CN103566966B - N-alkene isomerization catalyst and preparation method thereof - Google Patents
N-alkene isomerization catalyst and preparation method thereof Download PDFInfo
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Abstract
A kind of N-alkene isomerization catalyst, comprise carrier and modified compound, the mass ratio of described modified compound and carrier is 0.01 ~ 0.4:1, described carrier comprises mixed molecular sieve and binding agent, described modified compound is selected from phenol, monose or disaccharides, polyalcohol or organic acid ammonium salt, and described mixed molecular sieve comprises mesoporous molecular sieve and large pore molecular sieve.This catalyst uses modified compound to carry out modification to catalytic active component, can significantly improve the isomerisation selectivity of catalyst.
Description
Technical field
The present invention is a kind of olefin isomerization catalyst and preparation method thereof, specifically, is a kind of normal olefin skeleton isomerization Catalysts and its preparation method.
Background technology
Along with the increasingly stringent of environmental requirement, clean gasoline demand constantly increases.By the C of positive structure
4~ C
6the isobutene that alkene is obtained by skeletal isomerization, methylpentene and neohexene, through etherificate, can prepare high-knock rating gasoline additive, to improve gasoline quality.
USP5,382,743 disclose a kind of ZSM-35 molecular sieve that uses aligns the method that amylene carries out skeletal isomerization under the condition of facing hydrogen, finds that reaction is conducive to improving the reactivity of catalyst under hydro condition, reduce deactivation rate, the extending catalyst life-span.
USP5,817, the 907 a kind of methods disclosing straight-chain olefin skeleton isomerization, in used catalyst at least containing a kind of through pretreated molecular sieve, molecular screening is at least one in SAPO-11, the SAPO-31 of 0.4nm ~ 0.8nm, Theta-1, EU-1, OMEGA, modenite, Nu-10, Nu-86, Nu-87, ferrierite ZSM-35, ZSM-12 and ZSM-23 from aperture.Pretreated method is with containing C by described molecular sieve
4~ C
20hydrocarbon molecule contact in the presence of an inert gas, preferred hydrocarbon is C
4~ C
12monoolefine, polyene or alkane etc., more preferably C
4~ C
12alkane.Pretreated air speed is 0.1h
-1~ 45h
-1, temperature 300 DEG C ~ 550 DEG C, pressure 0.1MPa ~ 1.0MPa, 0.5 ~ 48 hour processing time.Pretreatment makes coke deposit in described molecular sieve pore passage, and the pore volume of molecular sieve significantly reduces, thus improves the selective of isomeric olefine, and has good stability.But, adopt hydro carbons to be the step that raw material carries out the process of High Temperature Pre carbon deposit add an inert atmosphere before olefin isomerization reaction under, cause reaction process complicated.
Summary of the invention
The object of this invention is to provide a kind of N-alkene isomerization catalyst and preparation method, this catalyst uses modified compound to carry out modification to catalytic active component, can significantly improve the isomerisation selectivity of catalyst.
N-alkene isomerization catalyst provided by the invention, comprise carrier and modified compound, the mass ratio of described modified compound and carrier is 0.01 ~ 0.4:1, described carrier comprises mixed molecular sieve and binding agent, described modified compound is selected from phenol, monose or disaccharides, polyalcohol or organic acid ammonium salt, and described mixed molecular sieve comprises mesoporous molecular sieve and large pore molecular sieve.
Large pore molecular sieve and mesoporous molecular sieve are mixed the active component as isomerization catalyst by the present invention, and with modified compound, modification is carried out to catalytic active component, method for preparing catalyst is simple, without the need to increasing the handling process that pair adds, be easy to control, gained catalyst is used for normal olefin skeleton isomerization reaction, isomerisation selectivity significantly improves, and isomerization product yield increases.
