CN103964994B - A kind of method of alkylated reaction - Google Patents
A kind of method of alkylated reaction Download PDFInfo
- Publication number
- CN103964994B CN103964994B CN201310038433.1A CN201310038433A CN103964994B CN 103964994 B CN103964994 B CN 103964994B CN 201310038433 A CN201310038433 A CN 201310038433A CN 103964994 B CN103964994 B CN 103964994B
- Authority
- CN
- China
- Prior art keywords
- alcohol
- molecular sieve
- zeolite
- organic bases
- alkylated reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Abstract
The invention provides a kind of method of alkylated reaction, it is characterized in that a kind of catalyzer exist and alkylated reaction condition under carry out the alkylated reaction of Trimethylmethane and butylene, wherein said catalyzer is prepared by the step of the step and introducing matrix that comprise modified molecular screen, the step of said modified molecular screen is by molecular sieve, is selected from after one or more material in water, alcohol, ester and organic bases mix, process under 100 ~ 250 DEG C and autogenous pressure in sealed reactor, after processing products therefrom recovery again, then exchange through rare earth ion salt.
Description
Technical field
The present invention relates to a kind of alkylation reaction method, relate to the method for Trimethylmethane/butene alkylation furtherly.
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 current industrial application has sulfuric acid process and hydrogen fluoride, and in the alkylation throughput of nearly 9,000 ten thousand t/a in the whole world, two kinds of methods about 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 about 0.4%.
Due to the harm of spent acid discharge to environment of the corrodibility of sulfuric acid and hydrofluoric acid itself, toxicity and technological process, the safety and environmental protection pressure that alkylate oil manufacturing enterprise is faced increases day by day.In order to address these problems, since last century the eighties, the world is permitted the research and development that great oil company and scientific research institution are devoted to solid acid alkylation processes always, 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, molecule screening can be realized to a certain extent and do.Owing to needing the molecular dynamics diameter difference identified much smaller than 0.1nm in research and production reality, and the varying aperture of zeolite is great-jump-forward, and rangeability, more than 0.1nm, is difficult to realize carrying out meticulous modulation to 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 carry out study on the modification to zeolite surface structure and acidity.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 relative acid treatment Dealumination zeolite is then a kind of method of modifying of desiliconization with base extraction zeolite.It also can change the SiO of zeolite
2/ M
2o
2(M=Al or Fe, B, Ca etc.).Thus reach and change the object of zeolite acidity, also there is impact to the specific surface area of catalyzer and micro pore volume simultaneously.The modifying function of base extraction to zeolite pore structure and Acidity is limited, and the too high or modified condition of concentration of lye is harsh can the structure of saboteur's sieve.
The adjustable change acidic zeolite of rare earth ion modification is carried out to molecular sieve.Rare earth ion, by polarization and inducing action, makes the water molecules around it polarize, effectively attracts OH
-, make H
+be in unbound state, produce B acid site, thus improve the cracking activity of catalyzer.Another vital role of rare earth ion is the stability increasing skeleton Al.Rare earth ion enters molecular sieve crystal inside by finishing, moves to β cage by supercage, interacts with skeleton Sauerstoffatom, inhibits molecular sieve skeleton under hydrothermal conditions to take off Al, thus enhances the stability of framework of molecular sieve structure.Rare earth modified degree is by the impact of rare earth loaded amount, and the too high meeting of rare earth loaded amount causes duct to block.
CN1775360A discloses a kind of method for improving ketone compound ammonia oxidation catalyst stability.In this method, nano-titanium si molecular sieves is through acidic cpd process, then uses organic bases process, or directly uses organic bases process.Molecular sieve after process defines the micropore and a large amount of cavitys and pit that a large amount of aperture is about 0.1-10nm.This method modification obtains molecular sieve and has excellent catalytic oxidation activity and activity stability.
Gained mixes through acid-treated TS-1 molecular sieve, organic bases and water by CN1245090A, and react 2 little of 8 day time in sealed reactor at the temperature of 120 ~ 200 DEG C and autogenous pressure, wherein said organic bases is fatty amines, alcamines or quaternary ammonium hydroxide compounds; Products therefrom is filtered, washs and drying.
USP6475465 discloses a kind of method HTS directly being used the process of organic bases compounds such as fatty amines, alcamines, quaternary ammonium bases.
USP4497969 discloses a kind of method of organic bases, organic acid, ethanol, glycerine, phenol, ester process crystalline silico-alumino molecular sieve.
