plant provides 10g ZSM-22 molecular sieve, SiO
2/ Al
2o
3=25, Na
2o%<0.1%, 550 DEG C of roasting 2h) add the pyridine of 20g arsenic and 50g ethanol, join in Pressure solution bullet 200 DEG C of heating 2h.By gained sample suction filtration, washing, after 110 DEG C of oven dry, more above-mentioned organic bases modified sample is added to 100g water, add lanthanum nitrate hexahydrate 15g, 90 DEG C of exchange 1h, washing suction filtration, after 110 DEG C of oven dry, gained sample is counted E, carries out the table 1 that the results are shown in of XRD, BET sign.
Embodiment 6
The present embodiment illustrates the modification procedure of SAPO-34 molecular sieve in method provided by the invention.
(Chang Ling catalyst plant provides 10g SAPO-34 molecular sieve, SiO
2/ Al
2o
3=25, Na
2o%<0.1%, 550 DEG C of roasting 2h) add 10g sodium ethylate and 50g ethanol, join in Pressure solution bullet 250 DEG C of heating 1h.By sample suction filtration, washing, after 110 DEG C of oven dry, more above-mentioned organic bases modified sample is added to 100g water, add lanthanum nitrate hexahydrate 15g, 100 DEG C of exchange 0.5h, washing suction filtration, after 110 DEG C of oven dry, gained sample is counted F, carries out the table 1 that the results are shown in of XRD, BET sign.
Table 1
As can be seen from Table 1, the molecular sieve that method modification provided by the invention obtains, its content of rare earth of measuring with XRF is with Re
2o
3% meter, is increased to 14% from 10% of comparative example 1, has increased by 40% rare earth loaded amount.
Embodiment 7～10 illustrates the preparation of method provided by the invention catalyzer used.
Embodiment 7
In 16.0Kg decationized Y sieve water, add 3.8Kg halloysite (Kaolin of Suzhou company produces, and solid content is 74.0 heavy %), stir 1h, kaolin is fully disperseed.Add 320mL hydrochloric acid (Beijing Chemical Plant produces, chemical pure, the heavy % of concentration 36-38), and 3.3Kg pseudo-boehmite (Shandong Aluminum Plant produces, containing Al
2o
3the heavy % of concentration 61.0), stir 1h, make after pseudo-boehmite colloidal sol, be warming up to 60 DEG C, keep 1h, cooling.
In 7.0Kg decationized Y sieve water, add 2.7Kg C, 1.1Kg A, and 0.5Kg B, after homogenizer fully disperses, join in above-mentioned pseudo-boehmite-clay slurry, stirs 0.5h.By above-mentioned slurries spray drying forming at 250 DEG C of exhaust temperatures, after 650 DEG C of roasting 2h, obtain micro-spherical catalyst G.
Embodiment 8
In 5.0Kg decationized Y sieve water, add 0.9Kg halloysite (Kaolin of Suzhou company produces, and solid content is 74.0 heavy %), stir 1h, kaolin is fully disperseed.Add 60mL hydrochloric acid (Beijing Chemical Plant produces, chemical pure, the heavy % of concentration 36-38), stir 1h, make after pseudo-boehmite colloidal sol, be warming up to 60 DEG C, keep 1h, be cooled to afterwards room temperature.
In 16.8Kg decationized Y sieve water, add 1.6KgF and 1.6Kg D, after homogenizer fully disperses, join in above-mentioned pseudo-boehmite-clay slurry, stir 0.5h, then (Shandong catalyst plant is produced, containing Al to add 36.2Kg aluminium colloidal sol
2o
3the heavy % of concentration 22.0), continue to stir 0.5h, obtain the heavy % of solid content 13.7, the catalyst slurry that pH value is 2.6.
By above-mentioned slurries spray drying forming at 250 DEG C of exhaust temperatures, after 650 DEG C of roasting 2h, obtain micro-spherical catalyst H.
Embodiment 9
In 6.0Kg decationized Y sieve water, add 0.9Kg halloysite (Kaolin of Suzhou company produces, and solid content is 74.0 heavy %), stir 1h, kaolin is fully disperseed.Add 60mL hydrochloric acid (Beijing Chemical Plant produces, chemical pure, the heavy % of concentration 36-38), and 0.7Kg pseudo-boehmite (Shandong Aluminum Plant produces, containing Al
2o
3the heavy % of concentration 61.0), stir 1h, make after pseudo-boehmite colloidal sol, be warming up to 60 DEG C, keep 1h, be cooled to afterwards room temperature.
In 6.8Kg decationized Y sieve water, add 0.3Kg B and 3.7KgE, after homogenizer fully disperses, join in above-mentioned pseudo-boehmite-clay slurry, stir 0.5h, then (Shandong catalyst plant is produced, containing Al to add 3.6Kg aluminium colloidal sol
2o
3the heavy % of concentration 22.0), continue to stir 0.5h, obtain the heavy % of solid content 26.2, the catalyst slurry that pH value is 3.9.By above-mentioned slurries spray drying forming at 250 DEG C of exhaust temperatures, after 650 DEG C of roasting 2h, obtain micro-spherical catalyst I.
Embodiment 10
In 6.0Kg decationized Y sieve water, add 0.9Kg halloysite (Kaolin of Suzhou company produces, and solid content is 74.0 heavy %), stir 1h, kaolin is fully disperseed.Add 60mL hydrochloric acid (Beijing Chemical Plant produces, chemical pure, the heavy % of concentration 36-38), and 0.7Kg pseudo-boehmite (Shandong Aluminum Plant produces, containing Al
2o
3the heavy % of concentration 61.0), stir 1h, make after pseudo-boehmite colloidal sol, be warming up to 60 DEG C, keep 1h, be cooled to afterwards room temperature.
The modified molecular screen A that adds 4Kg embodiment 1 to make in 6.8Kg decationized Y sieve water, after homogenizer fully disperses, joins in above-mentioned pseudo-boehmite-clay slurry, stirs 0.5h, then (Shandong catalyst plant is produced, containing Al to add 3.6Kg aluminium colloidal sol
2o
3the heavy % of concentration 22.0), continue to stir 0.5h, obtain the heavy % of solid content 26.2, the catalyst slurry that pH value is 3.9.By above-mentioned slurries spray drying forming at 250 DEG C of exhaust temperatures, after 650 DEG C of roasting 2h, obtain micro-spherical catalyst J.
Comparative example 2
In 6.0Kg decationized Y sieve water, add 0.9Kg halloysite (Kaolin of Suzhou company produces, and solid content is 74.0 heavy %), stir 1h, kaolin is fully disperseed.Add 60mL hydrochloric acid (Beijing Chemical Plant produces, chemical pure, the heavy % of concentration 36-38), and 0.7Kg pseudo-boehmite (Shandong Aluminum Plant produces, containing Al
2o
3the heavy % of concentration 61.0), stir 1h, make after pseudo-boehmite colloidal sol, be warming up to 60 DEG C, keep 1h, be cooled to afterwards room temperature.
The modified molecular screen that adds 4Kg comparative example 1 to make in 6.8Kg decationized Y sieve water, after homogenizer fully disperses, joins in above-mentioned pseudo-boehmite-clay slurry, stirs 0.5h, then (Shandong catalyst plant is produced, containing Al to add 3.6Kg aluminium colloidal sol
2o
3the heavy % of concentration 22.0), continue to stir 0.5h, obtain the heavy % of solid content 26.2, the catalyst slurry that pH value is 3.9.By above-mentioned slurries spray drying forming at 250 DEG C of exhaust temperatures, after 650 DEG C of roasting 2h, obtain micro-spherical catalyst Y.
Comparative example 3
In 16.0Kg decationized Y sieve water, add 3.8Kg halloysite (Kaolin of Suzhou company produces, and solid content is 74.0 heavy %), stir 1h, kaolin is fully disperseed.Add 320mL hydrochloric acid (Beijing Chemical Plant produces, chemical pure, the heavy % of concentration 36-38), and 3.3Kg pseudo-boehmite (Shandong Aluminum Plant produces, containing Al
2o
3the heavy % of concentration 61.0), stir 1h, make after pseudo-boehmite colloidal sol, be warming up to 60 DEG C, keep 1h, cooling.
(Zhou village catalyst plant provides, SiO in 7.0Kg decationized Y sieve water, to add 2.7Kg mordenite molecular sieve
2/ Al
2o
3=10, Na
2o%<0.1%, 550 DEG C of roasting 2h), (Zhou village catalyst plant provides 1.1Kg beta-molecular sieve, SiO
2/ Al
2o
3=25, Na
2o%<0.1%, 550 DEG C of roasting 2h, and 0.5Kg Y molecular sieve (Chang Ling catalyst plant provides, SiO
2/ Al
2o
3=5, Na
2o%<0.1%, 550 DEG C of roasting 2h), after homogenizer fully disperses, join in above-mentioned pseudo-boehmite-clay slurry, stir 0.5h.By above-mentioned slurries spray drying forming at 250 DEG C of exhaust temperatures, after 650 DEG C of roasting 2h, obtain micro-spherical catalyst Z.
Embodiment 11～14
Embodiment 11～14 explanation alkylation provided by the invention.
The catalyzer making with embodiment 7～10 carries out gas-phase reaction in continuous fixed bed reactor compressive reaction evaluating apparatus.Loaded catalyst is 1.5 grams, and catalyzer, after having loaded, first purges 5 hours by catalyzer with 200 DEG C of Trimethylmethanes before reaction.After reduction, be adjusted to temperature of reaction, under certain charging air speed, the gas mixture of Trimethylmethane/butylene passed into reactor.With the on-line analysis of HP7890 type gas chromatograph.Concrete operations condition, object product trimethylpentane (TMP) and catalyst life (raw material butylene 100% transformation time) are in table 2.
Comparative example 4,5
With comparative example 2,3 prepared catalyzer, with the method for embodiment 11.Concrete operations condition, object product trimethylpentane (TMP) and catalyst life (raw material butylene 100% transformation time) are in table 2.
Table 2
Claims (15)
1. the method for an alkylated reaction, it is characterized in that carrying out the alkylated reaction of Trimethylmethane and butylene under the condition of a kind of catalyzer existence and alkylated reaction, wherein said catalyzer is to be prepared with the step of introducing matrix by the step that comprises modified molecular screen, the step of said modified molecular screen is by molecular sieve, be selected from water, alcohol, after the material of one or more in ester and organic bases mix, in sealed reactor, under 100～250 DEG C and autogenous pressure, process, to process again after products therefrom recovery, exchange through rare earth ion salt again, the condition of said alkylated reaction is temperature 30-200 DEG C, pressure is 0.5-6.0MPa, charging air speed is 10-3000mL/g.h, alkane alkene is than being 1.0-1000.
2. according to the process of claim 1 wherein, one or more in FAU structural zeolite, BETA structural zeolite, MFI structural zeolite, CHA structural zeolite, mordenite, ZSM-11 zeolite, ZSM-22 zeolite and ZSM-48 zeolite of said molecular screening.
3. according to the process of claim 1 wherein, said molecular sieve, be selected from water, alcohol, ester one or more material and the weight ingredient proportion of organic bases be 1:2～10:0.5～3.
4. according to the method for claim 1 or 3, wherein, said molecular sieve be through hydrothermal crystallizing syntheticly obtain, through ammonium exchange by sodium ion wherein in sodium oxide≤0.2 % by weight, roasting removes the molecular sieve of organic formwork agent wherein.
5. according to the method for claim 1, wherein said alcohol is selected from the one comprising in saturated monohydroxy alcohol, unsaturated monohydroxy-alcohol, saturated dibasic alcohol, unsaturated dibasic alcohol, saturated trivalent alcohol and unsaturated trivalent alcohol, and said ester is selected from the one in unsaturated organic acid ester, unsaturated organic acid ester, saturated inorganic acid ester and unsaturated inorganic acid ester.
6. according to the method for claim 1 or 5, wherein, said alcohol is ethanol or methyl alcohol, and said ester is methyl-formiate.
7. according to the process of claim 1 wherein, said organic bases is in molecule, to contain amino organic basic compound.
8. according to the method for claim 1 and 7, wherein, said organic bases is selected from fatty amines, alcamines, quaternary ammonium bases, nitrogen heterocyclic ring organic bases or aromatic amine compound.
9. according to the process of claim 1 wherein, said organic bases is diethylamine, triethylamine, tetraethyl ammonium hydroxide or arsenic pyridine.
10. according to the process of claim 1 wherein, said organic bases is the alkoxide that is selected from I A, II A family metal.
11. according to the method for claim 10, and wherein, said alkoxide is sodium ethylate.
12. according to the process of claim 1 wherein, said rare earth ion salt is the soluble metallic salt containing lanthanum and/or cerium.
13. according to the process of claim 1 wherein, said processing is under 120～200 DEG C and autogenous pressure, to process 1 hour to 8 days in sealed reactor.
14. according to the process of claim 1 wherein, said matrix is selected from one or more in heat-resistant inorganic oxide.
15. according to the process of claim 1 wherein, taking catalyzer total amount as benchmark, the content of said matrix is no more than 95 % by weight, and said matrix is one or more in aluminum oxide, silicon oxide, silica-alumina.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN112808299A (en) * | 2019-11-18 | 2021-05-18 | 中国石油化工股份有限公司 | Solid acid alkylation catalyst and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3840613A (en) * | 1971-12-29 | 1974-10-08 | Exxon Research Engineering Co | Paraffin alkylation with olefin using highly active crystalline zeolite catalyst |
| US4447554A (en) * | 1980-05-29 | 1984-05-08 | Phillips Petroleum Company | Hydroalkylation catalyst and methods for producing and employing same |
| CN1201717A (en) * | 1997-06-06 | 1998-12-16 | 中国石油化工总公司 | Catalyst for alkylation of benzene and ethylbenzene manufactured from ethylene |
| CN102652121A (en) * | 2009-12-16 | 2012-08-29 | 环球油品公司 | Detergent alkylation using a rare earth exchanged catalyst |
-
2013
- 2013-01-31 CN CN201310038433.1A patent/CN103964994B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3840613A (en) * | 1971-12-29 | 1974-10-08 | Exxon Research Engineering Co | Paraffin alkylation with olefin using highly active crystalline zeolite catalyst |
| US4447554A (en) * | 1980-05-29 | 1984-05-08 | Phillips Petroleum Company | Hydroalkylation catalyst and methods for producing and employing same |
| CN1201717A (en) * | 1997-06-06 | 1998-12-16 | 中国石油化工总公司 | Catalyst for alkylation of benzene and ethylbenzene manufactured from ethylene |
| CN102652121A (en) * | 2009-12-16 | 2012-08-29 | 环球油品公司 | Detergent alkylation using a rare earth exchanged catalyst |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| US11951461B2 (en) | 2019-01-25 | 2024-04-09 | China Petroleum & Chemical Corporation | Solid acid catalyst, preparation therefor and use thereof |
| CN112808299A (en) * | 2019-11-18 | 2021-05-18 | 中国石油化工股份有限公司 | Solid acid alkylation catalyst and preparation method thereof |
| CN112808299B (en) * | 2019-11-18 | 2022-05-03 | 中国石油化工股份有限公司 | Solid acid alkylation catalyst and preparation method thereof |
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