CN103055860B - Composited crystal solid alkali supporter catalyst and preparation method - Google Patents
Composited crystal solid alkali supporter catalyst and preparation method Download PDFInfo
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- CN103055860B CN103055860B CN201210587870.4A CN201210587870A CN103055860B CN 103055860 B CN103055860 B CN 103055860B CN 201210587870 A CN201210587870 A CN 201210587870A CN 103055860 B CN103055860 B CN 103055860B
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Abstract
The invention discloses a composited crystal solid alkali supporter catalyst and a preparation method thereof. The preparation method comprises the following steps: (1) dissolving CaCl2, AlCl3, MgCl2, Zn(NO3)2 and CdCl2 into water to obtain a solution A, dissolving NaCO3 into water to obtain a solution B, and mixing nano SrCO3 with water to obtain a solution C; (2) adding dropwise the solution A and the solution B into the solution C, stirring at the temperature of 70-80 DEG C, standing, filtrating in a suction manner, collecting precipitates, washing, drying, roasting, and grinding into powder; (3) mixing the solutions of K2CO3 and AuCl3, roasting, and grinding into powder; (4) adding the K2OSO4 solution to mix, and evaporating a solvent to obtain the composited crystal solid alkali supporter catalyst. According to the invention, the strength of the alkaline is remarkably increased, and the composited crystal solid alkali supporter catalyst is applicable to an organic synthesis reaction and can remarkably increase the yield of the chemical reaction.
Description
Technical field
The present invention relates to a kind of compound brilliant solid base carried catalyst and preparation method, should say the preparation method who generates compound brilliant solid base carried catalyst by method for crystallising.
Background technology
Solid base catalyst is a kind of novel catalyst that the mankind find, easily separate because thering is high activity, high selectivity, chemical reaction condition gentleness, reaction system, not etching apparatus, environmental friendliness, the advantage such as can reuse and more and more be paid attention to, especially aspect synthetic at fine chemistry, Polymer Synthesizing, make the chemosynthesis reaction of a lot of severe reaction conditions can be easy to carry out, and make synthesis process serialization, reduce energy resource consumption, reduce the pollution to environment, in recent years the research and development of solid base have also been come extensively.But because solid base is novel catalyst, start to walk more late, especially preparing aspect solid base, preparation technology requires very meticulous, cost costliness, specific area and mechanically stable intensity are also restricted because preparation technology is meticulous simultaneously.
Summary of the invention
The object of the invention is the compound brilliant solid base carried catalyst of open one and preparation method, the above-mentioned defect existing to overcome prior art.
The preparation method of compound brilliant solid base carried catalyst of the present invention, comprises the steps: chemical constituent:
(1) by CaCl
2, AlCl
3, MgCl
2, Zn (NO
3)
2and CdCl
2be dissolved in 250 parts of deionized waters, obtain A solution;
By NaCO
3be dissolved in 250 parts of deionized waters, obtain B solution;
By nanometer SrCO
3mix with 500 parts of deionized waters, obtain C solution;
(2) at 20 DEG C～30 DEG C, described A solution and described B solution are added drop-wise in C solution simultaneously, dropwised in 20 minutes at 10 minutes, stir 2～3 hours, be then warming up to 70 DEG C～80 DEG C, continue to stir 2～3 hours, be down to normal temperature, after static 5～10 hours, suction filtration, collecting precipitation thing, washing, be dried to moisture at 100 DEG C～120 DEG C and all evaporate, 1150 DEG C～1250 DEG C roastings after 3～4 hours, by calcining matter grounds travel powder;
(3) by the powder of step (2), add K
2cO
3and AuCl
3after solution mixes, roasting after 1～2 hour at 950 DEG C～1150 DEG C, then by calcining matter grounds travel powder;
(4) powder of step (3) is added to K again
2osO
4after solution mixes, at 90 DEG C～100 DEG C, by solvent evaporated under reduced pressure, obtain compound brilliant solid base carried catalyst;
Described nanometer SrCO
3particle diameter be 20～30 nanometers, preferably 25 nanometers;
K
2osO
4be the molecular formula of potassium osmate, the parts by weight of each component are:
CaCl
215～25 parts, AlCl
35～10 parts, MgCl
21～3 part, Zn (NO
3)
25～10 parts, CdCl
20.5～1.5 part, nanometer SrCO
31～3 part, Na
2cO
320～30 parts, AuCl
3solution 1.67%(weight) 10～20 parts, K
2cO
35～10 parts, K
2osO
4solution 1%(weight) 5～10 parts;
The invention reside in by crystallochemical reaction and utilize the mode of crystal growing process generation mixed crystal to prepare compound brilliant solid base carried catalyst, increase mixed crystal solid base specific area, utilize plane of crystal porous increase oxide surface to accept the combination position of proton simultaneously, the intensity that significantly improves alkali is gone back other catalyst of load simultaneously, forms a kind of compound brilliant solid base carried catalyst.