Detailed description of the invention
The present invention mixes appropriate large pore molecular sieve in mesoporous molecular sieve, therefore comparatively cheap ZSM-5 can be used to replace ZSM-35, mixed molecular sieve is made to have the isomerization performance suitable with ZSM-35, in addition, by using modified compound, modification is carried out to mixed molecular sieve, modified compound is deposited on molecular sieve surface, can effectively improve its physico-chemical property, makes its isomerization performance improve.The present invention adopts simple in-situ treatment method Kaolinite Preparation of Catalyst, processing ease, and modified compound content is in the catalyst easy to control.
Molecular sieve of the present invention comprises mesoporous molecular sieve and large pore molecular sieve, described mesoporous molecular sieve preferred ZSM-5 and ZSM-22 and/or SAPO-11, namely at least ZSM-5 molecular sieve should be contained in preferred mesoporous molecular sieve combination, mesoporous molecular sieve combination can be ZSM-5 and ZSM-22, ZSM-5 and SAPO-11, or ZSM-5, ZSM-22 and SAPO-11, the preferred Beta molecular sieve of large pore molecular sieve.
Binding agent in carrier of the present invention is selected from one or more in aluminium oxide, silica, titanium oxide, magnesia, 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 clay, preferential oxidation aluminium.
Carrier of the present invention comprises the mixed molecular sieve of 50 ~ 99 quality % and the binding agent of 1 ~ 50 quality %, preferably includes the mixed molecular sieve of 60 ~ 95 quality % and the binding agent of 5 ~ 40 quality %.Modified compound in catalyst of the present invention and the mass ratio of carrier are preferably 0.01 ~ 0.3:1.In described mixed molecular sieve, the mass ratio of mesoporous molecular sieve and large pore molecular sieve is 5 ~ 60, preferably 5 ~ 50.
The modified compound contained in catalyst of the present invention has multiple, is selected from phenol, monose or disaccharides, polyalcohol or organic acid ammonium salt.
Phenolic compound shown in the first modified compound of the present invention-phenol preferred formula (I) and/or the naphthol compound shown in formula (II).
In formula (I) and formula (II) ,-OH represents the hydroxyl on phenyl ring or naphthalene nucleus, and its number can be 1 ~ 3, and Y is the substituting group on phenyl ring or naphthalene nucleus, and its number can be 1 ~ 3.In the present invention, be easy statement, Y also can be hydrogen, and when Y is hydrogen, formula (I) or formula (II) namely represent phenol or naphthols respectively, and described phenol can be phenol, benzenediol or benzenetriol.When Y is C
1~ C
3alkyl or-NH
2time, formula (I) is alkyl phenol or amino phenols, and formula (II) is alkyl naphthol or aminonaphthol.
Described phenol be preferably in phenol, benzenediol, benzenetriol, naphthols, cresols or amino phenols one or more.
The second modified compound of the present invention is monose or disaccharides, and the carbon number of described monose is preferably 3 ~ 6, preferred triose, tetrose, pentose or hexose, the preferred aldohexose of described hexose, as glucose, mannose, galactolipin, hexose also can be ketohexose, as fructose; Described disaccharides is sucrose, lactose, maltose or cellobiose, preferably sucrose.
The third modified compound of the present invention is polyalcohol, preferred C
2~ C
7polyalcohol.Described C
2~ C
7the preferred ethylene glycol of polyalcohol, propane diols, butanediol, pentanediol, hexylene glycol, glycerine, trimethylolethane, pentaerythrite, one or more in xylitol and sorbierite.
