CN102049298A - Composite solid acid catalyst as well as preparation method and application thereof in alkylation reaction - Google Patents
Composite solid acid catalyst as well as preparation method and application thereof in alkylation reaction Download PDFInfo
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Abstract
The invention provides a composite solid acid catalyst which comprises the following components in percentage by weight: 50-80 percent of porous inorganic carrier, 15-48 percent of heteropoly acid and 2-6 percent of inorganic acid, wherein the heteropoly acid and the inorganic acid are loaded on the porous inorganic carrier. The invention also provides a method for preparing the composite solid acid catalyst. The type of the acid center of the composite solid acid catalyst provided by the invention is acid, the density of the acid center is not less than 1.4molH+/g, the acid strength is uniformly distributed, and the composite solid acid catalyst is a solid acid catalytic material with excellent performance. The invention also provides the application of the composite solid acid catalyst in alkylation reaction.
Description
Technical field
The present invention relates to a kind of composite solid-acid catalyst, preparation method and the application in alkylated reaction thereof, specifically, relate to a kind of composite solid-acid catalyst, preparation method and application in alkylated reaction thereof that contains inorganic acid and heteropoly acid simultaneously.
Background technology
In the petrochemical industry catalytic field, most of hydrocarbon conversion reactions, as cracking, alkylation, reformation, superimposition, isomerization, etherificate, disproportionated reaction etc. all adopt the acidic catalyst material as catalyst (Hou Xianglin. " Chinese oil Refining Technologies ", Sinopec publishing house, 1991).Therefore, the acidic catalyst material has crucial status in the petrochemical industry catalytic field.The vital task that to research and develop more high performance acidic catalyst material be researcher.
The acid properties of acidic catalyst material mainly comprise acid site density, acid strength, acid site type (
Acid or Lewis acid), they are to (seeing Wu Yue, " catalytic chemistry ", Science Press, Beijing, 2000,162-196 with the acidic catalyst material as the influence of the catalytic reaction of catalyst is very remarkable and important; Han Weiping, " catalytic chemistry introduction ", Science Press, Beijing, 2003,172-238; Huang Zhongtao, Ceng Zhaohuai, " petrochemical process catalytic action ", Sinopec publishing house, Beijing, 1995,209-253).The acid site density of acidic catalyst is to hydrocarbon conversion reaction, most important as cracking reaction, alkylated reaction etc., it can improve significantly reaction selectivity (He Mingyuan. " petroleum refining and the synthetic Green Chemistry of basic organic chemicals ", Sinopec publishing house, Beijing, 2005,109-169).The acidic catalyst material can be divided into two big classes: liquid acid, and as sulfuric acid, hydrofluoric acid etc., and solid acid, as molecular sieve, super acids, support type acid catalytic material, acid ion resin etc.Liquid acid has very high acid site density (with mole H
+/ gram is counted), and be all
The acid site.Solid acid is owing to be subjected to the restriction of its structure, generally speaking their acid site density than low two orders of magnitude of liquid acid about, the density in the acid site of nearly all solid acid catalyst material of present prior art for preparing all can't reach the order of magnitude of liquid acid.Liquid acid and solid acid catalyst acid properties relatively see Table 1:
The acid properties of table 1 acid catalyst
B:
Acid; L:Lewis acid
Summary of the invention
The purpose of this invention is to provide the preparation method of a kind of composite solid-acid catalyst, this composite solid-acid catalyst and the application in alkylated reaction thereof.
Heteropoly acid is to comprise that, condensation acidified by two or more inorganic oxygen-containing acid ion, dehydration obtain having a class inorganic compound in cagelike structure and duct, and the compound of this class formation has highly acid.Very little (the 1-2m of the specific area of heteropoly acid itself
2/ g), therefore being not suitable as solid acid and using separately, adopt loads on use (Chinese patent CN 1232814A on the porous carrier more; U.S. Pat 5324881).Heteropoly acid is made up of cation and anion, and anion has very large molecular dimension (1.23nm), so has formed bigger stackeding space between the anion of heteropoly acid.