Compound brilliant solid base carried catalyst of the present invention is by the crystallization principle in chemical reaction process, react and prepare crystal and recrystallization doping chemical reaction and make oxide surface doping and chemical coordination by composite chemical, impel and between oxide, form mixed crystal, expand specific area, increase oxide surface and accept the combination position of proton, significantly improve also other catalyst of load of intensity of alkali, can be for the catalyst of organic synthesis, significantly improve the yield of chemical reaction, be easy to separate, can improve product purity and product yield.
Following examples or Application Example are weight portion:
Embodiment 1
One, mixed crystal solid super base combination catalyst, prepares by following steps;
(a). chemical constituent: 1000 parts of deionized waters, CaCl
215 parts, AlCl
310 parts, MgCl
21 part, Zn (NO
3)
210 parts, CdCl
20.5 part, nanometer SrCO
31 part, NaCO
330 parts, A
ucl
31.67%10 parts of solution, K
2cO
35 parts, K
2osO
41%10 parts of solution;
(b). by CaCl
2, AlCl
3, MgCl
2and Zn (NO
3)
2and CdCl
2after mixing, be dissolved in 250 parts of deionized waters, by NaCO
3be dissolved in 250 parts of deionized waters, in reactor, add 500 parts of deionized waters, then add nanometer SrCO
3, open high speed dispersor 1500 Zhuan ∕ and divide, all solution temperatures are controlled to 20 DEG C, by CaCl
2, Al Cl
3, MgCl
2and Zn (NO
3)
2and CdCl
2mixed liquor and NaCO
3the two notes of solution are added drop-wise in reactor, dropwise high-speed stirred 3 hours at 20 DEG C of temperature in 10 minutes, then be warming up to 80 DEG C, continue to stir 2 hours, impel crystal size and shape to reach unanimity by intensification, stop stirring, be down to normal temperature, after static 10 hours, suction filtration sediment cleans 3 times with 300 parts of deionized waters at every turn, foreign ion in washing and precipitating thing, and be dried to moisture at 120 DEG C and all evaporate;
(c). by the product of (b) process, at 1150 DEG C, roasting is after 4 hours, by calcining matter grounds travel powder;
(d). by the powder of (c) process, then add K
2cO
3and A
ucl
3after solution mixes, roasting after 1 hour at 1150 DEG C, then by calcining matter grounds travel powder;
(e) powder of (d) process is added to K again
2osO
4after solution mixes, at 90 DEG C, by solvent evaporated under reduced pressure, obtain compound brilliant solid base carried catalyst.。
Embodiment 2
One, mixed crystal solid super base combination catalyst, its feature is prepared by following steps;
(a). chemical constituent: 1000 parts of deionized waters, CaCl
225 parts, AlCl
35 parts, MgCl
23 parts, Zn (NO
3)
25 parts, CdCl
21.5 parts, nanometer SrCO
33 parts, NaCO
320 parts, A
ucl
31.67%20 parts of solution, K
2cO
37.5 parts, K
2osO
41%5 parts of solution;
(b). by CaCl
2, AlCl
3, MgCl
2and Zn (NO
3)
2and CdCl
2after mixing, be dissolved in 250 parts of deionized waters, by NaCO
3be dissolved in 250 parts of deionized waters, in reactor, add 500 parts of deionized waters, then add nanometer SrCO
3, open high speed dispersor 2000 Zhuan ∕ and divide, all solution temperatures are controlled to 30 DEG C, by CaCl
2, AlCl
3, MgCl
2and Zn (NO
3)
2and CdCl
2mixed liquor and NaCO
3the two notes of solution are added drop-wise in reactor, dropwise high-speed stirred 2 to 3 hours at 30 DEG C of temperature in 20 minutes, then be warming up to 70 DEG C, continue high-speed stirred 3 hours, impel crystal size and shape to reach unanimity by intensification, stop stirring, be down to normal temperature, after static 5 hours, suction filtration sediment cleans 3 times with 300 parts of deionized waters at every turn, foreign ion in washing and precipitating thing, and be dried to moisture at 100 DEG C and all evaporate;
(c). by the product of (b) process, at 1250 DEG C, roasting is after 3 hours, by calcining matter grounds travel powder;
(d). by the powder of (c) process, then add K
2cO
3and A
ucl
3after solution mixes, roasting after 1 hour at 950 DEG C, then by calcining matter grounds travel powder;
(e) powder of (d) process is added to K again
2osO
4after solution mixes, at 100 DEG C, by solvent evaporated under reduced pressure, obtain compound brilliant solid base carried catalyst.
Embodiment 3
Mixed crystal solid super base combination catalyst, its feature is prepared by following steps;
(a). chemical constituent: 1000 parts of deionized waters, CaCl
220 parts, AlCl
37.5 parts, MgCl
22 parts, Zn (NO
3)
27.5 parts, CdCl
21 part, nanometer SrCO
32 parts, NaCO
325 parts, A
ucl
31.67%15 parts of solution, K
2cO
310 parts, K
2osO
41%7.5 parts of solution;
(b). by CaCl
2, AlCl
3, MgCl
2and Zn (NO
3)
2and CdCl
2after mixing, be dissolved in 250 parts of deionized waters, by NaCO
3be dissolved in 250 parts of deionized waters, in reactor, add 500 parts of deionized waters, then add nanometer SrCO
3, open high speed dispersor 1750 Zhuan ∕ and divide, all solution temperatures are controlled to 25 DEG C, by CaCl
2, AlCl
3, MgCl
2and Zn (NO
3)
2and CdCl
2mixed liquor and NaCO
3the two notes of solution are added drop-wise in reactor, dropwise high-speed stirred 2.5 hours at 25 DEG C of temperature in 15 minutes, then be warming up to 75 DEG C, continue high-speed stirred 2.5 hours, impel crystal size and shape to reach unanimity by intensification, stop stirring, be down to normal temperature, after static 7.5 hours, suction filtration sediment cleans 3 times with 300 parts of deionized waters at every turn, foreign ion in washing and precipitating thing, and be dried to moisture at 110 DEG C and all evaporate;
(c). by the product of (b) process, at 1200 DEG C, roasting is after 3.5 hours, by calcining matter grounds travel powder;
(d). by the powder of (c) process, then add K
2cO
3and A
ucl
3after solution mixes, roasting after 1.5 hours at 1050 DEG C, then by calcining matter grounds travel powder;
(e) powder of (d) process is added to K again
2osO
4after solution mixes, at 95 DEG C, by solvent evaporated under reduced pressure, obtain compound brilliant solid base carried catalyst.
Application Example
Utilize compound brilliant solid base carried catalyst of the present invention ultra-violet absorber-menthyl salicylate for composed paper.
The preparation of menthyl salicylate:
Application Example 1(embodiment sample 1): in the reaction of salicylate menthyl ester, add compound brilliant solid base carried catalyst of the present invention.
In reactor, add 100 parts of gaultherolins, 100 parts of menthols, add 1 part of solid base carried catalyst, are warming up to 160 DEG C, 5 hours reaction time.After while being reacted to, separating solids alkali carried catalyst, then use the water-solubility impurity in deionized water extractive reaction product, draw upper strata transparent oily liquid, extract three times, measure the pH value of transparent oily liquid within the scope of 7-7.5, with distillation under vacuum, at 90 DEG C of moisture content of removing in transparent oily liquid, after the moisture content in transparent oily liquid is removed, the cut that is then collected in 143 DEG C of-144 DEG C/2.7kPa obtains colourless transparent liquid, yield 78.8%, purity 98.7%
Application Example 2(embodiment sample 2): in the reaction of salicylate menthyl ester, add compound brilliant solid base carried catalyst of the present invention.