4th kind of modified compound of the present invention is organic acid ammonium salt, optimization acid's ammonium or amino acid ammonium.Described carboxylic acid ammonium is aliphatic carboxylic acid ammonium or aromatic carboxylic acid ammonium, not containing aromatic ring in the carbochain that aliphatic carboxylic acid ammonium is connected with carboxyl, and containing aromatic ring in the carbochain that aromatic carboxylic acid ammonium is connected with carboxyl.The carbon number of described aliphatic carboxylic acid ammonium preferably 1 ~ 14, the carbon number of aromatic carboxylic acid ammonium preferably 6 ~ 10.Preferred carboxylic acid ammonium is ammonium formate, ammonium acetate, Triammonium citrate, ammonium oxalate, ammonium tartrate, malic acid ammonium, ammonium lactate, ethylenediamine tetra-acetic acid two ammonium, trans CDTA ammonium, ammonium benzoate, ammonium salicylate, caffeic acid ammonium.Amino acid ammonium preferred aminotriacetic acid three ammonium.
Be suitable for catalyst of the present invention and carry out the preferred C of isomerized normal olefine
4~ C
6normal olefine.
The preparation method of catalyst provided by the invention, comprise mesoporous molecular sieve and large pore molecular sieve and binding agent mixed-forming, dry, roasting obtains carrier, then uses the solution impregnation of modified compound, after dipping solid in 30 ~ 200 DEG C, dry under 0.01 ~ 0.1MPa condition.
Described mesoporous molecular sieve preferred ZSM-5 and ZSM-22 and/or SAPO-11, the preferred Beta molecular sieve of large pore molecular sieve, binding agent preferential oxidation aluminium.
The method of mixed molecular sieve and binding agent mixed-forming is extrusion, drips ball, spin or pressed disc method, preferred extruded moulding by the inventive method.Extruded moulding method is: mixed with binding agent or its precursor by mixed molecular sieve, adds appropriate extrusion aid and/or peptizing agent kneading, then extruded moulding.The preferred sesbania powder of described extrusion aid, peptizing agent preferred inorganic acid, example hydrochloric acid or nitric acid.After wet bar pelletizing, drying, roasting obtain carrier.The temperature of described roasting preferably 400 ~ 650 DEG C, roasting time preferably 1 ~ 10 hour.
In the inventive method, also can first by mixed molecular sieve, pretreatment is carried out with modified compound, and then with binding agent mixed-forming, drying, roasting obtain carrier, and then by the solution impregnation of carrier modified compound, after dipping, solid is in 30 ~ 200 DEG C, dry obtained catalyst under 0.01 ~ 0.1MPa condition, and the modified compound in catalyst does not comprise pretreatment modified compound used.
The preprocess method of above-mentioned mixed molecular sieve is: with the solution impregnation mixed molecular sieve of modified compound, then will flood solid drying afterwards, then with binding agent mixed-forming, drying, roasting obtain carrier.
During preparation catalyst of the present invention, also by the solution impregnation two of carrier modified compound that obtain after roasting to repeatedly, after flooding, all can need drying at every turn.The modified compound that each dipping uses may be the same or different.
Above-mentioned dipping is the solution impregnating carrier with modified compound, and can be saturated dipping, unsaturated dipping or supersaturation dipping, preferred saturated dipping, also claim incipient wetness method dipping, namely maceration extract volume equals the amount of liquid of carrier adsorption; Dip time preferably 0.1 ~ 24 hour, more preferably 0.5 ~ 8 hour.
During preparation maceration extract, the concentration of modified compound solution is 0.01 ~ 5.0 mol/L, preferably 0.01 ~ 3.0 mol/L.After dipping, dry desolvation.Control drying condition not decompose with non-volatile to make modified compound.Suitable baking temperature is 40 ~ 150 DEG C, preferably 60 ~ 130 DEG C, and drying time is 1 ~ 24 hour, is preferably 2 ~ 8 hours, and drying pressure is 0.01 ~ 0.1MPa.
In said method, when modified compound is phenol, the solvent preparing modified compound solution used is organic matter, the preferred C of described organic matter
6~ C
8alkane or aromatic hydrocarbons, or C
2~ C
4fatty alcohol.When described modified compound be monose or disaccharides, polyalcohol or organic acid ammonium salt time, preparation modified compound solution solvent used is water.