USP5705729 discloses a kind of method that USY molecular sieve partly or entirely carries out rare earth exchanged modification.This method modification obtains molecular sieve and have good alkylation activity and activity stability in Trimethylmethane/butene alkylation.
USP7550405 and USP7470645 discloses a kind of catalyzer for catalyzing iso-butane alkane/butene alkylation.The preparation method of this catalyzer is for carry out modification by the metal such as β, Y, mordenite, L zeolite Al, Ti, Mo, Ni, Co, Fe, Pa, Pt.
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 brought.The requirement of alkylated reaction to catalyzer can not be met, to realize best selectivity, transformation efficiency and life-span.
Summary of the invention
The present inventor is found by a large amount of tests, when molecular sieve organic bases and the common modification of rare earth, unexpectedly can while guarantee molecular sieve pore passage be unimpeded, the charge capacity of the rare earth atom of the molecular sieve that remarkable increase is modified, combines thus and introduces matrix and the catalyzer that obtains has better catalytic performance for during 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 a kind of catalyzer exist and alkylated reaction condition under carry out the alkylated reaction of Trimethylmethane and butylene, wherein said catalyzer is prepared by the step of the step and introducing matrix that comprise modified molecular screen, the step of said modified molecular screen is by molecular sieve, is selected from after one or more material in water, alcohol, ester and organic bases mix, process under 100 ~ 250 DEG C and autogenous pressure in sealed reactor, after processing products therefrom recovery again, then exchange through rare earth ion salt.
Alkylation provided by the invention, at identical introducing matrix condition with under 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 a kind of catalyzer exist and alkylated reaction condition under carry out the alkylated reaction of Trimethylmethane and butylene, wherein said catalyzer is prepared by the step of the step and introducing matrix that comprise modified molecular screen, the step of said modified molecular screen is by molecular sieve, is selected from after one or more material in water, alcohol, ester and organic bases mix, process under 100 ~ 250 DEG C and autogenous pressure in sealed reactor, after processing products therefrom recovery again, then exchange through rare earth ion salt.
In method provided by the invention, the step of said modified molecular screen, this step comprises molecular sieve, is selected from after one or more material in water, alcohol, ester and organic bases mix, process under 100 ~ 250 DEG C and autogenous pressure in sealed reactor, after processing products therefrom recovery again, then exchange through rare earth ion salt.
Said molecular sieve is Si-Al molecular sieve or aluminium silicophosphate molecular sieve, through hydrothermal crystallizing synthesis 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, also can be at a certain temperature, organic acid or mineral acid or water vapour are contacted the Si-Al molecular sieve obtained or aluminium silicophosphate molecular sieve with molecular sieve.Said Si-Al molecular sieve or aluminium silicophosphate molecular sieve can be selected from FAU structural zeolite, BETA structural zeolite, MFI structure zeolite, CHA structure zeolite, mordenite, ZSM-11 zeolite, ZSM-22 zeolite and ZSM-48 zeolite one or more.
In said one or more the material be selected from water, alcohol, ester, alcohol is selected from the one comprised 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 containing amino (-NH2) in molecule.Organic bases is fatty amines, alcamines, quaternary ammonium bases, nitrogen heterocyclic ring organic bases, aromatic amine compound, such as, be diethylamine, triethylamine, tetraethyl ammonium hydroxide, arsenic pyridine etc.
Said organic bases also can be selected from I A, II A race metal alkoxide substitute, preferred alkoxide is sodium ethylate.
Said molecular sieve, the weight ingredient proportion being selected from one or more material in water, alcohol, ester and organic bases are preferably 1:2 ~ 10:0.5 ~ 3.Said process, preferably in sealed reactor, temperature of reaction is 120 ~ 200 DEG C, and under autogenous pressure, reaction 1 is little of 8 day time.The said process that process products therefrom reclaims being typically referred to is washed and drying, such as 110 DEG C processes of drying.
