CN1509816A - Preparing method for catalyst with macroporous silica gel as carrier - Google Patents
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- CN1509816A CN1509816A CNA021593558A CN02159355A CN1509816A CN 1509816 A CN1509816 A CN 1509816A CN A021593558 A CNA021593558 A CN A021593558A CN 02159355 A CN02159355 A CN 02159355A CN 1509816 A CN1509816 A CN 1509816A
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Abstract
A catalyst using macroreticular silicon gel as carrier for hydrogenating CO to obtain oxygen-contained dicarbon compound is prepared through putting the silicon gel particles with small pore diameter in the alkaline solution prepared from alkali metal and the hydroxide, carbonate, dicarbonate, formate, or acetate of ammonium, drying or calcining to obtain carrier, immersing the carrier in the solution of Rh and cocatalyst, and drying or calcining. Its advantages are high activity and high selectivity.
Description
Technical field
The present invention relates to a kind ofly make the Preparation of catalysts method of carrier, relate in particular to a kind of from making preparing carriers from synthesis gas (H by the silica gel of the less ordinary granular silica gel preparation in sol method production and aperture with macro porous silica gel
2And CO) synthetic C
2The method of oxygenatedchemicals rhodium base catalyst.
Background technology
From synthesis gas (H
2/ CO) synthetic c_2-oxygen compound is to be subjected to the research topic paid attention to widely in recent years.It is found that silica gel is the good carrier of synthetic c_2-oxygen compound rhodium base catalyst, uses widely under study for action.These granular silica gel adopt sol method production usually.The BET average pore size of the silica gel of being produced by these methods is generally between 20～100 , and specific area is between 350～900 meters squared per gram.In order to study of the influence of silica gel pore structure to catalyst performance, seek the silica gel of how better structural behaviour, particularly the bigger silica gel easily in aperture is originated, the inventor of present patent application once found a kind of making usually to prepare the method for macro porous silica gel by the reaming of sol method production silica gel, and had applied for Chinese invention patent (application number: 02127599.8).
Summary of the invention
The object of the present invention is to provide and a kind ofly make the Preparation of catalysts method of carrier, make its reaming prepare larger aperture silica gel as the better synthetic c_2-oxygen compound catalyst of preparing carriers performance with macro porous silica gel.
The less silica gel in aperture that the technical solution used in the present invention is to use the solution-treated of organic solvents such as the aqueous solution of alkaline matter or methyl alcohol to be produced by sol method usually makes its reaming.By the particle silica gel that this method makes, its BET average pore size is that 100～300 , specific area are 150～350m
2/ g, pore volume are 0.9～1.1ml/g.Can control the structural property of parameter adjustment silica gel by kind, concentration, treatment temperature and the time etc. that change alkaline matter, to obtain the silica gel of overall target excellences such as its granularity, aperture, specific area and pore volume, thereby can be used in activity and the selectivity of improving synthetic c_2-oxygen compound rhodium base catalyst, or need the catalyst carrier of larger aperture silica gel as other.
1, the raw material silica gel particle of the present invention particle silica gel that can be various particle size range, can be by sol method preparation well known in the art, also can be purchased, for example, the silica gel of the various particle size range of 1～8mm that Haiyang Chemical Plant, Qingdao and Erdos, Huhehaote, Inner Mongol silica gel factory produce.Can select the particle size range of raw material silica gel according to the average grain diameter of needed final macroporous particle silica gel.The particle diameter of the common silica gel particle that the present invention adopts can be 0.1～8mm.
2, the example of alkaline solution of the present invention includes but not limited to the hydroxide of alkali metal and ammonium, as lithium hydroxide, NaOH, potassium hydroxide and ammonium hydroxide etc.; Alkali-metal carbonate, bicarbonate, formates and acetate are as the solution of lithium carbonate, sodium carbonate, potash etc.The used liquid medium of alkaline substance solution is water preferably, but also be not limited to water.The addition of solution is minimum will flood all silica gel, can be more than 2～10 times of silica gel volume, preferably 2～5 times.
The molar percent of solution neutral and alkali material and silicon is 1～30%, and more suitably molar percent is 2～15%.The pH value of alkaline solution can be 8～14.