Catalyst provided by the invention, is applicable to the skeletal isomerization of normal olefine, is particularly suitable for C
4~ C
6the skeletal isomerization of normal olefine, to prepare isomeric olefine.
Use catalyst of the present invention to carry out normal olefine isomerization reaction to carry out in presence of hydrogen.Reaction temperature is 200 ~ 550 DEG C, preferably 250 ~ 350 DEG C, and pressure is 0.05 ~ 1MPa, preferably 0.1 ~ 0.5MPa, and feed volume air speed is 0.5 ~ 6.0 hour
-1, be preferably 1 ~ 4 hour
-1, hydrogen/hydrocarbon volume ratio is 100 ~ 5000, preferably 200 ~ 2000.
Further illustrate the present invention below by example, but the present invention is not limited to this.
In example, prepare catalyst of the present invention and in carrier, introduce modified compound all adopt saturated infusion process, be i.e. incipient wetness method dipping.In example, molecular sieve used builds long catalyst plant by Hunan provides, and boehmite is provided by German Condea company, and its butt alumina content is 74 quality %.
Example 1
3568 grams, SAPO-11 molecular sieve, 3946 grams, HZSM-5 molecular sieve, 2326 grams, HZSM-22 molecular sieve, 948 grams, Beta molecular sieve are mixed with 1637.8 grams of boehmites, add nitric acid and 10770 grams of water that 65.5 grams of concentration are 65 quality %, the trilobal bar that diameter is 1.1 millimeters is extruded into double screw banded extruder, pelletizing, 120 DEG C of dryings 4 hours, 550 DEG C of roastings 2 hours, obtain carrier S
1, wherein molecular sieve content is 90 quality %, alumina content is 10 quality %.
Get 2000 grams of carrier S
1, with the n-heptane solution 1952 milliliters containing 283.1 grams of (2.618mol) orthoresols in 25 DEG C of dippings 0.5 hour, 90 DEG C, under 0.01MPa condition dry 2 hours, obtain catalyst C
1, its weight is 2280.9 grams, and catalyst C is described
1in containing the orthoresol of 280.9 grams, contained phenol and carrier S
1mass ratio be 0.14.
Example 2
3879.0 grams, SAPO-11 molecular sieve, 3790.0 grams, HZSM-5 molecular sieve, 2898.0 grams, HZSM-22 molecular sieve, 221.0 grams, Beta molecular sieve are mixed with 1637.8 grams of boehmites, add nitric acid and 10770 grams of water that 65.5 grams of concentration are 65 quality %, the trilobal bar that diameter is 1.1 millimeters is extruded into double screw banded extruder, pelletizing, 120 DEG C of dryings, 4 hours, 550 DEG C roastings 2 hours, obtain carrier S
2, wherein molecular sieve content is 90 quality %, alumina content is 10 quality %.
Get 2000 grams of carrier S
2, with the n-heptane solution 1955 milliliters containing 326.5 grams of (2.965mol) catechols in 25 DEG C of dippings 0.5 hour, then in 130 DEG C, under 0.01MPa condition dry 2 hours, obtain catalyst C
2, its weight is 2323.2 grams, and catalyst C is described
2in containing the catechol of 323.2 grams, contained phenol and carrier S
2mass ratio be 0.162.
Example 3
Get 2000 grams of carrier S
1, with the toluene solution 1952 milliliters containing 567.1 grams of (3.934mol) naphthols in 25 DEG C of dippings 0.5 hour, then in 90 DEG C, under 0.01MPa condition dry 2 hours, obtain catalyst C
3, its weight is 2562.1 grams, and catalyst C is described
3in containing the naphthols of 562.1 grams, contained phenol and carrier S
1mass ratio be 0.281.
Example 4
Get 2000 grams of carrier S
1, with the aqueous solution 1952 milliliters containing 172.5 grams of (0.870mol) D-Glucoses in 25 DEG C of dippings 0.5 hour, then in 90 DEG C, under 0.01MPa condition dry 2 hours, obtain catalyst C
4, its weight is 2171.8 grams, and catalyst C is described
4in containing the D-Glucose of 171.8 grams, sugary and carrier S
1mass ratio be 0.086.