In the step of said modified molecular screen, said rare earth ion salt exchanges, and is that molecular sieve is contacted the process exchanged with rare earth ion.Said rare earth ion salt is that one or more are selected from the salt of 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, be 50 ~ 200 DEG C, preferably 50 ~ 100 DEG C in temperature, said exchange, can carry out 1-5 time; After each exchange, carry out washing, 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 the catalyst.Described matrix optionally can be commonly used for one or more in the various heat-resistant inorganic oxides of support of the catalyst and/or matrix certainly.Such as, one or more in aluminum oxide, silicon oxide, titanium oxide, magnesium oxide, alumina-silica magnesium, silica-alumina, silica-magnesias, silica-zirconia, silica thoria, silica-berylias, silica-titania, silica-zirconia, titania-zirconia, silica-alumina thoria, silica-alumina-titania, silicaalumina-magnesia, silica-alumina, zirconia, natural zeolite, synthesis zeolite, non-zeolitic molecular sieves and clay are selected from.A kind of or their mixture in preferred synthesis zeolite, non-zeolitic molecular sieves, silicon oxide, aluminum oxide, silica-alumina; Be more preferably one or more in aluminum oxide, silicon oxide, silica-alumina.With catalyzer total amount for benchmark, the content of described matrix components is no more than 95 % by weight, is 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 that the molecular sieve described matrix and described modification obtained mixes with water and pulls an oar under the condition of the molecular sieve being enough to described modification procedure to obtain and matrix pulp, dry afterwards and roasting.And the method for said drying and roasting and condition are this area customary way and condition, such as described maturing temperature can be 400 ~ 1000 DEG C, is preferably 450 ~ 800 DEG C.Molecular sieve in said catalyzer, the mixture of the molecular sieve that can obtain through modification procedure for different kinds of molecules sieve, such as, 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, also can be the mixture of Y molecular sieve and ZSM-22 molecular sieve.
Method provided by the invention, depending on different object or require also can comprise the step of the forming composition making various easy handling, such as, forms the forming step etc. of microballoon, spherical, tablet or bar shaped.Forming step can carry out according to a conventional method, as methods such as spray drying forming, compression molding, roller forming, extruded mouldings.
In method provided by the invention, the method for said alkylated reaction, its reaction conditions is temperature of reaction is 30-200 DEG C, pressure is 0.5-6.0MPa, and Feed space velocities 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 x ray fluorescence spectrometry (XRF) measures, and content of rare earth is with RE
2o
3% counts.
The specific surface area of molecular sieve and pore volume are measured by static state low temperature N2 adsorption volumetry (BET), and laboratory apparatus used is the static n2 absorption apparatus of Micromeritics company of U.S. ASAP-2405.Test process is: liquid nitrogen under 77K with adsorbent contact, leave standstill reach adsorption equilibrium.The amount of adsorbent nitrogen is gone out by the tolerance mathematic interpolation remained in gas phase after nitrogen air input and absorption.Specific surface area adopts two parameter BET Equation for Calculating, and pore distribution adopts BJH method to calculate.
Except as expressly described raw materials used 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 300g water, add lanthanum nitrate hexahydrate 40g, 50 DEG C exchange 5h, washing suction filtration, after 110 DEG C of oven dry, A counted by gained sample, and that carries out XRD, BET sign the results are shown in table 1.
Comparative example 1
This comparative example illustrates only carries 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 exchange 5h, washing suction filtration, and after 110 DEG C of oven dry, X counted by gained sample, and that carries out XRD, BET sign the results are shown in table 1.
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 200g water, add six nitric hydrate cerium 30g, 60 DEG C exchange 4h, washing suction filtration, after 110 DEG C of oven dry, B counted by gained sample, and that carries out XRD, BET sign the results are shown in table 1.
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 200g water, add lanthanum nitrate hexahydrate 30g, 70 DEG C exchange 3h, washing suction filtration, after 110 DEG C of oven dry, C counted by gained sample, and that carries out XRD, BET sign the results are shown in table 1.
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 100g water, add lanthanum nitrate hexahydrate 15g, 80 DEG C exchange 2h, washing suction filtration, after 110 DEG C of oven dry, D counted by gained sample, and that carries out XRD, BET sign the results are shown in table 1.
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 100g water, add lanthanum nitrate hexahydrate 15g, 90 DEG C exchange 1h, washing suction filtration, after 110 DEG C of oven dry, E counted by gained sample, and that carries out XRD, BET sign the results are shown in table 1.
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, 110 DEG C dry after, more above-mentioned organic bases modified sample is added 100g water, add lanthanum nitrate hexahydrate 15g, 100 DEG C exchange 0.5h, washing suction filtration, after 110 DEG C of oven dry, F counted by gained sample, and that carries out XRD, BET sign the results are shown in table 1.
Table 1
As can be seen from Table 1, the molecular sieve that method modification provided by the invention obtains, its with XRF measure content of rare earth with Re
2o
3% counts, and is increased to 14%, adds the rare earth loaded amount of 40% from 10% of comparative example 1.