We discover: when using the hydrocarbons that has dissolved certain content inorganic acid, as saturated alkane, cycloalkane, under certain conditions with load the porous inorganic carrier material of heteropoly acid when contacting, these inorganic acids (molecular dimension of HF is 0.13nm, and the molecular dimension of HCl is 0.18nm) that are dissolved in the little molecular dimension in the hydrocarbon can be absorbed in the stackeding space that forms between the heteropolyacid anions with big molecular dimension; H in stackeding space in these inorganic acid molecules
+H with heteropoly acid molecule itself
+All be the acid centre of catalysis material, and all these acid centres all are typical
Acid site, this catalyzed by mixed solid acid material have the acid site density higher than the solid acid catalyst material of prior art for preparing, and acid site density is not less than 1.4 moles of H
+/ gram, and acid strength distribution homogeneous.
The invention provides a kind of composite solid-acid catalyst, form by the heteropoly acid of the porous inorganic carrier of the heavy % of 50-80 and the load heavy % of 15-48 on it and the inorganic acid of the heavy % of 2-6.
Wherein said porous inorganic carrier is selected from one or more the mixture in silica, aluminium oxide, active carbon, magnesia, titanium oxide, natural or artificial synthetic aluminosilicate zeolite, molecular sieve, carbon fiber and the natural clay.Described zeolite, molecular sieve can be one or more the mixtures in A type zeolite, X type zeolite, y-type zeolite, modenite, ZSM-series zeolite, Beta zeolite, offretite zeolite, omega zeolite, phosphate aluminium molecular sieve, the HTS; Described clay can be non-lamellar claies such as kaolin, diatomite, also can be expandable lamellar claies such as imvite, rectorite.In the preferred active carbon of porous inorganic carrier, silica, aluminium oxide or the zeolite one or more.Porous inorganic carrier is the heavy % of 50-80 at the content of composite solid-acid catalyst.
Heteropoly acid general formula of the present invention is H
8-n[AM
12O
40], wherein A is P or Si, and M is W or Mo, and n is the valence state of A, and its value is 4 or 5.General used heteropoly acid is selected from a kind of in phosphotungstic acid, phosphomolybdic acid, silico-tungstic acid or the silicomolybdic acid, preferred phosphotungstic acid.The content of heteropoly acid in composite solid-acid catalyst is the heavy % of 15-48.
Inorganic acid of the present invention is HF or HCl, and the content in composite solid-acid catalyst is the heavy % of 2-6, the heavy % of preferred 2-5.
Composite solid-acid catalyst of the present invention, its acid site type is
Acid, the density in acid site is not less than 1.4 * 10
-3Mole H
+/ gram, than the high order of magnitude of solid-acid material of prior art for preparing, and acid strength distribution homogeneous.
The present invention also provides the preparation method of above-mentioned composite solid-acid catalyst, comprises following steps:
(1) adopt conventional infusion process that heteropoly acid is loaded on the porous inorganic carrier equably, obtain the carried heteropoly acid material, the load capacity of heteropoly acid is the heavy % of 15-50.
(2) with inorganic acid solution in hydrocarbon;
(3) hydrocarbon that contains inorganic acid is contacted with the carried heteropoly acid material, promptly contained the composite solid-acid catalyst of inorganic acid and heteropoly acid simultaneously.
According to method provided by the invention, the conventional infusion process of said employing loads on heteropoly acid on the porous inorganic carrier equably, and concrete steps are:
(A) the porous inorganic carrier particle of a certain amount of porous inorganic carrier powder or moulding was handled 0.5-2.0 hour cool to room temperature under 20-100 ℃ of normal pressure;
(B) under normal pressure with a certain amount of heteropoly acid solution impregnation porous inorganic carrier 0.2-4.0 hour;
(C) under normal pressure and in the inert atmosphere, in 30-200 ℃, preferred 50-150 ℃, dry 10-35 hour, described inert atmosphere refers to not the atmosphere that reacts with heteropoly acid or carrier as nitrogen, just to obtain the carried heteropoly acid material, the load capacity of heteropoly acid is for being generally the heavy % of 15-50, the heavy % of preferred 20-50.
