CN101108355A - Method of manufacturing high isomerization active solid super acidic catalyst - Google Patents
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Abstract
The invention relates to a preparation method of a solid super-strong acidic catalyst containing zirconia and sulfate radical. The invention is characterized in that during the preparation process of the catalyst, after hydrothermal treatment, metallic hydroxide is treated by organic alcohol solvent, organic ether solvent or organic alcohol ether solvent. The catalyst prepared by the method of the invention has the advantages of the large specific surface area, the good stability, the good low-temperature and light-weight alkane isomerizate catalyzing activity and selectivity. The mass ratio of alumina and zirconia in the catalyst is 5-40:95-60, the content of valuable metal Pt or Pd is 0.1-5.0%wt, and the sulfur content is 1.0-5.0%wt.
Description
Technical field
The present invention relates to a kind of preparation method of high isomerization active solid super acidic catalyst, particularly a kind of preparation method who comprises the solid super acid catalyst of zirconia and sulfate radical.
Background technology
In recent years, along with the raising of the growing and environmental requirement of motor petrol demand, the gasoline forward is unleaded, low to be polluted, the high-octane rating direction develops.The production of clean gasoline also is the important topic that China faces environmental requirement, and China has had reformation, catalytic cracking, alkylation, methyl tertiary butyl ether(MTBE) manufacturing process such as (MTBE) in clean gasoline producing process at present.According to the concrete condition of China, the olefin(e) centent that reduces in the catalytic gasoline is an important channel, suitably increases the addition of reformation gasoline simultaneously, just can solve gasoline olefin and the higher problem of benzene content substantially, and octane number can meet the demands substantially.But can bring gasoline product density higher to high trade mark gasoline, for reaching the anti-knock index requirement, and cause problems such as research octane number (RON) surplus.An amount of MTBE that adds (U.S. will substep stop the use of MTBE in rise 5 years calendar year 2001) and alkylate oil all are antiknock components, but their addition is subjected to the restriction of the octane number of oxygen content and requirement, therefore the addition of such component is less, and is little to the influence of the olefin(e) centent of gasoline and density.This shows, lack at present a kind of low alkene, low sulfur content, low-density, blending component that road octane is high in China's clean gasoline prescription, the just right this requirement of C5/C6 isomerized oil.The alkane isomerization processing technology has advantages such as expense is low, flexible operation, saving resource as the means that improve octane number, is subjected to people's attention day by day.After the China joined WTO, the international competition that petrochemical industry faces will be fierce more, and therefore exploitation cheapness, environmental friendliness and advanced C5/C6 isomerization catalyst and technology thereof are very important and instant.
SO
4 2-/ ZrO
2(SZ) the type solid super-strong acid has environmentally friendly, advantage such as heat endurance is higher and easy and product is separated, it is the new catalytic material that a class has application potential very much, especially they can activate the c h bond of covalency at a lower temperature, are considered to up-and-coming isomerization catalyst.Yet the SZ catalyst is very fast inactivation in catalytic reaction, and catalytic activity is not very high.A spot of Al adds the alkane isomerization performance that SZ can very well improve catalyst by co-precipitation.The introducing method of aluminium oxide has multiple, and the activity of such catalysts and the stability that make with water-soluble aluminum salt co-precipitation introducing method are not higher.In numerous aluminium oxide introducing methods, higher with boehmite (a kind of hydrated alumina) with the catalyst catalytic performance of hydronium(ion) oxidation zirconium moulding introducing method preparation, and hydronium(ion) oxidation zirconium obtains further to improve the performance of catalyst by the hydrothermal treatment consists method, as: CN 1524616A report.Yet there are no report and obtain high performance Pt-SO for other aluminium oxide introducing method
4 2-/ ZrO
2-Al
2O
3(PSZA) catalyst.