3, according to the present invention, the heat treatment temperature of silica gel in alkaline solution is 50～200 ℃, preferred 80～130 ℃.Concrete heat treatment temperature depends on the alkaline solution that adopted and required silica gel product.The time of in alkaline solution silica gel being heat-treated has no particular limits, and its length is relevant with the concentration of used heat treatment temperature and alkaline substance solution.When heat treatment temperature and/or alkaline substance solution concentration were low, the time of processing needed suitably to prolong, otherwise when heat treatment temperature and/or alkaline substance solution concentration were high, the processing time can suitably shorten.Heat treated temperature and alkaline substance solution concentration are high more and the processing time is long more, and the aperture of the silica gel that obtains is big more, specific area is more little.Heat treatment time among the present invention is preferably 1 hour～and 5 days.How long concrete employing can be determined according to the alkaline solution that is adopted, heat treatment temperature and required silica gel product.
According to the present invention, handle with alkaline solution in the implementation process of silica gel particle, in order to make the macro porous silica gel that obtains more even, can adopt mechanical agitation or air-flow to stir.
4, then carry out post-processing step through the heat treated silica gel of alkaline solution.Any post-processing approach that is suitable for producing catalyst carrier may be used to the present invention.According to a preferred embodiment, the solution in the mixture that aqueous slkali heat treatment can be obtained is removed, with media such as silica gel water washings, then under proper temperature dry or double roasting to produce the bigger particle silica gel in aperture that is fit to do catalyst carrier.
5, with rhodium salt with as the silica-gel carrier of the solution impregnation method for preparing of other slaine of auxiliary agent, then drying or double roasting etc. usually the step of preparation catalyst make the rhodium base catalyst of synthetic c_2-oxygen compound.Said rhodium salt can be the salt of solubilities such as rhodium chloride, rhodium nitrate, and said auxiliary agent can be the soluble-salt of transition metal (as Ir, Ru, Co, Fe, Mn, Ti, Zr, V), rare earth metal (as Ce, Sm, La), alkali metal (as Li, Na), alkaline-earth metal (as Mg, Ba).Said dipping method can be used co-impregnation, also can use the method for step impregnation; Baking temperature can be room temperature～150 ℃, and the time can be 1 hour～and 20 days; Sintering temperature can be 150～500 ℃, and the time can be 1～50 hour.
The specific embodiment
Utilize embodiment that the present invention is carried out more detailed description below.Should be pointed out that the purpose of enumerating these embodiment only is in order to explain the present invention, rather than limitation of the present invention.
Embodiment 1: Preparation of Catalyst 1
Is 20 grams that 98 and specific area are that 380 meters squared per gram and pore volume are the mixed solution that the common silica gel of 0.86ml/g 20～40 purposes places 90 ℃ and 90 ml waters and 1.8 gram NaOH to form by the BET average pore size of sol method preparation, 90 ℃ handle 12 hours after water flush away residual NaOH, after 120 ℃ of dryings, obtain wide-aperture silica gel.With containing aequum RhCl
3, Mn (NO
3)
2, LiNO
3And Fe (NO3)
2The aqueous solution flood this silica gel altogether, and the 1%Rh-1%Mn-0.075%Li-0.05%Fe/SiO that made in 6 hours in 120 ℃ of dryings
2Catalyst.
Embodiment 2: Preparation of Catalyst 2
The BET average pore size that 20 grams are prepared by sol method is that 98 and specific area are about 380 meters squared per gram and pore volume is that 0.86ml/g and the common silica gel of 20～40 purposes place the mixed solution of being made up of 4.5 gram concentrated ammonia liquors and 90 ml waters, 95 ℃ handle 19 hours after the residual ammonium hydroxide of water flush away, obtain the silica gel of larger aperture after 6 hours 120 ℃ of dryings.With containing aequum RhCl
3, Mn (NO
3)
2, LiNO
3And Fe (NO
3)
2The aqueous solution flood this silica gel altogether, and the 1%Rh-1%Mn-0.075%Li-0.05%Fe/SiO that made in 6 hours in 120 ℃ of dryings
2Catalyst.
Embodiment 3: Preparation of Catalyst 3
The BET average pore size that 20 grams are prepared by sol method is that 98 , specific area are that 380 meters squared per gram and pore volume are that 0.86ml/g and the common silica gel of 20-40 purpose place the mixed solution of being made up of 2 gram potassium hydroxide and 90 ml waters, 95 ℃ handle 21 hours after the residual potassium hydroxide of water flush away, after 120 ℃ of dryings, obtain more wide-aperture silica gel.With containing aequum RhCl
3, Mn (NO
3)
2, LiNO
3And Fe (NO
3)
2The aqueous solution flood this silica gel altogether, and the 1%Rh-1%Mn-0.075%Li-0.05%Fe/SiO that made in 6 hours in 120 ℃ of dryings
2Catalyst.
Embodiment 4: Preparation of Catalyst 4
The BET average pore size that 15 grams are prepared by sol method is that 98 , specific area are that 380 meters squared per gram and pore volume are the mixed solution that 0.86ml/g and the common silica gel of 20～40 purposes place 1.8 gram sodium carbonate and 90 ml waters to form, 95 ℃ handle 24 hours after the residual sodium carbonate of water flush away, after 120 ℃ of dryings, obtain more wide-aperture silica gel.With containing aequum RhCl
3, Mn (NO
3)
2, LiNO
3And Fe (NO
3)
2The aqueous solution flood this silica gel altogether, and the 1%Rh-1%Mn-0.075%Li-0.05%Fe/SiO that made in 6 hours in 120 ℃ of dryings
2Catalyst.
Embodiment 5: Preparation of Catalyst 5
Containing aequum RhCl
3.xH
2O, Mn (NO
3)
2, LiNO
3, Fe (NO
3)
2, H
2IrCl
6The silica gel of aqueous solution dipping embodiment 4, after 120 ℃ of dryings 6 are little, obtain 1%Rh-1%Mn-0.075%Li-0.1%Fe-0.5%Ir/SiO
2Catalyst.
Embodiment 6: Preparation of Catalyst 6
Containing aequum RhCl
3.xH
2O, Mn (NO
3)
2, LiNO
3, Fe (NO
3)
2, RuCl
3The silica gel of aqueous solution dipping embodiment 4, after 120 ℃ of dryings 6 are little, obtain 1%Rh-1%Mn-0.075%Li-0.1%Fe-0.5%Ru/SiO
2Catalyst.
Comparative example
Available from the silica gel of silica gel factory without the reaming processing.
The silica gel that silica gel that the foregoing description is made and comparative example are handled without reaming, the BET average pore size, specific area and the pore volume that record with U.S. Micromeritics ASAP 2010 analyzers and nitrogen adsorption method, and be that carrier is by RhCl with these silica gel
3, Mn (NO
3)
2, LiNO
3And Fe (NO
3)
2The aqueous solution flood above-mentioned silica gel altogether, and the 1%Rh-1%Mn-0.075%Li-0.05%Fe/SiO that made in 6 hours in 120 ℃ of dryings
2Catalyst.
The reaction result of the synthetic c_2-oxygen compound of the structural property of above-mentioned catalyst and CO hydrogenation is listed in the table 1.
The macroporous particle silica gel that makes by the inventive method is used as CO hydrogenation system C
2The carrier of the rhodium base catalyst of oxygenatedchemicals, the activity and the selectivity of its synthetic c_2-oxygen compound all increase significantly (seeing Table 1), this disposal methods silica gel is described, it is effectively that the performance of improving former silica gel makes the carrier that is fit to do catalyst, can become the new source that obtains catalyst carrier silica gel.
Table 1: the catalytic performance of the rhodium base catalyst of Different Pore Structures silica-gel carrier preparation
| Sequence number | Silica gel character | ??C 2-oxy selectivity C% | ??C 2-oxy space-time yield g/kg.h | ||
| BET aperture nm | Specific area m 2/g | Pore volume cm 3/g | |||
| Embodiment | |||||
| Embodiment 1 | ????17.2 | ??251.9 | ??1.082 | ??58.2 | ??389.1 |
| Embodiment 2 | ????19.3 | ??198.4 | ??1.065 | ??60.7 | ??421.9 |
| Embodiment 3 | ????20.5 | ??182.7 | ??0.89 | ??59.9 | ??458.4 |
| Embodiment 4 | ????21.0 | ??187.1 | ??0.98 | ??59.7 | ??431.4 |
| Embodiment 5 | ????21.0 | ??187.1 | ??0.98 | ??62.3 | ??498.2 |
| Embodiment 6 | ????21.0 | ??187.1 | ??0.98 | ??58.4 | ??462.5 |
| Comparative example | ????10.5 | ??341.2 | ??0.86 | ??51.2 | ??290.5 |
Reaction condition: H
2/ CO=2 (volume ratio), GHSV=12000h
-1, 320 ℃ and 3.0MPa.
Annotate: C
2 +Oxy=C
2H
5OH+CH
3CHO+CH
3COOH reaches the OXO products that contains two above carbon atoms on a small quantity.
C
2 +Oxy STY is the space-time yield that contains the OXO products of two and two above carbon atoms.
Claims (17)
1, a kind of Preparation of catalysts method of making carrier with macro porous silica gel, common silica gel is placed alkaline solution, heating, drying or roasting, make the macro porous silica gel carrier, with rhodium salt with as the solution impregnation silica-gel carrier of the slaine of co-catalyst, dry, roasting make the rhodium base catalyst that macro porous silica gel is a carrier.
2, preparation method as claimed in claim 1 is characterized in that, described common silica gel is the aperture smaller particles shape silica gel of being produced by sol method.
3, preparation method as claimed in claim 1 is characterized in that, its BET average pore size of described macro porous silica gel is that 100-300 , BET specific area are 150～350m
2/ g, pore volume are 0.9～1.1ml/g.
4, preparation method as claimed in claim 1 is characterized in that, described alkaline solution is one or more a mixed solution in carbonate, bicarbonate, formates and the acetate solution of solution, alkali metal and the ammonium of the hydroxide of alkali metal and ammonium.
As claim 1 or 4 described preparation methods, it is characterized in that 5, described alkaline solution is at least a in lithium hydroxide, NaOH, potassium hydroxide, ammonium hydroxide, lithium carbonate, sodium carbonate and the solution of potassium carbonate.
6, preparation method as claimed in claim 1 is characterized in that, the molar percent of described alkaline solution neutral and alkali material and silicon is 1～30%.
As claim 1 or 6 described preparation methods, it is characterized in that 7, the molar percent of described alkaline solution neutral and alkali material and silicon is 2～15%.
8, preparation method as claimed in claim 1 is characterized in that, described alkaline solution is the aqueous solution, its pH=8-14.
9, preparation method as claimed in claim 1 is characterized in that, the heat treated temperature is 50～200 ℃ in the described alkaline solution.
10, preparation method as claimed in claim 1 is characterized in that, the heat treated temperature is 80～130 ℃ in the described alkaline solution.
11, preparation method as claimed in claim 1 is characterized in that, the heat treated time is 1 hour～5 days in the described alkaline solution.
12, preparation method as claimed in claim 1 is characterized in that, the particle diameter of described common silica gel particle is 0.1～8mm.
13, preparation method as claimed in claim 1 is characterized in that, described rhodium salt is the soluble-salt of rhodium chloride or rhodium nitrate.
14, preparation method as claimed in claim 1, described promoter metal salt is one or more soluble-salts in transition metal, rare earth metal, alkali metal and the alkaline-earth metal.
As claim 1 or 14 described preparation methods, it is characterized in that 15, described promoter metal salt is one or more soluble-salts among Ir, Ru, Co, Fe, Mn, Ti, Zr, V, Ce, Sm, La, Li, Na, Mg and the Ba.
16, preparation method as claimed in claim 1 is characterized in that, said dipping is co-impregnation or step impregnation method.
17, preparation method as claimed in claim 1 is characterized in that, the baking temperature of described impregnated catalyst is room temperature～150 ℃, and the time is 1 hour～20 days; Sintering temperature is 150～500 ℃, and the time is 1～50 hour.
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| CN103159220A (en) * | 2011-12-15 | 2013-06-19 | 中国石油天然气股份有限公司 | Preparation method of macroporous silica gel |
| CN103159220B (en) * | 2011-12-15 | 2015-05-13 | 中国石油天然气股份有限公司 | Preparation method of macroporous silica gel |
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| CN108816223B (en) * | 2018-07-09 | 2021-08-20 | 江苏凌飞科技股份有限公司 | Catalyst for preparing polyoxyethylene nonyl cyclohexanol ether and preparation method thereof |
| CN111252772A (en) * | 2018-11-30 | 2020-06-09 | 中国科学院大连化学物理研究所 | Method for adjusting aperture of silicon dioxide |
| CN111252772B (en) * | 2018-11-30 | 2022-03-22 | 中国科学院大连化学物理研究所 | Method for adjusting aperture of silicon dioxide |
| CN111434382A (en) * | 2019-01-15 | 2020-07-21 | 天津大学 | Carrier-supported vanadium oxide promoted Rh-based catalyst and preparation method and application thereof |
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Assignee: JIANGSU SOPO (Group) Co.,Ltd. Assignor: Dalian Institute of Chemical Physics, Chinese Academy of Sciences Contract record no.: 2012320000391 Denomination of invention: Preparing method for catalyst with macroporous silica gel as carrier Granted publication date: 20060419 License type: Exclusive License Open date: 20040707 Record date: 20120405 |
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