According to method provided by the invention, said hydrocarbon is selected from saturated alkane, cycloalkane, aromatic hydrocarbons or benzinum; Preferably propane, normal butane, iso-butane, pentane, hexane, pentamethylene, cyclohexane, benzene, toluene and dimethylbenzene.
According to method provided by the invention, described inorganic acid is HF or HCl; The load capacity of inorganic acid can and be controlled by the concentration of inorganic acid in hydrocarbon, contact temperature, contact pressure, hydrocarbon stream speed time of contact.As long as reach required load capacity, the present invention does not have special restriction to above-mentioned condition.
According to method provided by the invention, the content maximum of inorganic acid in hydrocarbon can reach the saturated concentration of inorganic acid in hydrocarbon, preferably with H
+Count 20-2000ppm, preferred again 100-1500ppm; After the carried heteropoly acid material contacted, the load capacity of inorganic acid was along with contact conditions is unusual at the heavy % of 2-6, and preferred 2-5 weighs %.
According to method provided by the invention, the hydrocarbon that contains inorganic acid can carry out in general device with contacting of carried heteropoly acid material, as carrying out in fixed bed reactors, moving bed, fluid bed or three-phase slurry bed reactor; When the carried heteropoly acid material is shaped granule, preferably in fixed bed reactors, carry out.Make the hydrocarbon stream that has dissolved inorganic acid cross this shaped granule bed with measuring pump.Said contact temperature is 20-250 ℃, preferred 30-200 ℃; Pressure is 0.05-7.0MPa, preferred 0.1-6.0MPa; The weight space velocity that has carried the hydrocarbon of inorganic acid is 0.1-10h
-1, preferred 1.0-8.0h
-1Be 1-120h time of contact, preferred 4-80h.
When the carried heteropoly acid material was the fine grained powder, preferred intermittently tank reactor made the inertia hydrocarbons that has dissolved inorganic acid contact with this fine grained powder mixing, stirring.
In order to prevent the influence of moisture to the catalyzed by mixed solid acid material, before carrying inorganic acid, can also carry out inert gas to the carried heteropoly acid material handles, promptly under normal pressure, 50-200 ℃ of temperature, make inert gas (as nitrogen) flow through the carried heteropoly acid material under preferred 80-160 ℃, handle 1-50h.
According to method provided by the invention, after preparation is finished, can under the protection of inert gas, composite solid-acid catalyst be drawn off storage.
Using composite solid-acid catalyst to carry out carrying out Preparation of catalysts in the same reactor of catalytic reaction if select for use, after then preparation is finished, do not needing catalyst just drawn off and directly to carry out follow-up catalytic reaction.
Preparation method provided by the invention can make preparation process avoid the influence of external environment, the composite solid-acid catalyst for preparing can directly carry out catalytic reaction, avoid operations such as transfer, storage and transport, thereby can keep high catalytic activity and selectivity.
The present invention also provides the application of a kind of described composite solid-acid catalyst in alkylated reaction, it is characterized in that described composite solid-acid catalyst is made up of the heteropoly acid of the porous inorganic carrier of the heavy % of 50-80 and the load heavy % of 15-48 on it and the inorganic acid of the heavy % of 2-6.In alkylated reaction, adopt this catalyst, compare, under same reaction condition, can access the purpose product of higher yield, reduce accessory substance and generate with the solid acid catalyst that only contains single heteropoly acid of routine.
The specific embodiment
By above elaboration full disclosure the present invention, following example will give further instruction to method provided by the invention, but therefore the present invention is not subjected to any restriction.
Phosphotungstic acid, phosphomolybdic acid, silico-tungstic acid, silicomolybdic acid are for analyzing pure (production of Tianjin fine chemistry Co., Ltd); Silica is that Haiyang Chemical Plant, Qingdao produces; Activated carbon is Beijing brilliance timber mill production; Gama-alumina is the catalyst plant production of Chang Ling, Hunan.