Embodiment 7 ~ 10 illustrates the preparation of the catalyzer that method provided by the invention is 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, after making pseudo-boehmite colloidal sol, be warming up to 60 DEG C, keep 1h, cooling.
2.7Kg C is added, 1.1Kg A in 7.0Kg decationized Y sieve water, and 0.5Kg B, after homogenizer fully disperses, join in above-mentioned pseudo-boehmite-clay slurry, stir 0.5h.By above-mentioned slurries spray drying forming at exhaust temperature 250 DEG C, 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, after making pseudo-boehmite colloidal sol, be warming up to 60 DEG C, keep 1h, be cooled to room temperature afterwards.
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 Alumina gel
2o
3the heavy % of concentration 22.0), continue to stir 0.5h, obtain the heavy % of solid content 13.7, pH value is the catalyst slurry of 2.6.
By above-mentioned slurries spray drying forming at exhaust temperature 250 DEG C, 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, after making pseudo-boehmite colloidal sol, be warming up to 60 DEG C, keep 1h, be cooled to room temperature afterwards.
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 Alumina gel
2o
3the heavy % of concentration 22.0), continue to stir 0.5h, obtain the heavy % of solid content 26.2, pH value is the catalyst slurry of 3.9.By above-mentioned slurries spray drying forming at exhaust temperature 250 DEG C, 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, after making pseudo-boehmite colloidal sol, be warming up to 60 DEG C, keep 1h, be cooled to room temperature afterwards.
In 6.8Kg decationized Y sieve water, add the modified molecular screen A that 4Kg embodiment 1 is obtained, 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 Alumina gel
2o
3the heavy % of concentration 22.0), continue to stir 0.5h, obtain the heavy % of solid content 26.2, pH value is the catalyst slurry of 3.9.By above-mentioned slurries spray drying forming at exhaust temperature 250 DEG C, 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, after making pseudo-boehmite colloidal sol, be warming up to 60 DEG C, keep 1h, be cooled to room temperature afterwards.
In 6.8Kg decationized Y sieve water, add the modified molecular screen that 4Kg comparative example 1 is obtained, 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 Alumina gel
2o
3the heavy % of concentration 22.0), continue to stir 0.5h, obtain the heavy % of solid content 26.2, pH value is the catalyst slurry of 3.9.By above-mentioned slurries spray drying forming at exhaust temperature 250 DEG C, 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, after making pseudo-boehmite colloidal sol, be warming up to 60 DEG C, keep 1h, cooling.
In 7.0Kg decationized Y sieve water, adding 2.7Kg mordenite molecular sieve, (Zhou village catalyst plant provides, SiO
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 exhaust temperature 250 DEG C, after 650 DEG C of roasting 2h, obtain micro-spherical catalyst Z.
Embodiment 11 ~ 14
Embodiment 11 ~ 14 illustrates alkylation provided by the invention.
With the catalyzer that embodiment 7 ~ 10 is obtained, in continuous fixed bed reactor compressive reaction evaluating apparatus, carry out gas-phase reaction.Loaded catalyst is 1.5 grams, and catalyzer Trimethylmethane 200 DEG C, after having loaded, is first purged 5 hours before reaction by catalyzer.Be adjusted to temperature of reaction after reduction, under certain Feed space velocities, 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 the catalyzer obtained by comparative example 2,3, 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 (14)
1. the method for an alkylated reaction, it is characterized in that a kind of catalyzer exist and alkylated reaction condition under carry out the alkylated reaction of Trimethylmethane and butylene, wherein said catalyzer is prepared by the step of the step and introducing matrix that comprise modified molecular screen, the step of said modified molecular screen will be for obtaining through hydrothermal crystallizing synthesis, the molecular sieve of being down to by sodium ion wherein and having removed organic formwork agent wherein in sodium oxide≤0.2 % by weight roasting is exchanged through ammonium, be selected from water, alcohol, after one or more material in ester and organic bases mix, process under 100 ~ 250 DEG C and autogenous pressure in sealed reactor, after products therefrom recovery will be processed again, 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, Feed space velocities 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 structure zeolite, CHA structure 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, the weight ingredient proportion being selected from one or more material in water, alcohol, ester and organic bases are 1:2 ~ 10:0.5 ~ 3.
4. according to the method for claim 1, wherein said alcohol is selected from the one comprised 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.