Summary of the invention
The purpose of this invention is to provide a kind of preparation method of new high isomerization active solid super acidic catalyst, a kind of preparation method who comprises the solid super acid catalyst of zirconia and sulfate radical is provided especially.Solid super acid catalyst comprises the mixed-metal oxides of sulfide sulfur acidification, and mixed-metal oxides is made up of zirconia and alumina mixture.This catalyst is applicable to C4～C8 light paraffins isomerization reaction, has high isomerization activity and selectivity.Significant advantage of the present invention is in the Preparation of catalysts process, after hydrothermal treatment consists, adopt organic alcohol, organic ether or organic alcohol ether solvents to handle metal hydroxides, catalyst after treatment has big specific area, catalyst stability is good, have higher low temperature light paraffins isomerization catalytic activity and selectivity, also widened the introducing method of aluminium.The method according to this invention can obtain bigger serface, higher sulfur content and high performance catalyst.
The present invention is achieved by the following scheme:
A kind of preparation method of high isomerization active solid super acidic catalyst is characterized in that, its preparation process comprises the steps:
1, will contain the solution of Zr and contain Al solution or/and colloidal sol mix, making the alumina and zirconia mass ratio is 5-40: 95-60, to wherein adding alkaline precipitating agent, at 85-250 ℃ of following hydrothermal treatment consists 3-100h, the gained gel after filtration, the washing, the gained filter cake uses the mixture that is selected from one or more organic solvents in organic alcohol, organic ketone, organic ether or the organic alcohol ether solvents to soak 1-48h, filtration drying;
Perhaps: the solution that will contain Zr, add alkaline precipitating agent, at 85-250 ℃ of following hydrothermal treatment consists 3-100h, the gained gel washs after filtration, the gained filter cake uses the mixture that is selected from one or more organic solvents in organic alcohol, organic ketone, organic ether or the organic alcohol ether solvents to soak 1-48h, behind the filtration drying, with the aluminium oxide mixed-forming, making the alumina and zirconia mass ratio is 5-40: 95-60;
2, with above-mentioned gained solid impregnating in the aqueous solution of the sulfuric acid of 0.4-1.0mol/l or sulfate; Afterwards, filter the solid of dipping sulfate radical, dry back is at 500-700 ℃ of following roasting 2-10h; At last, the metal oxide impregnated that roasting is obtained the sulfur loaded acid group contains the aqueous solution that one or more contain Pt or Pd, promptly obtains solid super acid catalyst 400-600 ℃ of following roasting behind the filtration drying.
Wherein, the solution of the described Al of containing is or/and the mixture of colloidal sol is meant that the solution of precursor of oxide of Al element is or/and colloidal sol, the solution of Al is or/and colloidal sol can be meta-aluminic acid, aluminum sulfate, aluminum nitrate, various hydrated alumina, the solution of Zr is various inorganic or organic zirconium salting liquids, can be: ZrOCl
2, Zr (NO
3)
4, ethyoxyl zirconium, propoxyl group zirconium, butoxy zirconium etc.;
Described alkaline precipitating agent is the ammonia spirit or the urea aqueous solution, and the pH value is 9-10;
Described organic alcohol, organic ketone, organic ether or organic alcohol ether solvents are selected from alcohol, ketone, ether or the alcohol ether of C1-C8;
Described sulfate is selected from ammonium sulfate or ammonium hydrogen sulfate.
In the above-mentioned steps 1, preferred 12h-100h of the time of hydrothermal treatment consists with an organic solvent handles the preferred 12h-48h of time of gained filter cake;
In the above-mentioned steps 2, the solid of dipping sulfate radical, behind the filtration drying, the preferred 600-650 of sintering temperature ℃, roasting time is 3-5h; The metal oxide impregnated of sulfur loaded acid group is contained one or more be selected from the aqueous solution that contains Pt and Pd, behind the filtration drying, the preferred 450-530 of sintering temperature ℃, roasting time is 2-5h.
The catalyst that said method makes, its specific area are 140-250m
2/ g.The alumina and zirconia mass ratio is 5-40: 95-60 in this catalyst, and precious metal Pt or Pd content are 0.1-5.0%wt, and sulfur content is 1.0-5.0%wt.
The catalyst of method preparation of the present invention has big specific area, and catalyst stability is good, has good low-temperature light paraffins isomerization catalytic activity and selectivity.
The specific embodiment
The invention will be further elaborated below by embodiment, its objective is that the cited case does not limit protection scope of the present invention for better understanding content of the present invention.
Embodiment 1: by ZrOCl
28H
2O and Al (NO
3)
38H
2The O aqueous solution, wherein aluminium oxide and zirconic mass ratio are 5: 95, drip concentrated ammonia liquor in solution, regulate the pH value to pH=9-10,90 ℃ of cyclic washing filtrations behind hydrothermal treatment consists 24h of sediment do not have Cl in filtrate
-Till.The gained filter cake uses methanol solvate to soak 24h and filters, and the gained sediment in 110 ℃ of dry 24h, is used the H of 0.5mol/l
2SO
4Solution impregnation Zr (OH)
4Carrier (every gram ZrO
2Use 15mlH
2SO
4Solution) 24h confides all redundant solution, in 110 ℃ of dry 24h, at 650 ℃ of roasting 3h, promptly obtains SO again
4 2-/ ZrO
2-Al
2O
3Subsequently, with certain density H
2PtCl
6Solution impregnation SO
4 2-/ ZrO
2-Al
2O
3, leave standstill 24h, again in 110 ℃ of dry 24h,, promptly make the Pt-SO of platinum content 0.1% at last at 525 ℃ of roasting 3h
4 2-/ ZrO
2-Al
2O
3(PSZA) catalyst C1.
Embodiment 2 key steps are with embodiment 1, and wherein aluminium oxide and zirconic mass ratio are 10: 90, and used organic solvent is an ethanol, make the PSZA catalyst C2 of platinum content 0.5%.
Embodiment 3 key steps are with embodiment 1, and wherein aluminium oxide and zirconic mass ratio are 40: 60, and used organic solvent is an isopropyl alcohol, make the PSZA catalyst C3 of platinum content 1.0%.
Embodiment 4 key steps are with embodiment 1, and wherein aluminium oxide and zirconic mass ratio are 10: 90, and used organic solvent is an isobutanol, make the PSZA catalyst C4 of platinum content 0.5%.
Embodiment 5 key steps are with embodiment 1, and wherein aluminium oxide and zirconic mass ratio are 10: 90, and used organic solvent is an isooctanol, make the PSZA catalyst C5 of platinum content 0.5%.
Embodiment 6 key steps are with embodiment 1, and wherein aluminium oxide and zirconic mass ratio are 10: 90, and used organic solvent is an ether, make the PSZA catalyst C6 of platinum content 0.5%.
Embodiment 7 key steps are with embodiment 1, and wherein aluminium oxide and zirconic mass ratio are 10: 90, and used organic solvent is a butyl glycol ether, make platinum content PSZA catalyst C7.
Embodiment 8 key steps are with embodiment 1, and wherein aluminium oxide and zirconic mass ratio are 10: 90, and used organic solvent is an ethylene glycol, make the PSZA catalyst C8 of platinum content 0.5%.
Embodiment 9 key steps are with embodiment 1, and wherein aluminium oxide and zirconic mass ratio are 10: 90, and used organic solvent is an acetone, make the PSZA catalyst C9 of platinum content 0.5%.
Embodiment 10 key steps are with embodiment 1, and wherein aluminium oxide and zirconic mass ratio are 10: 90, and used organic solvent is a methyln-hexyl ketone, make the PSZA catalyst C10 of platinum content 0.5%.
The key step of Comparative Examples 1 is with embodiment 1, and wherein aluminium oxide and zirconic mass ratio are 5: 95, but does not with an organic solvent handle, and makes the PSZA comparative catalyst D1 of platinum content 0.1%.
The key step of Comparative Examples 2 is with embodiment 2, and wherein aluminium oxide and zirconic mass ratio are 10: 90, but does not with an organic solvent handle, and makes the PSZA comparative catalyst D2 of platinum content 0.5%.
The key step of Comparative Examples 3 is with embodiment 3, and wherein aluminium oxide and zirconic mass ratio are 40: 60, but does not with an organic solvent handle, and makes the PSZA comparative catalyst D3 of platinum content 1.0%.
Embodiment 11: zirconium nitrate is dissolved in the deionized water, and boehmite added wherein stir 3h, wherein aluminium oxide and zirconic mass ratio are 5: 95, drip the urea aqueous solution to 120 ℃ of cyclic washing filtrations behind hydrothermal treatment consists 24h of pH=9-10 sediment.The gained filter cake uses isopropyl alcohol and 1: 1 (v/v) mixed solvent of ether to soak 24h and filters, and in 110 ℃ of dry 24h, obtains Zr (OH)
4And Al
2O
3Mixture.Then, use the H of 0.5mol/l
2SO
4This mixture of solution impregnation (every gram ZrO
2Use 15mlH
2SO
4Solution) 24h confides all redundant solution, in 110 ℃ of dry 24h, is SO at 650 ℃ of roasting 5h again
4 2-/ ZrO
2-Al
2O
3With certain density H
2PtCl
6Solution impregnation SO
4 2-/ ZrO
2-Al
2O
3, leave standstill 24h, again in 110 ℃ of dry 24h,, promptly make the PSZA catalyst C11 of platinum content 0.5% at last at 500 ℃ of roasting 3h.
Embodiment 12 key steps are with embodiment 11, and wherein aluminium oxide and zirconic mass ratio are 40: 60, and used organic solvent is the diethylene glycol butyl ether, make the PSZA catalyst C12 of platinum content 0.5%.
Embodiment 13 key steps are with embodiment 11, and wherein aluminium oxide and zirconic mass ratio are 10: 90, and used organic solvent is an isooctanol, make the PSZA catalyst C13 of platinum content 0.5%.
Embodiment 14 key steps are with embodiment 11, and wherein aluminium oxide and zirconic mass ratio are 10: 90, and used organic solvent is isopropyl alcohol and isoamyl ether 1: 1 (v/v), make the PSZA catalyst C14 of platinum content 0.5%.
The key step of Comparative Examples 4 is with implementing 11, and wherein aluminium oxide and zirconic mass ratio are 5: 95, but does not with an organic solvent handle, and makes the PSZA comparative catalyst D4 of platinum content 0.5%.
The key step of Comparative Examples 5 is with embodiment 12, and wherein aluminium oxide and zirconic mass ratio are 40: 60, but does not with an organic solvent handle, and makes the PSZA comparative catalyst D5 of platinum content 0.5%.
Embodiment 15: zirconium nitrate is dissolved in the deionized water, drips concentrated ammonia liquor to pH=9-10,110 ℃ of cyclic washing filtrations behind hydrothermal treatment consists 24h of sediment.The gained filter cake uses glycol propyl ether to soak 24h and filters, and filter cake obtains the Zr (OH) that organic solvent is handled in 110 ℃ of dry 48h
4With Zr (OH)
4Same Al
2O
3Mixed-forming, wherein aluminium oxide and zirconic mass ratio are 5: 95,110 ℃ of dry 3h; Then, use the H of 0.5mol/l
2SO
4The dried solid of solution impregnation (every gram ZrO
2Use 15mlH
2SO
4Solution) 24h confides all redundant solution, in 110 ℃ of dry 24h, again at 650 ℃ of roasting 5h; Secondly, the dipping chloroplatinic acid, 110 ℃ of dry 3h at 480 ℃ of following roasting 3h, promptly make the PSZA catalyst C15 of platinum content 0.5%.
Embodiment 16 key steps are with embodiment 15, and wherein aluminium oxide and zirconic mass ratio are 40: 60, and used organic solvent is an octanol, make the PSZA catalyst C16 of platinum content 0.5%.
Embodiment 17 key steps are with embodiment 15, and wherein aluminium oxide and zirconic mass ratio are 10: 90, and used organic solvent is isopropyl alcohol and 1: 1 (v/v) mixed solvent of acetone, make the PSZA catalyst C17 of platinum content 0.5%.
Embodiment 18 key steps are with embodiment 15, and wherein aluminium oxide and zirconic mass ratio are 10: 90, and used organic solvent is 2, and the 3-diacetyl makes the PSZA catalyst C18 of platinum content 0.5%.
Embodiment 19 key steps are with embodiment 15, and wherein aluminium oxide and zirconic mass ratio are 10: 90, and used organic solvent is an isooctanol, make the PSZA catalyst C19 of platinum content 0.5%.
Embodiment 20 key steps are with embodiment 15, and wherein aluminium oxide and zirconic mass ratio are 10: 90, and used organic solvent is an ether, make the PSZA catalyst C20 of platinum content 0.5%.
The key step of Comparative Examples 6 is with embodiment 15, and wherein aluminium oxide and zirconic mass ratio are 5: 95, but does not with an organic solvent handle, and makes the PSZA comparative catalyst D6 of platinum content 0.5%.
The key step of Comparative Examples 7 is with embodiment 16, and wherein aluminium oxide and zirconic mass ratio are 40: 60, but does not with an organic solvent handle, and makes the PSZA comparative catalyst D7 of platinum content 0.5%.
The key step of Comparative Examples 8 is with embodiment 17, and wherein aluminium oxide and zirconic mass ratio are 10: 90, but does not with an organic solvent handle, and makes the PSZA comparative catalyst D8 of platinum content 1%.
The isomerization activity evaluation of solid super acid catalyst the MR-100 type continuously little anti--carry out on the chromatogram arrangement, the GC-920 type gas chromatograph that used chromatogram is produced for the Shanghai Institute of Computing Technology in the experiment, wherein the capillary chromatographic column column length is 60 meters, with OV-101 is fixing phase, nitrogen is as carrier gas, and product is detected by FID hydrogen flame ion detector.Catalyst activates 3h in 450 ℃ of flow air atmosphere before reaction, be cooled to 250 ℃ of reductase 12 h under the nitrogen atmosphere that flows then.Reaction condition is: catalytic amount is 1.0g, WHSV=2h
-1, reaction pressure 2Mpa, n-C6: H
2Mol ratio is 1: 3, and reaction temperature is 170 ℃.The composition of above-mentioned each catalyst and specific area and successive reaction the results are shown in Table 1 after 12 hours.Can find that therefrom catalyst of the present invention has than bigger specific area of conventional method and the sulfur content of Geng Gao, and selection of catalysts is higher.
Table 1:
| The catalyst numbering | S/％ | Pt /％ | Al 2O 3/ZrO 2Mass ratio | Solvent | Specific area m 2/g | Hexane conversion rate/% | Selectivity/% | |
| C1 | 1.91 | 0.1 | 5 | 95 | Methyl alcohol | 177 | 82.6 | 92.4 |
| D1 | 1.44 | 0.1 | 5 | 95 | 143 | 77.7 | 88.4 | |
| C2 | 2.21 | 0.5 | 10 | 90 | Ethanol | 183 | 83.4 | 100 |
| D2 | 1.71 | 0.5 | 10 | 90 | 156 | 63.6 | 92.7 | |
| C3 | 3.27 | 1.0 | 40 | 60 | Isopropyl alcohol | 232 | 84.5 | 100 |
| D3 | 2.55 | 1.0 | 40 | 60 | 193 | 58.8 | 94.9 | |
| C4 | 1.99 | 0.5 | 10 | 90 | Isobutanol | 185 | 84.1 | 100 |
| C5 | 2.07 | 0.5 | 10 | 90 | Isooctanol | 189 | 83.7 | 100 |
| C6 | 2.23 | 0.5 | 10 | 90 | Ether | 183 | 83.5 | 100 |
| C7 | 2.08 | 0.5 | 10 | 90 | Butyl glycol ether | 185 | 84.2 | 100 |
| C8 | 2.02 | 0.5 | 10 | 90 | Ethylene glycol | 181 | 82.7 | 100 |
| C9 | 2.09 | 0.5 | 10 | 90 | Acetone | 188 | 82.2 | 100 |
| C10 | 1.96 | 0.5 | 10 | 90 | Methyln-hexyl ketone | 189 | 83.3 | 100 |
| C11 | 2.17 | 0.5 | 5 | 95 | Isopropyl alcohol and ether | 191 | 82.4 | 100 |
| D4 | 1.51 | 0.5 | 5 | 95 | 147 | 72.7 | 86.1 | |
| C12 | 2.63 | 0.5 | 40 | 60 | The diethylene glycol butyl ether | 230 | 83.3 | 100 |
| D5 | 2.14 | 0.5 | 40 | 60 | 169 | 64.5 | 95.7 | |
| C13 | 2.04 | 0.5 | 10 | 90 | Isooctanol | 193 | 83.7 | 100 |
| C14 | 2.07 | 0.5 | 10 | 90 | Isopropyl alcohol and isoamyl ether | 197 | 82.5 | 100 |
| C15 | 1.89 | 0.5 | 5 | 95 | Glycol propyl ether | 192 | 83.4 | 100 |
| D6 | 1.39 | 0.5 | 5 | 95 | 159 | 74.8. | 90.7 | |
| C16 | 2.79 | 0.5 | 40 | 60 | Octanol | 234 | 82.3 | 100 |
| D7 | 2.11 | 0.5 | 40 | 60 | 174 | 54.7 | 100 | |
| C17 | 2.18 | 0.5 | 10 | 90 | Isopropyl alcohol and acetone | 202 | 84.7 | 100 |
| D8 | 1.56 | 0.5 | 10 | 90 | 166 | 78.4 | 95.3 | |
| C18 | 2.16 | 0.5 | 10 | 90 | 2, the 3-diacetyl | 202 | 84.5 | 100 |
| C19 | 2.11 | 0.5 | 10 | 90 | Isooctanol | 207 | 84.5 | 100 |
| C20 | 2.25 | 0.5 | 10 | 90 | Ether | 203 | 84.1 | 100 |
Embodiment 21: the isomerization activity evaluation of solid super acid catalyst the MR-100 type continuously little anti--carry out on the chromatogram arrangement, the GC-920 type gas chromatograph that used chromatogram is produced for the Shanghai Institute of Computing Technology in the experiment, wherein the capillary chromatographic column column length is 60 meters, with OV-101 is fixing phase, nitrogen is as carrier gas, and product is detected by FID hydrogen flame ion detector.Catalyst C2 activates 3h in 450 ℃ of flow air atmosphere before reaction, be cooled to 250 ℃ of reductase 12 h under the nitrogen atmosphere that flows then.Reaction condition is: catalytic amount is 1.0g, WHSV=2h
-1, reaction pressure 2Mpa, n-C5: H
2Mol ratio is 1: 3, and reaction temperature is 170 ℃.Above-mentioned each catalyst successive reaction the results are shown in Table 2 after 12 hours.
Embodiment 22: experimental provision and reaction condition are with embodiment 21, and catalyst system therefor is catalyst C11.
Embodiment 23: experimental provision and reaction condition are with embodiment 21, and catalyst system therefor is catalyst C17.
Comparative Examples 9～11: adopt above-mentioned experimental provision and reaction condition with embodiment 21, catalyst system therefor is respectively comparative catalyst D2, comparative catalyst D4 and comparative catalyst D8.
Table 2
| The catalyst numbering | S/％ | Pt /％ | Al 2O 3/ZrO 2Mass ratio | Solvent | Specific area m 2/g | Pentane conversion ratio/% | Selectivity/% | |
| C2 | 2.21 | 0.5 | 10 | 90 | Ethanol | 183 | 72.6 | 98.3 |
| C11 | 2.17 | 0.5 | 5 | 95 | Isopropyl alcohol and ether | 191 | 75.5 | 98.2 |
| C17 | 2.18 | 0.5 | 10 | 90 | Isopropyl alcohol and acetone | 202 | 76.8 | 98.0 |
| D2 | 1.71 | 0.5 | 10 | 90 | 156 | 61.5 | 92.5 | |
| D4 | 1.51 | 0.5 | 5 | 95 | 147 | 63.7 | 91.7 | |
| D8 | 1.56 | 0.5 | 10 | 90 | 166 | 66.3 | 94.3 | |
Claims (3)
1. the preparation method of a high isomerization active solid super acidic catalyst is characterized in that, its preparation process comprises the steps:
1), will contain the solution of Zr and contain Al solution or/and colloidal sol mix, making the alumina and zirconia mass ratio is 5-40: 95-60, to wherein adding alkaline precipitating agent, at 85-250 ℃ of following hydrothermal treatment consists 3-100h, the gained gel after filtration, the washing, the gained filter cake uses the mixture that is selected from one or more organic solvents in organic alcohol, organic ketone, organic ether or the organic alcohol ether solvents to soak 1-48h, filtration drying;
Perhaps: the solution that will contain Zr, add alkaline precipitating agent, at 85-250 ℃ of following hydrothermal treatment consists 3-100h, the gained gel washs after filtration, the gained filter cake uses the mixture that is selected from one or more organic solvents in organic alcohol, organic ketone, organic ether or the organic alcohol ether solvents to soak 1-48h, behind the filtration drying, with the aluminium oxide mixed-forming, making the alumina and zirconia mass ratio is 5-40: 95-60;
2), with above-mentioned gained solid impregnating in the aqueous solution of the sulfuric acid of 0.4-1.0mol/l or sulfate; Afterwards, filter the solid of dipping sulfate radical, dry back is at 500-700 ℃ of following roasting 2-10h; At last, the metal oxide impregnated that roasting is obtained the sulfur loaded acid group contains the aqueous solution that one or more contain Pt or Pd, promptly obtains solid super acid catalyst 400-600 ℃ of following roasting behind the filtration drying.
Wherein, the solution of the described Al of containing is or/and colloidal sol is meta-aluminic acid, aluminum sulfate, aluminum nitrate, various hydrated alumina, and the solution that contains Zr is ZrOCl
2, Zr (NO
3)
4, ethyoxyl zirconium, propoxyl group zirconium, butoxy zirconium;
Described alkaline precipitating agent is the ammonia spirit or the urea aqueous solution, and the pH value is 9-10;
Described organic alcohol, organic ketone, organic ether or organic alcohol ether solvents are selected from alcohol, ketone, ether or the alcohol ether of C1-C8;
Described sulfate is selected from ammonium sulfate or ammonium hydrogen sulfate.
2. the preparation method of a kind of high isomerization active solid super acidic catalyst as claimed in claim 1 is characterized in that, in the described step 1, the time of hydrothermal treatment consists is 12h-100h, and the time of with an organic solvent handling the gained filter cake is 12h-48h.
3. the preparation method of a kind of high isomerization active solid super acidic catalyst as claimed in claim 1 is characterized in that, in the described step 2, and the solid of dipping sulfate radical, behind the filtration drying, sintering temperature is 600-650 ℃, roasting time is 3-5h; The metal oxide impregnated of sulfur loaded acid group is contained one or more be selected from the aqueous solution that contains Pt and Pd, behind the filtration drying, sintering temperature is 450-530 ℃, and roasting time is 2-5h.
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| CN1032573C (en) * | 1993-04-23 | 1996-08-21 | 中国石油化工总公司 | Production method for super strong acids in noble metal/ZrO2/SO2-(4) system |
| CN1040846C (en) * | 1993-05-11 | 1998-11-25 | 中国石油化工总公司 | Method for preparation of superstrong acid of carried oxide system |
| CN1234454C (en) * | 2003-02-28 | 2006-01-04 | 中国石油化工股份有限公司 | Solid strong acid catalyst and its preparing method |
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