The X-quantitative fluorescence analysis method is the effective ways of constituent content in a kind of quantitative assay solid sample.Measure HF in the catalyzed by mixed solid acid material sample for preparing or the load capacity of HC l with this method, HF load capacity or the HCl load capacity that obtains according to mensuration, and the load capacity of heteropoly acid on carrier then calculates acid site density (the mol H of catalyzed by mixed solid acid material
+/ g).
The acid strength H of catalyzed by mixed solid acid material
oAssay method be: the 0.7g sample is placed in the little glass measuring cup, put into a glass three-necked bottle then, the temperature of sample is controlled by the heating jacket heating glass three-necked bottle that can accurately control temperature, vacuumizes simultaneously, removes the water in the sample fully.Indicator is placed in the indicator drop bottle that is in three-necked bottle central authorities, slowly opens the glass cock on it, and indicator is dropped on the sample, observes change color then, and change in color is determined the acid strength H of sample per sample
oIndicator is to be the corresponding solution of 0.5 heavy % indicator of solvent configuration with dried cyclohexane.
Embodiment 1-6 provides the example of composite solid-acid catalyst and preparation thereof.
Embodiment 1
Take by weighing 14.0 gram phosphotungstic acid (H
3PW
12O
40.22H
2O) be dissolved in the 80.0ml deionized water, be made into phosphotungstic acid aqueous solution.With 37g 20-40 order silica gel SiO
2Put into Salkowski's solution, flooded 1.0 hours, 80 ℃ of dryings 12 hours in baking oven obtain containing 25 heavy %H then
3PW
12O
40Carried heteropoly acid material with 75 heavy % silica gel is designated as 25%HPW/SiO
2
With 10.0 gram 25%HPW/SiO
2Pack in the fixed bed reactors, under normal pressure, allow nitrogen flow through 25%HPW/SiO under 110 ℃
2Bed was handled 5 hours.After finishing dealing with, cool to 136 ℃, the iso-butane that will contain 350ppm HF with measuring pump pumps into fixed bed reactors, and temperature is controlled at 136 ℃, and pressure is 4.5MPa, and iso-butane flows through 25%HPW/SiO
2The weight space velocity of bed is 3.0h
-1, the processing time is 18 hours, purges through high pure nitrogen, under the protection of high pure nitrogen the catalyzed by mixed solid acid material is drawn off.
After measured, the HF load capacity in the catalyzed by mixed solid acid material sample for preparing is 2.58 heavy %, and acid site density is 1.55 * 10
-3Mol H
+/ g, its character sees Table 2.
Embodiment 2
Method according to example 1 changes phosphotungstic acid into silico-tungstic acid, obtains containing 25 heavy %H
4SiW
12O
40Carried heteropoly acid material with 75 heavy % silica gel is designated as 25%HSiW/SiO
2
With 10.0 gram 25%HSiW/SiO
2Pack in the fixed bed reactors, under normal pressure, allow nitrogen flow through 25%HSiW/SiO under 90 ℃
2Bed was handled 22 hours.After finishing dealing with, be warmed up to 190 ℃, the normal butane that will contain 1450ppm HF with measuring pump pumps into fixed bed reactors, and temperature is controlled at 190 ℃, and pressure is 5.5MPa, and normal butane flows through 25%HSiW/SiO
2The weight space velocity of bed is 0.5h
-1, the processing time is 15 hours, purges through high pure nitrogen, under the protection of high pure nitrogen the catalyzed by mixed solid acid material is drawn off.
After measured, the HF load capacity in the catalyzed by mixed solid acid material sample for preparing is 2.78 heavy %, and acid site density is 1.74 * 10
-3Mol H
+/ g, its character sees Table 2.
Embodiment 3
Method according to example 1 changes phosphotungstic acid into phosphomolybdic acid, obtains containing 25 heavy %H
3PMo
12O
40Carried heteropoly acid material with 75 heavy % silica gel is designated as 25%HPMo/SiO
2
With 10.0 gram 25%HPMo/SiO
2Pack in the fixed bed reactors, under normal pressure, allow nitrogen flow through 25%HPMo/SiO under 120 ℃
2Bed was handled 8 hours.After finishing dealing with, cool to 75 ℃, the propane that will contain 650ppm HF with measuring pump pumps into fixed bed reactors, and temperature is controlled at 75 ℃, and pressure is 3.5MPa, and propane stream is crossed 25%HPW/SiO
2The weight space velocity of bed is 7.5h
-1, the processing time is 4 hours, purges through high pure nitrogen, under the protection of high pure nitrogen the catalyzed by mixed solid acid material is drawn off.
After measured, the HF load capacity in the catalyzed by mixed solid acid material sample for preparing is 3.05 heavy %, and acid site density is 1.94 * 10
-3Mol H
+/ g, its character and composition see Table 2.
Embodiment 4
Method according to example 1 changes phosphotungstic acid into silicomolybdic acid, obtains containing 25 heavy %H
4SiMo
12O
40Carried heteropoly acid material with 75 heavy % silica gel is designated as 25%HSiMo/SiO
2
With 10.0 gram 25%HSiMo/SiO
2Pack in the fixed bed reactors, under normal pressure, allow nitrogen flow through 25%HSiMo/SiO under 130 ℃
2Bed was handled 6 hours.After finishing dealing with, cool to 75 ℃, the cyclohexane that will contain 252ppm HCl with measuring pump pumps into fixed bed reactors, and temperature is controlled at 135 ℃, and pressure is 6.5MPa, and cyclohexane flows through 25%HSiMo/SiO
2The weight space velocity of bed is 3.5h
-1, the processing time is 20 hours, purges through high pure nitrogen, under the protection of high pure nitrogen the catalyzed by mixed solid acid material is drawn off.
After measured, the HCl load capacity in the catalyzed by mixed solid acid material sample for preparing is 4.68 heavy %, and acid site density is 1.89 * 10
-3Mol H
+/ g, its character sees Table 2.
Embodiment 5
With 28.4 gram H
3PW
12O
40.21H
2O is dissolved in the 82ml water, is made into phosphotungstic acid aqueous solution.25 gram 20-40 purpose activated carbon are put into bottle,suction, under 0.095Mpa (gauge pressure) vacuum and 85 ℃ of temperature, outgased 1.0 hours.After cooling to room temperature, under condition of normal pressure, add the phosphotungstic acid aqueous solution prepare, the Immesion active carbon carrier is after 3.0 hours, takes out to be placed in the drying box, and 60 ℃ of dryings 10 hours obtain 50 heavy %H
3PW
12O
40The carried heteropoly acid material of/50 heavy % activated carbon is designated as 50%HPW/C.
10.0 gram 50%HPW/C are packed in the fixed bed reactors, under normal pressure, allow nitrogen flow through the 50%HPW/C bed under 110 ℃, handled 10 hours.After finishing dealing with, cool to 75 ℃, the benzene that will contain 156ppm HF with measuring pump pumps into fixed bed reactors, and temperature is controlled at 75 ℃, and pressure is 2.5MPa, and the weight space velocity that benzene flows through the 50%HPW/C bed is 4.5h
-1, the processing time is 36 hours, purges through high pure nitrogen, under the protection of high pure nitrogen the catalyzed by mixed solid acid material is drawn off.
After measured, the HF load capacity in the catalyzed by mixed solid acid material sample for preparing is 4.05 heavy %, and acid site density is 2.55 * 10
-2Mol H
+/ g, its character sees Table 2.
Embodiment 6
With 28.4 gram H
3PW
12O
40.21H
2O is dissolved in the 82ml water, is made into phosphotungstic acid aqueous solution.25 gram 20-40 purpose gama-aluminas are put into bottle,suction, under 0.095Mpa (gauge pressure) vacuum and 85 ℃ of temperature, outgased 1.0 hours.After cooling to room temperature, under condition of normal pressure, add the phosphotungstic acid aqueous solution prepare, the dipping gamma-aluminium oxide carrier takes out after 2.0 hours and is placed in the drying box, and 80 ℃ of dryings 20 hours obtain 50 weight %H
3PW
12O
40Carried heteropoly acid material with 50 heavy % gama-aluminas is designated as 50%HPW/Al
2O
3
With 10.0 gram 50%HPW/Al
2O
3Pack in the fixed bed reactors, under normal pressure, allow nitrogen flow through 50%HPW/Al under 110 ℃
2O
3Bed was handled 10 hours.After finishing dealing with, cool to 25 ℃, the normal butane that will contain 350ppm HF with measuring pump pumps into fixed bed reactors, and temperature is controlled at 25 ℃, and pressure is 0.5MPa, and normal butane flows through 50%HPW/Al
2O
3The weight space velocity of bed is 3.5h
-1, the processing time is 110 hours, purges through high pure nitrogen, under the protection of high pure nitrogen the catalyzed by mixed solid acid material is drawn off.
After measured, the HF load capacity in the catalyzed by mixed solid acid material sample for preparing is 3.94 heavy %, and acid site density is 2.56 * 10
-3Mol H
+/ g, its character sees Table 2.
Comparative Examples 1
Adopting the acid site density of the USY molecular sieve catalyst of prior art for preparing is 0.4 * 10
-3Mol H
+/ g, its character sees Table 2.
Comparative Examples 2
Adopt the 25 heavy %H that contain of embodiment 1 method preparation
3PW
12O
40Carried heteropoly acid material 25%HPW/SiO with 75 heavy % silica gel
2Acid site density be 0.26 * 10
-3Mol H
+/ g, its character sees Table 2.
The composition of table 2 solid-acid material and acid properties
B:
Acid; L is Lewis acid.
The example that embodiment 7 provides composite solid-acid catalyst to use in alkylated reaction.
Embodiment 7
The preparation condition that repeats embodiment 1 obtains composite solid-acid catalyst, but does not draw off from reactor; Carry out (seeing Table 3) under the required temperature and pressure of alkylated reaction at iso-butane and butylene then, with measuring pump iso-butane and butylene are transported to and carry out alkylated reaction in the same reactor.After stable reaction, analyze the composition of product liquid and reaction end gas with gas chromatograph.In the reaction result tabulation 3.
Comparative Examples 3
According to the preparation condition of embodiment 1, at first obtain 25%HPW/SiO
2Again with 10.0 these solid acid catalysts of gram fixed bed reactors of packing into, feed nitrogen, then iso-butane and butylene carry out alkylated reaction required, with embodiment 7 under the identical temperature and pressure (seeing Table 3), with measuring pump iso-butane and butylene are transported to and carry out alkylated reaction in the reactor, stop nitrogen simultaneously.After stable reaction, analyze the composition of product liquid and reaction end gas with gas chromatograph.In the reaction result tabulation 3.
Table 3 alkylated reaction result
TMP: trimethylpentane, DMH: dimethylhexane, RON: research octane number (RON), MON: motor octane number
From the reaction result of table 3 as can be seen, adopt the composite solid-acid catalyst with high acid site density of the present invention's preparation to compare with conventional load type heteropolyacid catalyst, in alkylated reaction, show higher TMP/DMH ratio and high-octane rating, illustrate that the composite solid-acid catalyst of high acid site density has better catalytic activity and reaction selectivity in alkylated reaction.
Claims (19)
1. composite solid-acid catalyst is made up of the heteropoly acid of the porous inorganic carrier of the heavy % of 50-80 and the load heavy % of 15-48 on it and the inorganic acid of the heavy % of 2-6.