5. according to the method for claim 1 or 4, wherein, said alcohol is ethanol or methyl alcohol, and said ester is methyl-formiate.
6., according to the process of claim 1 wherein, said organic bases is containing amino organic basic compound in molecule.
7. according to the method for claim 1 or 6, wherein, said organic bases is selected from fatty amines, alcamines, quaternary ammonium bases, nitrogen heterocyclic ring organic bases or aromatic amine compound.
8., according to the process of claim 1 wherein, said organic bases is diethylamine, triethylamine, tetraethyl ammonium hydroxide or pyridine.
9., according to the process of claim 1 wherein, said organic bases is the alkoxide being selected from I A, II A race metal.
10. according to the method for claim 9, wherein, said alkoxide is sodium ethylate.
11. according to the process of claim 1 wherein, said rare earth ion salt is the soluble metallic salt containing lanthanum and/or cerium.
12. according to the process of claim 1 wherein, said process is that under 120 ~ 200 DEG C and autogenous pressure, process 1 is little of 8 days in sealed reactor.
13. according to the process of claim 1 wherein, said matrix is selected from one or more in heat-resistant inorganic oxide.
14. according to the process of claim 1 wherein, with catalyzer total amount for 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.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310038433.1A CN103964994B (en) | 2013-01-31 | 2013-01-31 | A kind of method of alkylated reaction |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310038433.1A CN103964994B (en) | 2013-01-31 | 2013-01-31 | A kind of method of alkylated reaction |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103964994A CN103964994A (en) | 2014-08-06 |
| CN103964994B true CN103964994B (en) | 2015-10-28 |
Family
ID=51235056
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310038433.1A Active CN103964994B (en) | 2013-01-31 | 2013-01-31 | A kind of method of alkylated reaction |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103964994B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP7444894B2 (en) | 2019-01-25 | 2024-03-06 | 中国石油化工股▲ふん▼有限公司 | Solid acid catalyst, its production, and its use |
| 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 |
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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103964994A (en) | 2014-08-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103962177B (en) | A kind of preparation method of the catalyst containing molecular sieve | |
| CN102020289B (en) | Super-stable Y zeolite, preparation method and application thereof | |
| CN101745418B (en) | Catalytic cracking catalyst, preparation and application thereof | |
| CN102173436B (en) | Preparation method of rare earth (RE) yttrium (Y) molecular sieve | |
| CN104556120B (en) | Preparation method of metal modified Y type molecular sieve | |
| RU2755891C2 (en) | Catalytic cracking catalyst and its preparation | |
| JP6509877B2 (en) | Two metal-exchanged zeolite beta by synthesis without using organic template, and method of using it in selective catalytic reduction of NOx | |
| CN101767028B (en) | Preparation method of fluid catalytic cracking catalyst | |
| CN106140296A (en) | A kind of method of catalytic cracking spent catalyst recycling | |
| RU2624443C2 (en) | Catalyst for catalytic cracking of hydrocarbons | |
| CN104043477A (en) | ZSM-5/MCM-48 composite molecular sieve, preparation method and application thereof | |
| CN103964459B (en) | A kind of method of modifying of molecular sieve | |
| CN107362824B (en) | Iron and copper containing zeolite beta obtained from an organotemplate-free synthesis process | |
| CN101670295B (en) | Preparation method of cracking catalyst | |
| CN108452825A (en) | Magnesium-modified high silicon super-stable Y molecular sieves of one kind and preparation method thereof | |
| CN110193376A (en) | A kind of catalytic cracking petroleum hydrocarbons catalyst | |
| JP2013095653A (en) | Zeolite having copper and alkali metal | |
| CN102553630B (en) | High- silica alumina ratio small- crystal grain Y zeolite catalytic cracking catalyst and preparation method thereof | |
| CN103964994B (en) | A kind of method of alkylated reaction | |
| CN102091648B (en) | Method for preparing carclazyte olefin removing catalyst | |
| CN102059138A (en) | ZSM-5 zeolite catalyst for preparing propylene by methanol dehydration as well as preparation method and application thereof | |
| CN106140255B (en) | A kind of Modified Zeolite Y and its preparation and application | |
| CN101209423A (en) | Preparation method of molecular sieve catalyst with superpower acidity | |
| CN106140277B (en) | A kind of modified beta zeolite and preparation method thereof | |
| JP6879680B2 (en) | Method for producing high silica chabazite type zeolite and high silica chabazite type zeolite |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |