CN1569335A - Solid acid complex catalyst and its preparing process - Google Patents
Solid acid complex catalyst and its preparing process Download PDFInfo
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Abstract
The invention is a solid acid compound catalyst whose component is: 10-80% sulfuric acid or phosphoric acid, 1-10% fluosulfonic acid resin and oxide of silicon, aluminum, titanium or zirconium; the fluosulfonic acid resin the polymer of perfluoroethylene and sulfonated perfluoroethylene, its average molecular weight is 300-500 thousands, the sulfonating rate is 1-5%. The mol rate of carbon element and fluorin element is 1:2. The catalyst blends the liquid acid and solid acid into a compound evenly, it maintains the nature of the liquid acid and the solid acid, and it has higher acid intensity and acid center quantity, the distribution of the acid center is even, the liquid acid will not be lost in the reaction.
Description
Technical field
The invention relates to a kind of solid acid complex catalyst and preparation method thereof.More specifically, be about a kind of solid acid complex catalyst that constitutes by liquid acid, solid acid and inorganic oxide and preparation method thereof.
Technical background
Sulfuric acid, phosphoric acid, hydrofluoric acid and alchlor etc. are the acid catalysts of industrial extensive use.Process that some are important such as alkylation, esterification, isomerization etc. were all once used these catalyst or were still being used them now.Though these catalyst all have good catalytic activity, but because they all use under homogeneous phase condition, compare with heterogeneous, they exist such as being difficult to realize shortcomings such as continuous production, catalyst are difficult for separating with product with raw material, equipment is perishable on the technology; In these more external important chemical processes, also can produce a large amount of accessory substances.Turn to example with alkyl, traditional handicraft prepares detergent alkylate with sulfuric acid or hydrofluoric acid as catalyst, has serious equipment corrosion and problem of environmental pollution; The old technical process of benzene alkylation with propylene synthesizing iso-propylbenzene uses alchlor to be catalyst, has critical defects such as equipment corrosion, high pollution and operating difficulties; In iso-butane/butene alkylation, outside the problems such as depollution, corrosion, 1 ton of product of every production will by-product 100 kilograms spent acid.In the Beckmann rearrangement of the raw material caprolactam of producing nylon-6,1 ton of caprolactam of every production will 2.3 tons of sulphur ammoniums of by-product or the like.
In order to overcome above-mentioned shortcoming, with the solid acid catalyst focus that to substitute these traditional acidic catalysts are many research work.Commonly used have two kinds of methods: the one, these liquid acid are loaded on the carrier; The 2nd, adopt acidic oxide such as solid acid catalysts such as molecular sieve, amorphous silicon aluminium to substitute liquid acid.But these two kinds of methods all also have some shortcomings: in the last method liquid acid be difficult to immobilized, very easy loss; In one method of back acid site skewness, activated centre few, need higher reaction temperature, therefore need the reaction of strong acid or low temperature, as also being difficult to replace liquid acid in the alkylated reaction of iso-butane butylene at present at some.In fact in the reaction of this class, though the acid strength of solid super-strong acid far above the acid strength of sulfuric acid, solid super-strong acid still can't reach the reactivity of liquid acid as 95% sulfuric acid.This is because liquid acid has more and mobile activated centre is arranged, and the acid site of solid acid is fixed, in case be capped, has just lost activity.
People such as KAZUKI HIRATA exist " Preparation and Characterization of HighlyProton-Conductive Composites Composed of Phosphoric Acid-Doped SilicaGel and Styrene-Ethylene-Butylene-Styrene Elastomer " (Journal ofSol-Gel Science and Tecnology 17,61-69,2000) disclose in the literary composition a kind of shown in its article title the preparation of compositions method, be with Si (OEt)
4, ethanol, water, hydrochloric acid and [(C
2H
5)
4N] BF
4At room temperature mix, stir and add phosphoric acid and make colloidal sol, under 60-80 ℃ of vacuum, just obtained the silica dioxide gel of phosphoric acid coating then in dry 8 hours, this gel adds the SEBS rubber that is dissolved in the toluene after 25-250 ℃ of heat treatment, thereby forms r c phosphoric acid/silicon dioxide compositions.Wherein used SEBS rubber accounts for the 5-20 weight % of final products composition, is the EVA of styrene-ethylene-butylene-styrene, and its mean molecule quantity is 150,000, and wherein styrene-content is 15 weight %.Said composition has very high current potential as solid electrolyte, can be used in the electrochemical appliance, for example double layer capacitor, fuel cell, chargeable solid electrolyte battery.
Summary of the invention
The objective of the invention is on the basis of above-mentioned prior art, at problem to be solved, a kind of novel solid acid complex catalyst that has liquid acid and solid acid advantage concurrently is provided, the preparation method of this solid acid complex catalyst is provided simultaneously.
Solid acid complex catalyst provided by the invention has following weight and forms: the sulfuric acid of 10-80% or phosphoric acid, the oxide that is selected from one of silicon, aluminium, titanium or zirconium of the perfluorinated sulfonic resin of 1-10% and surplus; Wherein said perfluorinated sulfonic resin is the EVA of perfluoroethylene and perfluor sulfonated ethylene, and its mean molecule quantity is 30-50 ten thousand, and its sulfonation degree is 1-5%, and the mol ratio of its carbon and fluorine element is 1: 2.
The preparation method of above-mentioned solid acid complex catalyst provided by the invention is: will be selected from silicon, aluminium, the precursor of the oxide of one of titanium or zirconium and alcohol or saliferous aqueous acid are according to oxide: alcohol=1: weight ratio (0.1-4.0) or oxide: hydrochloric acid: water=1: (0.01-4): weight ratio (0.1-4.0) mixes makes solution, again according to oxide: sulfuric acid or phosphoric acid: perfluorinated sulfonic resin=1: (0.1-4.0): weight ratio (0.1-2.0) adds sulfuric acid or the concentration that concentration is 5-98% in above-mentioned solution be the phosphoric acid of 5-85%, and concentration is the alcoholic solution of the perfluorinated sulfonic resin of 5-10%, under 10-90 ℃, be stirred to the generation gel, gel at 50-100 ℃ of following vacuum drying 1-48 hour, or was promptly got solid acid complex catalyst provided by the invention in constant pressure and dry 10-60 hour.The catalyst that makes should be preserved in drier.
The precursor of the oxide of said silicon is the carboxylate of silicon or the colloidal sol of silica among the preparation method of the present invention, preferably methyl orthosilicate, ethyl orthosilicate, orthosilicic acid propyl ester, orthosilicic acid butyl ester, waterglass, Ludox; The precursor of the oxide of said aluminium is an aluminium colloidal sol; The precursor of said titanyl compound is the carboxylate of titanium, preferably metatitanic acid methyl esters, tetraethyl titanate, titanium propanolate, butyl titanate; The precursor of the oxide of said zirconium is the carboxylate of zirconium, preferably zirconic acid methyl esters, zirconic acid ethyl ester, zirconic acid propyl ester, tetrabutyl zirconate.
The alcohol that the said precursor that is used for the oxide of silicon, aluminium, titanium, zirconium forms solution among the preparation method of the present invention is C
1-C
10Saturated hydrocarbons alcohol, as methyl alcohol, ethanol, propyl alcohol or isopropyl alcohol, butanols etc.; Be used for to be selected from the C identical or different with the former with the alcohol of perfluorinated sulfonic resin formation alcoholic solution
1-C
10Saturated hydrocarbons alcohol.
Solid acid complex catalyst provided by the invention is organic with liquid acid and solid acid, be combined in the same compound equably, not only kept the original character of liquid acid, and perfluorinated sulfonic resin is except that self providing certain acid site, fluorin radical can also induce that H dissociates in the adjacent group, thereby make complex catalyst have higher acid strength and acid site number, and the acid site is evenly distributed, liquid acid can not run off in reaction, be applicable to that nonpolar reaction medium, reaction temperature are lower than 150 ℃ reaction, liquid acid catalysts such as desirable thiosulfuric acid.
The preparation method of solid acid complex catalyst provided by the invention is simple and easy to do, synthesizes the carrier and the active component of catalyst simultaneously, so both is uniformly dispersed mutually between each component, organically combines closely again.
The specific embodiment
The following examples will illustrate further to complex catalyst provided by the invention and preparation method thereof, but not thereby limiting the invention.
The acid strength of sample is measured with the Hammett indicator method in embodiment and the Comparative Examples; The surface acid amount goes up at DuPont Instruments 951 thermogravimetric analyzers (U.S.'s product) with the ammonia absorption method and measures; The total acid content determination of acid-basetitration.
Used perfluorinated sulfonic resin alcoholic solution is that (particle mean size (2mm) is dissolved in to be made in the alcoholic solution for du pont company product, trade mark NR50 by perfluorinated sulfonic resin among the embodiment.Concentration is that the concrete preparation method of 5% resinol solution is as follows: 1: 1 propyl alcohol of 95 grams-aqueous solution is added in the autoclave, add 5 gram perfluorinated sulfonic acid resins again, after the autoclave sealing, use N
2Air displacement is wherein come out, be warming up to 240 ℃, under this temperature, stirred 4 hours, can use after the cooling.
The reactivity worth of sample is that alkyl with iso-butane-butylene turns to model reaction and estimates in embodiment and the Comparative Examples.Be reflected on the fixed bed reactors and carry out, this reaction system comprises feeding part, reactive moieties, gas-liquid separation part and analysis part, and the each several part brief introduction is as follows:
Feeding part: feed pump is that Japanese exact science Co., Ltd. produces SP-D2505 trace feed pump, and reactant enters before the reactor earlier by the molecular sieve drying pipe, and reactant is dewatered to the 20ppm.
Reactive moieties: comprise reactor and accurate pressure control, temperature regulating device.The reactor loading amount is 10ml, and control section can be controlled at reacting system pressure ± and 0.01MPa, temperature be controlled at ± and 0.1 ℃.
Separating part: reacted material separates with the low pressure separator of product through a 0.1MPa, and product is collected by the outlet of separator again and analyzes, and tail gas is separated the back sample analysis.
Analysis part: fluid product is analyzed by HP5890 type chromatograph, and chromatographic column is the long OV-01 of 50m; Tail gas is analyzed by HP5880 type chromatograph, and chromatographic column is that refinery gas is analyzed special product.
The alkylation catalytic activity of reaction condition: embodiment is all at 1MPa, 15 ℃, air speed 3h
-1, material alkane alkene weight ratio 25 condition under estimate.The reaction condition of Comparative Examples is seen an example respectively.
Comparative Examples 1
The explanation of this Comparative Examples is the situation that catalyst carries out alkylated reaction with the concentrated sulfuric acid.
With 5 gram concentration is in the sulfuric acid adding reactor of 98wt%, with the reactor good seal, feed 30 gram alkane alkene weight ratios again and be iso-butane-butene mixture of 25, charging into nitrogen makes the still internal pressure reach 0.7MPa, reacted 2 hours, reacted effluent separates through the low pressure separator of 0.1MPa, and isolated product and tail gas are taken a sample respectively, analyzed.Reaction result sees Table 1.
Table 1
| Olefin conversion, weight % | ?????????C 5 +Product is formed, weight % | ???TMP *Content weight % | ||
| ????C 7Below | ????C 8 | ??C 9More than | ||
| 100％ | ????13.40 | ????73.39 | ??13.21 | ???46.42 |
*TMP is a trimethylpentane
Comparative Examples 2
The explanation of this Comparative Examples is the situation that catalyst carries out alkylated reaction with the solid super-strong acid.
Press document Solid Catalyst Treated with Anion (Applied Catalysis, V59,1990,205-212) make solid super-strong acid SO
4 2-/ ZrO
2Catalyst.Record this catalyst acid intensity H
0＜-14.6, the surface acid amount is 0.032mmol/g.Estimate its alkylation activity in the fixed bed reaction system, reaction temperature is 30 ℃, and pressure is 1.5MPa, and material alkane alkene ratio is 30, and the charging air speed is 2h
-1, react 8 hours the results are shown in Table 2.
Table 2
| Olefin conversion, weight % | ?????????????C 5 +Product is formed, weight % | TMP content weight % | ||
| ????C 7Below | ????C 8 | ??C 9More than | ||
| 41％ | ????13.40 | ????40.44 | ??46.16 | ??20.38 |
Comparative Examples 3
The explanation of this Comparative Examples is the situation that catalyst carries out alkylated reaction with the carried heteropoly acid.
Preparation carried heteropoly acid HPW/SiO
2, concrete grammar is as follows: 3.3g phosphotungstic acid (brief note is HPW, and Beijing Chemical Plant's product is analyzed pure) is dissolved in the 30ml water, adds 10g20-40 order SiO
2(gross porosity, specific area are 488m
2/ g, Haiyang Chemical Plant, Qingdao's product), stir evaporate to dryness at dipping in 60 ℃ of water-baths after 2 hours, make the HPW appendix at SiO
2On, and then 100 ℃ of dryings 4 hours promptly make heteropoly acid HPW load capacity and are 25% catalyst.
The above-mentioned catalyst that makes after 2 hours, records its acid strength H through 175 ℃ of processing
0Reach-13.75, the surface acid amount is 0.23mmol/g.Estimate its alkylation activity in the fixed bed reaction system, reaction temperature is 30 ℃, and pressure is 1.5MPa, and material alkane alkene ratio is 30, and the charging air speed is 2h
-1, react 8 hours the results are shown in Table 3.
Table 3
| Olefin conversion, weight % | ???????????C 5 +Product is formed, weight % | TMP content, weight % | ||
| ????C 7Below | ????C 8 | ??C 9More than | ||
| 60.3％ | ????13.60 | ????48.13 | ??38.27 | ??20.25 |
Comparative Examples 4
The explanation of this Comparative Examples is the situation that catalyst carries out alkylated reaction with the sulfuric acid of silica gel load.
According to the method described in document Applied Catalysis A:General 180 (1999) 359-366 barium white is loaded on the silica gel.This solid acid acid strength H that records
0＜-12, the surface acid amount is 2.7mmol/g.Estimate its alkylation activity in the fixed bed reaction system, reaction temperature is 30 ℃, and pressure is 1.5MPa, and material alkane alkene ratio is 30, and the charging air speed is 2h
-1, react 8 hours the results are shown in Table 4.
The load capacity of sulfuric acid is 10 weight % on the silica gel that records before the reaction, reacts the only surplus 2 weight % of the load capacity that records after 8 hours, has run off 80%.
Table 4
| Olefin conversion, weight % | ?????????C 5 +Product is formed, weight % | TMP content weight % | ||
| ????C 7Below | ????C 8 | ????C 9More than | ||
| 100％ | ????8.63 | ????61.52 | ????29.83 | ??27.26 |
Comparative Examples 5
The situation of alkylated reaction is only carried out in the explanation of this Comparative Examples by the oxide catalyst that constitute, that do not contain perfluorinated sulfonic resin of sulfuric acid and silicon.
.1 gram ethanol (Beijing Chemical Plant's product is analyzed pure) and 5 gram water are mixed in the 100ml beaker respectively with a) with 20 gram ethyl orthosilicates (Beijing chemical reagents corporation product is analyzed pure); B) .5 gram water and 6 gram concentration are the hydrochloric acid of 0.04M, are mixed in the 100ml beaker.
After being stirred to the solution clarification, again the 0.5 gram concentrated sulfuric acid is added in the above-mentioned mixed solution rapidly, be stirred to the formation gel under the room temperature, put into vacuum drying oven together with beaker, be 50 ℃ of dry processing 48 hours under the condition of 10mmHg in vacuum, then it preserved in drier.
Record the acid strength H that dual mode makes sample respectively
0Be-12, the surface acid amount is 0.3mmol/g.Estimate its alkylation activity in the fixed bed reaction system, reaction temperature is 30 ℃, and pressure is 1.5MPa, and material alkane alkene ratio is 30, and the charging air speed is 2h
-1, react 8 hours the results are shown in Table 5.
This numerical value all drops to 0.2 weight % after recording total acid content that dual mode makes sample before the reaction respectively and being 1 weight %, reaction.
Table 5
| Preparation method | Olefin conversion weight % | ???????????C 5 +Product is formed, weight % | TMP content weight % | ||
| ????C 7Below | ????C 8 | ????C 9More than | |||
| a | ??100％ | ????13.40 | ????72.92 | ????13.68 | ??25.37 |
| b | ??100％ | ????12.89 | ????73.74 | ????13.37 | ??24.54 |
Example 1-6
These examples illustrate the preparation and the catalytic performance thereof of liquid acid-perfluorinated sulfonic resin provided by the invention-silica solid acid complex catalyst.
Ortho-silicate and alcohol are mixed in the beaker, and being stirred to after the solution clarification sulfuric acid or phosphoric acid and a certain amount of content is that the perfluorinated sulfonic resin alcoholic solution of 5 weight % adds in the above-mentioned mixed solution, is stirred to the generation gel at a certain temperature.The gel that forms being told, put into vacuum drying oven, is 50 ℃ of dry processing 48 hours under the condition of 10mmHg in vacuum, promptly obtains silica-based solid acid complex catalyst provided by the invention, and it is preserved in drier.The concrete operations condition of each example sees Table 6.
Each example make sample acid strength, surface acid amount, 8 hours forward and backward total acid content measurement results of alkylation evaluation response see Table 7 in the fixed bed reaction system.
Each example makes sample in the fixed bed reaction system, and 8 hours reaction result sees Table 8.
Table 6
| Example | Ortho-silicate | The alcohol medium | Liquid acid | Resin demand, g | Become the glue temperature, ℃ | ||||
| Kind | Consumption, g | Kind | Consumption, g | Kind | Concentration, % | Consumption, g | |||
| ??1 | Ethyl ester | ??100 | Ethanol | ??50 | Sulfuric acid | ??98 | 15 | ??1.5 | ??20 |
| ??2 | Ethyl ester | ??10 | Propyl alcohol | ??3 | Phosphoric acid | ??10 | 6 | ??2.0 | ??20 |
| ??3 | Propyl ester | ??20 | Propyl alcohol | ??40 | Sulfuric acid | ??98 | 2 | ??0.2 | ??40 |
| ??4 | Ethyl ester | ??100 | N-heptanol | ??100 | Sulfuric acid | ??50 | 50 | ??10.0 | ??50 |
| ??5 | Ethyl ester | ??10 | N-butanol | ??2 | Sulfuric acid | ??25 | 6 | ??0.6 | ??20 |
| ??6 | Ethyl ester | ??30 | N-butanol | ??5 | Phosphoric acid | ??70 | 13 | ??1.3 | ??20 |
Table 7
| Example | Acid strength H 0 | Surface acid amount mmol/g | Total acid content weight % before the reaction | Reaction back total acid content weight % |
| ????1 | ????-12 | ????3 | ??50 | ??50 |
| ????2 | ????＜-10 | ????3 | ??5 | ??5 |
| ????3 | ????＜-12 | ????5.1 | ??10 | ??10 |
| ????4 | ????＜-12 | ????5.1 | ??60 | ??60 |
| ????5 | ????＜-12 | ????5.1 | ??35 | ??35 |
| ????6 | ????＜-12 | ????5.1 | ??45 | ??45 |
Table 8
| Example | Olefin conversion, weight % | ????????????C 5 +Product is formed, weight % | TMP content weight % | ||
| ????C 7Below | ????C 8 | ????C 9More than | |||
| ????1 | ????100％ | ????15.33 | ????55.42 | ????29.25 | ????29.47 |
| ????2 | ????100％ | ????14.16 | ????56.42 | ????29.42 | ????30.35 |
| ????3 | ????100％ | ????10.45 | ????62.27 | ????27.28 | ????37.36 |
| ????4 | ????100％ | ????11.58 | ????70.99 | ????17.43 | ????40.33 |
| ????5 | ????100％ | ????16.85 | ????71.49 | ????12.66 | ????46.25 |
| ????6 | ????100％ | ????14.17 | ????70.26 | ????15.57 | ????43.17 |
Embodiment 7-9
These examples illustrate the preparation and the catalytic performance thereof of sulfuric acid-perfluorinated sulfonic resin provided by the invention-titanium dioxide solid acid complex catalyst.
Titanate esters and alcohol are mixed in the 100ml beaker, aqueous sulfuric acid is added in the above-mentioned mixed solution rapidly, being stirred to a certain amount of content of solution clarification back adding is the perfluorinated sulfonic resin alcoholic solution of 5 weight %, is stirred to the generation gel at a certain temperature.Gel is put into vacuum drying oven, is 50 ℃ of dry processing 48 hours under the condition of 10mmHg in vacuum, promptly obtains titanium based solid acid complex catalyst provided by the invention, and it is preserved in drier.The concrete operations condition of each example sees Table 9.
Each example make sample acid strength, surface acid amount, 8 hours forward and backward total acid content measurement results of alkylation evaluation response see Table 10 in the fixed bed reaction system.
Each example makes sample in the fixed bed reaction system, and 8 hours reaction result sees Table 11.
Table 9
| Example | Titanate esters | The alcohol medium | Sulfuric acid | Resin demand, g | Become the glue temperature, ℃ | |||
| Kind | Consumption, g | Kind | Consumption, g | Concentration, % | Consumption, g | |||
| ??7 | Ethyl ester | 10 | Ethanol | 2 | ??40 | ??8 | ????0.8 | ??50 |
| ??8 | Methyl esters | 10 | Butanols | 10 | ??50 | ??20 | ????2.0 | ??30 |
| ??9 | Propyl ester | 10 | Ethanol | 20 | ??10 | ??6.5 | ????0.6 | ??80 |
Table 10
| Example | Acid strength H 0 | Surface acid amount mmol/g | Total acid content weight % before the reaction | Reaction back total acid content weight % |
| ????7 | ????＜-12 | ????5.1 | ??33 | ??33 |
| ????8 | ????＜-12 | ????5.0 | ??70 | ??70 |
| ????9 | ????＜-12 | ????5.1 | ??30 | ??30 |
Table 11
| Example | Olefin conversion, weight % | ????????????C 5 +Product is formed, weight % | TMP content weight % | ||
| ????C 7Below | ????C 8 | ??C 9More than | |||
| ????7 | ??100％ | ????16.70 | ????70.33 | ??12.97 | ??40.16 |
| ????8 | ??100％ | ????15.36 | ????65.27 | ??19.37 | ??36.12 |
| ????9 | ??100％ | ????14.15 | ????73.29 | ??12.56 | ??46.50 |
Embodiment 10-11
These examples illustrate the preparation and the catalytic performance thereof of sulfuric acid-perfluorinated sulfonic resin provided by the invention-ZrO 2 solid acid complex catalyst.
Zirconate and alcohol are mixed in the 100ml beaker, and being stirred to after the solution clarification sulfuric acid and a certain amount of content is that the perfluorinated sulfonic resin alcoholic solution of 5 weight % adds in the above-mentioned mixed solution, is stirred to the generation gel at a certain temperature.Gel is put into vacuum drying oven, is 50 ℃ of dry processing 30 hours under the condition of 10mmHg in vacuum, promptly obtains Zirconium-base solid acid complex catalyst provided by the invention, and it is preserved in drier.The concrete operations condition of each example sees Table 12.
Each example make sample acid strength, surface acid amount, 8 hours forward and backward total acid content measurement results of alkylation evaluation response see Table 13 in the fixed bed reaction system.
Each example makes sample in the fixed bed reaction system, and 8 hours reaction result sees Table 14.
Table 12
| Example | Zirconate | The alcohol medium | Sulfuric acid | Resin demand, g | Become the glue temperature, ℃ | |||
| Kind | Consumption, g | Kind | Consumption, g | Concentration, % | Consumption, g | |||
| 10 | Propyl ester | 10 | Propyl alcohol | 10 | ??98 | 5 | ??0.3 | ??20 |
| 11 | Ethyl ester | 10 | Methyl alcohol | 2 | ??30 | 3 | ??0.3 | ??60 |
Table 13
| Example | Acid strength H 0 | Surface acid amount mmol/g | Total acid content weight % before the reaction | Reaction back total acid content weight % |
| ????10 | ????＜-12 | ??5.1 | ??50 | ??50 |
| ????11 | ????＜-12 | ??5.1 | ??10 | ??10 |
Table 14
| Example | Olefin conversion, weight % | ????????????C 5 +Product is formed, weight % | TMP content weight % | ||
| ??C 7Below | ????C 8 | ??C 9More than | |||
| ????10 | ??100％ | ??12.35 | ????71.98 | ??15.67 | ??46.55 |
| ????11 | ??100％ | ??9.61 | ????75.20 | ??15.19 | ??43.50 |
Embodiment 12-16
These examples illustrate the preparation and the catalytic performance thereof of liquid acid-perfluorinated sulfonic resin provided by the invention-silica solid acid complex catalyst.
With ortho-silicate and water, concentration is that the mixed in hydrochloric acid of 0.04M is in beaker, being stirred to after the solution clarification sulfuric acid or phosphoric acid and a certain amount of content is that the perfluorinated sulfonic resin alcoholic solution of 5 weight % adds in the above-mentioned mixed solution, is stirred to the generation gel at a certain temperature.The gel that forms being told, put into vacuum drying oven, is 50 ℃ of dry processing 48 hours under the condition of 10mmHg in vacuum, promptly obtains silica-based solid acid complex catalyst provided by the invention, and it is preserved in drier.The concrete operations condition of each example sees Table 15.
Each example make sample acid strength, surface acid amount, 8 hours forward and backward total acid content measurement results of alkylation evaluation response see Table 16 in the fixed bed reaction system.
Each example makes sample in the fixed bed reaction system, and 8 hours reaction result sees Table 17.
Table 15
| Example | Ortho-silicate | Medium | Liquid acid | Resin demand, g | Become the glue temperature, ℃ | ||||
| Kind | Consumption, g | Water, g | Hydrochloric acid, g | Kind | Concentration, % | Consumption, g | |||
| ??12 | Ethyl ester | ?100 | ??50 | ?30 | Sulfuric acid | ??98 | ?15 | ??1.5 | ??20 |
| ??13 | Methyl esters | ?10 | ??10 | ?6 | Sulfuric acid | ??98 | ?2 | ??0.2 | ??40 |
| ??14 | Ethyl ester | ?100 | ??100 | ?6 | Sulfuric acid | ??50 | ?50 | ??10.0 | ??50 |
| ??15 | Ethyl ester | ?10 | ??2 | ?3 | Sulfuric acid | ??25 | ?6 | ??0.6 | ??20 |
| ??16 | Ethyl ester | ?20 | ??10 | ?6 | Phosphoric acid | ??70 | ?13 | ??1.3 | ??20 |
Table 16
| Example | Acid strength H 0 | Surface acid amount mmol/g | Total acid content weight % before the reaction | Reaction back total acid content weight % |
| ????12 | ????-12 | ??3 | ??50 | ??50 |
| ????13 | ????＜-12 | ??5.1 | ??10 | ??10 |
| ????14 | ????＜-12 | ??5.1 | ??60 | ??60 |
| ????15 | ????＜-12 | ??5.1 | ??35 | ??35 |
| ????16 | ????＜-12 | ??5.1 | ??45 | ??45 |
Table 17
| Example | Olefin conversion, weight % | ?????????????C 5 +Product is formed, weight % | TMP content weight % | ||
| ????C 7Below | ????C 8 | ????C 9More than | |||
| ????12 | ??100％ | ????15.45 | ????61.29 | ????23.26 | ????31.52 |
| ????13 | ??100％ | ????10.34 | ????68.17 | ????21.49 | ????39.23 |
| ????14 | ??100％ | ????10.61 | ????74.82 | ????14.57 | ????48.54 |
| ????15 | ??100％ | ????15.73 | ????72.89 | ????11.38 | ????46.25 |
| ????16 | ??100％ | ????12.71 | ????73.54 | ????13.75 | ????46.22 |
Embodiment 17-18
These examples illustrate the preparation and the catalytic performance thereof of sulfuric acid-perfluorinated sulfonic resin provided by the invention-titanium dioxide solid acid complex catalyst.
With titanate esters and water, concentration is that the mixed in hydrochloric acid of 0.04M is in the 100ml beaker, add aqueous sulfuric acid in the above-mentioned mixed solution rapidly, being stirred to a certain amount of content of solution clarification back adding is the perfluorinated sulfonic resin alcoholic solution of 5 weight %, is stirred to the generation gel at a certain temperature.Gel is put into vacuum drying oven, is 50 ℃ of dry processing 48 hours under the condition of 10mmHg in vacuum, promptly obtains titanium based solid acid complex catalyst provided by the invention, and it is preserved in drier.The concrete operations condition of each example sees Table 18.
Each example make sample acid strength, surface acid amount, 8 hours forward and backward total acid content measurement results of alkylation evaluation response see Table 19 in the fixed bed reaction system.
Each example makes sample in the fixed bed reaction system, and 8 hours reaction result sees Table 20.
Table 18
| Example | Titanate esters | Medium | Sulfuric acid | Resin demand, g | Become the glue temperature, ℃ | |||
| Kind | Consumption, g | Water, g | Hydrochloric acid, g | Concentration, % | Consumption, g | |||
| 17 | Ethyl ester | ?10 | ??2 | ?6 | ??40 | ?8 | ??0.8 | ??50 |
| 18 | Methyl esters | ?10 | ??10 | ?6 | ??50 | ?20 | ??2.0 | ??30 |
Table 19
| Example | Acid strength H 0 | Surface acid amount mmol/g | Total acid content weight % before the reaction | Reaction back total acid content weight % |
| ????17 | ??＜-12 | ??5.1 | ??33 | ??33 |
| ????18 | ??＜-12 | ??5.0 | ??70 | ??70 |
Table 20
| Example | Olefin conversion, weight % | ????????????C 5 +Product is formed, weight % | TMP content weight % | ||
| ????C 7Below | ????C 8 | ??C 9More than | |||
| ????17 | ??100％ | ????16.33 | ????71.21 | ??12.46 | ????40.39 |
| ????18 | ??100％ | ????15.31 | ????70.45 | ??14.24 | ????40.12 |
Embodiment 19
Present embodiment is in order to investigate the stability of catalyst provided by the invention in nonaqueous solvents.
Accurately take by weighing 5 sulfuric acid contents that make of gram embodiment 10 and 12 respectively and be 50% solid acid complex catalyst sample, place tool plug triangular flask, add 30 milliliter isopentane again, 30 ℃ were stirred 24 hours, leave standstill 1 hour after, accurately pipette 10 milliliters of supernatant liquors, add 10 ml deionized water, stir, extract after 30 minutes, detect institute's acid content in the water with acid-base titration, testing result shows, does not contain acid in the water; Wherein solid acid accurately takes by weighing 3 grams 50 ℃ of oven dry 5 hours, and with wherein acid amount of determination of acid-basetitration, the result shows that institute's sulfur acid acid amount does not become.
Claims (9)
1, a kind of solid acid complex catalyst is characterized in that having following weight and forms: the sulfuric acid of 10-80% or phosphoric acid, the oxide that is selected from one of silicon, aluminium, titanium or zirconium of the perfluorinated sulfonic resin of 1-10% and surplus; Wherein said perfluorinated sulfonic resin is the EVA of perfluoroethylene and perfluor sulfonated ethylene, and its mean molecule quantity is 30-50 ten thousand, and its sulfonation degree is 1-5%, and the mol ratio of its carbon and fluorine element is 1: 2.
2, claim 1 Preparation of catalysts method, it is characterized in that to be selected from silicon, aluminium, the precursor of the oxide of one of titanium or zirconium and alcohol or saliferous aqueous acid are according to oxide: alcohol=1: weight ratio (0.1-4.0) or oxide: hydrochloric acid: water=1: (0.01-4): weight ratio (0.1-4.0) mixes makes solution, again according to oxide: sulfuric acid or phosphoric acid: perfluorinated sulfonic resin=1: (0.1-4.0): weight ratio (0.1-2.0) adds sulfuric acid or phosphoric acid in above-mentioned solution, and the alcoholic solution of perfluorinated sulfonic resin, be stirred to the generation gel, with the gained gel drying.
3, according to the method for claim 2, it is characterized in that used sulfuric acid concentration is 5-98%, phosphoric acid concentration is 5-85%.
4, according to the method for claim 2, the alcoholic solution concentration that it is characterized in that used perfluorinated sulfonic resin is 5-10%.
5,, it is characterized in that the said glue that stirs into carries out under 10-90 ℃ according to the method for claim 2.
6,, it is characterized in that said gel drying condition is 50-100 ℃ of following vacuum drying 1-48 hour or constant pressure and dry 10-60 hour according to the method for claim 2.
7, according to the method for claim 2, the precursor that it is characterized in that the oxide of said silicon is the carboxylate of silicon or the colloidal sol of silica; The precursor of the oxide of aluminium is an aluminium colloidal sol; The precursor of titanyl compound is the carboxylate of titanium; The precursor of the oxide of zirconium is the carboxylate of zirconium.
8,, it is characterized in that the precursor of the oxide of said silicon is selected from methyl orthosilicate, ethyl orthosilicate, orthosilicic acid propyl ester, orthosilicic acid butyl ester, waterglass, Ludox according to the method for claim 7; The carboxylate of titanium is selected from metatitanic acid methyl esters, tetraethyl titanate, titanium propanolate, butyl titanate; The carboxylate of zirconium is selected from zirconic acid methyl esters, zirconic acid ethyl ester, zirconic acid propyl ester, tetrabutyl zirconate.
9,, it is characterized in that the alcohol that the said precursor that is used for the oxide of silicon, aluminium, titanium, zirconium forms solution is C according to the method for claim 2
1-C
10Saturated hydrocarbons alcohol; Be used for being selected from the C identical or different with the former with the alcohol of perfluorinated sulfonic resin formation alcoholic solution
1-C
10Saturated hydrocarbons alcohol.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101717321A (en) * | 2009-12-10 | 2010-06-02 | 复旦大学 | Method for catalyzing iso-butane/n-butene alkylation by solid acid |
| CN107282140A (en) * | 2016-03-31 | 2017-10-24 | 华东理工大学 | A kind of perfluorinated sulfonic resin/PES/TiO2-ZrO2The preparation method of solid acid doughnut catalyst filling |
| CN113880712A (en) * | 2021-09-16 | 2022-01-04 | 泰兴金江化学工业有限公司 | Preparation method of ethyl acetate |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05255176A (en) * | 1992-03-11 | 1993-10-05 | Toagosei Chem Ind Co Ltd | Production of monochloroacetic acid |
| CN1142027C (en) * | 2001-05-30 | 2004-03-17 | 中国石油化工股份有限公司 | Soild catalyst containing liquid acid and its prepn |
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- 2003-07-16 CN CNB03146470XA patent/CN1322931C/en not_active Expired - Lifetime
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101717321A (en) * | 2009-12-10 | 2010-06-02 | 复旦大学 | Method for catalyzing iso-butane/n-butene alkylation by solid acid |
| CN101717321B (en) * | 2009-12-10 | 2013-06-12 | 复旦大学 | Method for catalyzing iso-butane/n-butene alkylation by solid acid |
| CN107282140A (en) * | 2016-03-31 | 2017-10-24 | 华东理工大学 | A kind of perfluorinated sulfonic resin/PES/TiO2-ZrO2The preparation method of solid acid doughnut catalyst filling |
| CN107282140B (en) * | 2016-03-31 | 2019-11-19 | 华东理工大学 | A kind of perfluorinated sulfonic resin/PES/TiO2-ZrO2The preparation method of solid acid doughnut catalyst filling |
| CN113880712A (en) * | 2021-09-16 | 2022-01-04 | 泰兴金江化学工业有限公司 | Preparation method of ethyl acetate |
| CN113880712B (en) * | 2021-09-16 | 2023-08-04 | 泰兴金江化学工业有限公司 | Preparation method of ethyl acetate |
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