2. according to the composite solid-acid catalyst of claim 1, it is characterized in that wherein said porous inorganic carrier is selected from one or more the mixture in silica, aluminium oxide, active carbon, magnesia, titanium oxide, natural or artificial synthetic aluminosilicate zeolite, molecular sieve, carbon fiber and the natural clay.
3. according to the composite solid-acid catalyst of claim 2, it is characterized in that wherein said porous inorganic carrier is selected from one or more in active carbon, silica, aluminium oxide or the zeolite.
4. according to the composite solid-acid catalyst of claim 1, it is characterized in that described heteropoly acid is selected from phosphotungstic acid, phosphomolybdic acid, silico-tungstic acid or silicomolybdic acid.
5. according to the composite solid-acid catalyst of claim 4, it is characterized in that described heteropoly acid is a phosphotungstic acid.
6. according to the composite solid-acid catalyst of claim 1, it is characterized in that described inorganic acid is HF or HCl, its content is the heavy % of 2-5.
7. according to the composite solid-acid catalyst of claim 1, it is characterized in that the acid site type of described composite solid-acid catalyst is
Acid, the density in acid site is not less than 1.4 * 10
-3Mole H
+/ gram.
8. the preparation method of the described composite solid-acid catalyst of claim 1 comprises following steps:
(1) adopt conventional infusion process that heteropoly acid is loaded on the porous inorganic carrier equably, obtain the carried heteropoly acid material, the load capacity of heteropoly acid is the heavy % of 15-50.
(2) with inorganic acid solution in hydrocarbon;
(3) hydrocarbon that contains inorganic acid is contacted with the carried heteropoly acid material, promptly contained the composite solid-acid catalyst of inorganic acid and heteropoly acid simultaneously, the load capacity of inorganic acid is the heavy % of 2-6.
9. the load capacity of heteropoly acid is the heavy % of 20-50 in the method according to Claim 8, step (1).
10. method according to Claim 8 is characterized in that, the said hydrocarbon of step (2) is selected from saturated alkane, cycloalkane, aromatic hydrocarbons or benzinum.
11. the method according to claim 10 is characterized in that, the said hydrocarbon of step (2) is selected from propane, normal butane, iso-butane, pentane, hexane, pentamethylene, cyclohexane, benzene, toluene and dimethylbenzene.
12. method according to Claim 8 is characterized in that, described inorganic acid is HF or HCl, and load capacity is the heavy % of 2-5.
13. method according to Claim 8 is characterized in that, the content of inorganic acid is with H in the hydrocarbon
+Count 20-2000ppm.
14. the method according to claim 13 is characterized in that, the content of inorganic acid is with H in the hydrocarbon
+Count 100-1500ppm.
15. method according to Claim 8, described contact is carried out in fixed bed reactors, moving bed, fluid bed or three-phase slurry bed reactor.
16. according to the method for claim 15, described contact is carried out in fixed bed reactors.
17. according to Claim 8, the method for 15-16, it is characterized in that the condition of described contact is: temperature is 20-250 ℃, and pressure is 0.05-7.0MPa, and the weight space velocity that contains the hydrocarbon of inorganic acid is 0.1-10h
-1, be 1-120h time of contact.
18. the method according to claim 17 is characterized in that, the condition of described contact is: temperature is 30-200 ℃, and pressure is 0.1-6.0MPa, and the weight space velocity that contains the hydrocarbon of inorganic acid is 1.0-8.0h
-1, be 4-80h time of contact.
19. the application of the composite solid-acid catalyst of a claim 1 in alkylated reaction.
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| CN2009102095325A CN102049298A (en) | 2009-10-29 | 2009-10-29 | Composite solid acid catalyst as well as preparation method and application thereof in alkylation reaction |
| US12/915,534 US8309486B2 (en) | 2009-10-29 | 2010-10-29 | Composite solid acid catalyst, preparing process and application in the alkylation |
| EP10189387A EP2324912A1 (en) | 2009-10-29 | 2010-10-29 | A composite solid acid catalyst comprising a heteropoly compound and an inorganic acid on an inorganic porous support, its preparation porcess and use in alkylation reactions |
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