Example 5
Get 2000 grams of carrier S
2, with the aqueous solution 1955 milliliters containing 182.6 grams of (0.533mol) sucrose in 25 DEG C of dippings 0.5 hour, then in 90 DEG C, under 0.01MPa condition dry 2 hours, obtain catalyst C
5, its weight is 2182.1 grams, and catalyst C is described
5in containing the sucrose of 182.1 grams, sugary and carrier S
2mass ratio be 0.091.
Example 6
Get 2000 grams of carrier S
1, with the aqueous solution 1952 milliliters of the triose (D-glyceraldehyde and dihydroxyacetone (DHA) mass ratio are 1:1) containing 253.1 grams (2.812mol) in 25 DEG C of dippings 0.5 hour, then in 90 DEG C, under 0.01MPa condition dry 2 hours, obtain catalyst C
6, its weight is 2251.0 grams, and catalyst C is described
6in containing the triose of 251.0 grams, sugary and carrier S
1mass ratio be 0.126.
Example 7
Get 2000 grams of carrier S
1, with the aqueous solution 1952 milliliters containing 299.5 grams of (3.252mol) glycerine in 25 DEG C of dippings 0.5 hour, then in 90 DEG C, under 0.01MPa condition dry 2 hours, obtain catalyst C
7, its weight is 2298.9 grams, and catalyst C is described
7in containing the glycerine of 298.9 grams, contained alcohol and carrier S
1mass ratio be 0.15.
Example 8
Get 2000 grams of carrier S
2, with the aqueous solution 1955 milliliters containing 297.6 grams of (2.518mol) hexylene glycols in 25 DEG C of dippings 0.5 hour, then in 90 DEG C, under 0.01MPa condition dry 2 hours, obtain catalyst C
8, its weight is 2296.9 grams, and catalyst C is described
8in containing the hexylene glycol of 296.9 grams, contained alcohol and carrier S
2mass ratio be 0.148.
Example 9
Get 2000 grams of carrier S
1, with the aqueous solution 1952 milliliters containing 289.3 grams of (1.721mol) malic acid ammoniums in 25 DEG C of dippings 0.5 hour, then in 90 DEG C, under 0.01MPa condition dry 2 hours, obtain catalyst C
9, its weight is 2288.5 grams, and catalyst C is described
9in containing the malic acid ammonium of 288.5 grams, institute's ammonium salt-containing and carrier S
1mass ratio be 0.144.
Example 10
Get 2000 grams of carrier S
2, with the aqueous solution 1955 milliliters containing 290.5 grams of (1.872mol) ammonium salicylates in 25 DEG C of dippings 0.5 hour, then in 90 DEG C, under 0.01MPa condition dry 2 hours, obtain catalyst C
10, its weight is 2289.7 grams, and catalyst C is described
10in containing the ammonium salicylate of 289.7 grams, institute's ammonium salt-containing and carrier S
2mass ratio be 0.145.
Example 11
7980 grams of HZSM-5 molecular sieves, 1120 grams of SAPO-11 and 1688 gram of Beta molecular sieve n-heptane solutions 10798 milliliters of 120.0 grams of (1.110mol) orthoresols are flooded 0.5 hour in 25 DEG C, again in 90 DEG C, under 0.01MPa condition dry 2 hours, obtain pretreated mixed molecular sieve.
Above-mentioned pretreated mixed molecular sieve is mixed with 1637.8 grams of boehmites, add nitric acid and 10770 grams of water that 65.5 grams of concentration are 65 quality %, the trilobal bar that diameter is 1.1 millimeters is extruded into double screw banded extruder, pelletizing, 120 DEG C of dryings, 4 hours, 550 DEG C roastings 2 hours, obtain carrier S 3, wherein molecular sieve content is 90 quality %, alumina content 10 quality %.
Get 2000 grams of carrier S
3, with the n-heptane solution 1939 milliliters containing 123.0 grams of (1.137mol) orthoresols in 25 DEG C of dippings 0.5 hour, then in 90 DEG C, under 0.01MPa condition dry 2 hours, obtain catalyst C
11, its weight is 2121.5 grams, and catalyst C is described
11in containing the orthoresol of 121.5 grams, contained phenol and carrier S
3mass ratio be 0.061.
Example 12
Get 2000 grams of carrier S
3, with the aqueous solution 1939 milliliters containing 90.2 grams of (0.455mol) D-Glucoses in 25 DEG C of dippings 0.5 hour, then in 90 DEG C, under 0.01MPa condition dry 2 hours, obtain catalyst C
12, its weight is 2089.7 grams, and catalyst C is described
12in containing the D-Glucose of 89.7 grams, sugary and carrier S
3mass ratio be 0.045.
Example 13
Get 2000 grams of carrier S
3, with the aqueous solution 1939 milliliters containing 134.3 grams of (1.459mol) glycerine in 25 DEG C of dippings 0.5 hour, then in 90 DEG C, under 0.01MPa condition dry 2 hours, obtain catalyst C
13, its weight is 2133.8 grams, and catalyst C is described
13in containing the glycerine of 133.8 grams, contained alcohol and carrier S
3mass ratio be 0.067.
Example 14
Get 2000 grams of carrier S
3, with the aqueous solution 1939 milliliters containing 131.6 grams of (0.541mol) Triammonium citrates in 25 DEG C of dippings 0.5 hour, then in 90 DEG C, under 0.01MPa condition dry 2 hours, obtain catalyst C
14, its weight is 2131.1 grams, and catalyst C is described
14in containing the Triammonium citrate of 131.1 grams, institute's ammonium salt-containing and carrier S
3mass ratio be 0.066.
Example 15 ~ 31
Following instance evaluates the isomerization reaction performance of catalyst of the present invention.
With 1-amylene for reaction raw materials, with the carrier of non-modified compound treatment for comparative catalyst, small fixed hydrogenation reaction device evaluates catalyst of the present invention and comparative catalyst respectively.
Concrete operation method is: by the flat-temperature zone of Catalyst packing in reactor, introduces hydrogen and reaction pressure is adjusted to 0.3MPa.Temperature of reactor is risen to 400 DEG C, stablize 2 hours, then the temperature of reactor is adjusted to 300 DEG C, after temperature stabilization, inject 1-amylene in reactor, controlling reaction temperature is 300 DEG C, feed volume air speed 1.7h
-1, reaction pressure is 0.3MPa, hydrogen/hydrocarbon volume ratio is 600, reacts after 12 hours and samples, and adopt gas-chromatography sampling on-line analysis, reaction result is in table 1.
Table 1
From table 1 data, the catalyst that the present invention obtains after modified compound process, than the comparative catalyst of non-modified process, iso-amylene yield and iso-amylene is selective is all significantly improved.
Claims (22)
1. a N-alkene isomerization catalyst, comprise carrier and modified compound, the mass ratio of described modified compound and carrier is 0.01 ~ 0.4:1, described carrier comprises mixed molecular sieve and binding agent, described modified compound is selected from phenol, monose or disaccharides, polyalcohol or organic acid ammonium salt, and described mixed molecular sieve comprises mesoporous molecular sieve and large pore molecular sieve.
2. according to catalyst according to claim 1, it is characterized in that described mesoporous molecular sieve is selected from ZSM-5 and ZSM-22 and/or SAPO-11, large pore molecular sieve is Beta molecular sieve.
3., according to catalyst according to claim 1, it is characterized in that the mass ratio of described mesoporous molecular sieve and large pore molecular sieve is 5 ~ 50.
4., according to catalyst according to claim 1, it is characterized in that described carrier comprises the mixed molecular sieve of 50 ~ 99 quality % and the binding agent of 1 ~ 50 quality %.
5., according to catalyst according to claim 1, it is characterized in that described phenol is for having the phenolic compound of formula (I) structure expression and/or having the naphthol compound of formula (II) structure expression,
In formula (I) and formula (II), the number of hydroxyl is 1 ~ 3, and Y is the substituting group on phenyl ring or naphthalene nucleus, and its number is 1 ~ 3, and Y is selected from hydrogen, C
1~ C
3alkyl or-NH
2.
6. according to catalyst according to claim 5, it is characterized in that described phenol is selected from phenol, benzenediol, benzenetriol, naphthols, cresols and amino phenols one or more.
7., according to catalyst according to claim 1, it is characterized in that described monose carbon number is 3 ~ 6, described disaccharides is sucrose.
8., according to catalyst according to claim 1, it is characterized in that described polyalcohol is C
2~ C
7polyalcohol.
9., according to catalyst according to claim 8, it is characterized in that described C
2~ C
7polyalcohol be selected from ethylene glycol, propane diols, butanediol, pentanediol, hexylene glycol, glycerine, trimethylolethane, pentaerythrite, xylitol and sorbierite one or more.
10., according to catalyst according to claim 1, it is characterized in that described organic acid ammonium salt is selected from carboxylic acid ammonium or amino acid ammonium.
11. according to catalyst according to claim 10, it is characterized in that described carboxylic acid ammonium is for aliphatic carboxylic acid ammonium or aromatic carboxylic acid ammonium.
12. according to catalyst according to claim 11, it is characterized in that the carbon number of described aliphatic carboxylic acid ammonium is 1 ~ 14, the carbon number of aromatic carboxylic acid ammonium is 6 ~ 10.
13. according to catalyst according to claim 1, it is characterized in that described binding agent is aluminium oxide.
14. according to catalyst according to claim 1, it is characterized in that described normal olefine is C
4~ C
6normal olefine.
The preparation method of catalyst described in 15. 1 kinds of claims 1, comprise mesoporous molecular sieve and large pore molecular sieve and binding agent mixed-forming, dry, roasting obtains carrier, then uses the solution impregnation of modified compound, after dipping solid in 30 ~ 200 DEG C, dry under 0.01 ~ 0.1MPa condition.
16. in accordance with the method for claim 15, it is characterized in that described mesoporous molecular sieve is selected from ZSM-5 and ZSM-22 and/or SAPO-11, and large pore molecular sieve is Beta molecular sieve, and binding agent is aluminium oxide.
17. in accordance with the method for claim 15, it is characterized in that first mixed molecular sieve modified compound being carried out pretreatment, preprocess method is the solution impregnation with modified compound, solid drying after then flooding, again with binding agent mixed-forming, dry, roasting obtains carrier.
18. in accordance with the method for claim 15, and it is characterized in that the solution impregnation two of carrier modified compound that obtains after roasting, to repeatedly, all needs drying after each dipping.
19. in accordance with the method for claim 15, it is characterized in that the concentration of modified compound solution is 0.01 ~ 3.0 mol/L.
20. in accordance with the method for claim 18, it is characterized in that the modified compound that each dipping uses is identical or different.
21. according to the method described in claim 15 or 17, and when it is characterized in that described modified compound is phenol, the solvent preparing modified compound solution used is organic matter, and described organic matter is C
6~ C
8alkane or aromatic hydrocarbons, or C
2~ C
4fatty alcohol.
22. according to the method described in claim 15 or 17, it is characterized in that described modified compound be monose or disaccharides, polyalcohol or organic acid ammonium salt time, preparation modified compound solution solvent used is water.
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| 铵盐改性对β分子筛的酸性及其催化二异丙苯异构化反应性能的影响;赵培侠等;《石油化工》;20051231;第34卷(第6期);527-531 * |
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