In reactor, add 100 parts of gaultherolins, 100 parts of menthols, add 1 part of solid base carried catalyst, are warming up to 160 DEG C, 5 hours reaction time.After while being reacted to, separating solids alkali carried catalyst, then use the water-solubility impurity in deionized water extractive reaction product, draw upper strata transparent oily liquid, extract three times, measure the pH value of transparent oily liquid within the scope of 7-7.5, with distillation under vacuum, at 90 DEG C of moisture content of removing in transparent oily liquid, after the moisture content in transparent oily liquid is removed, the cut that is then collected in 143 DEG C of-144 DEG C/2.7kPa obtains colourless transparent liquid, yield 76.7%, purity 98.6%
Application Example 3(embodiment sample 3): in the reaction of salicylate menthyl ester, add compound brilliant solid base carried catalyst of the present invention.
In reactor, add 100 parts of gaultherolins, 100 parts of menthols, add 1 part of solid base carried catalyst, are warming up to 160 DEG C, 5 hours reaction time.After while being reacted to, separating solids alkali carried catalyst, then use the water-solubility impurity in deionized water extractive reaction product, draw upper strata transparent oily liquid, extract three times, measure the pH value of transparent oily liquid within the scope of 7-7.5, with distillation under vacuum, at 90 DEG C of moisture content of removing in transparent oily liquid, after the moisture content in transparent oily liquid is removed, the cut that is then collected in 143 DEG C of-144 DEG C/2.7kPa obtains colourless transparent liquid, yield 77.2%, purity 98.7%
Comparative sample: do not add compound brilliant solid base carried catalyst of the present invention in the reaction of salicylate menthyl ester, add Anhydrous potassium carbonate as catalyst.
In reactor, add 100 parts of gaultherolins, 100 parts of menthols, add 1 part of Anhydrous potassium carbonate, are warming up to 160 DEG C, 5 hours reaction time.After while being reacted to, separate potassium carbonate catalyst, then use the water-solubility impurity in deionized water extractive reaction product, draw upper strata transparent oily liquid, extract three times, measure the pH value of transparent oily liquid within the scope of 7-7.5, with distillation under vacuum, at 90 DEG C of moisture content of removing in transparent oily liquid, after the moisture content in transparent oily liquid is removed, the cut that is then collected in 143 DEG C of-144 DEG C/2.7kPa obtains colourless transparent liquid, yield 70.1%, purity 98.3%.
Ultra-violet absorber for solid base Basicity Determination and paper-menthyl salicylate testing result is in table 1.
Table 1
Can find out from above-mentioned application result: use the paper ultra-violet absorber-menthyl salicylate of the synthetic preparation of catalyst of the present invention compared with typical catalyst, product yield is high, catalyst effect is remarkable, product purity advantages of higher, compound brilliant solid base carried catalyst of the present invention is described, catalytic action is remarkable, is desirable solid base carried catalyst.
Claims (5)
1. the preparation method of compound brilliant solid base carried catalyst, is characterized in that, comprises the steps:
(1) by CaCl
2, AlCl
3, MgCl
2, Zn (NO
3)
2and CdCl
2be dissolved in 250 parts of deionized waters, obtain A solution; By NaCO
3be dissolved in 250 parts of deionized waters, obtain B solution; By nanometer SrCO
3mix with 500 parts of deionized waters, obtain C solution;
(2) described A solution and described B solution are added drop-wise in C solution simultaneously, stir, be then warming up to 70 DEG C～80 DEG C, continue to stir, be down to normal temperature, static, suction filtration, collecting precipitation thing, washing, dry, roasting, by calcining matter grounds travel powder;
(3) by the powder of step (2), add K
2cO
3and AuCl
3solution mixes, roasting, then by calcining matter grounds travel powder;
(4) powder of step (3) is added to K again
2osO
4solution mixes, and evaporating solvent, obtains compound brilliant solid base carried catalyst;
The parts by weight of each component are: CaCl
215～25 parts, AlCl
35～10 parts, MgCl
21～3 part, Zn (NO
3)
25～10 parts, CdCl
20.5～1.5 part, nanometer SrCO
31～3 part, Na
2cO
320～30 parts, AuCl
31.67%10～20 parts of solution weight concentration, K
2cO
35～10 parts, K
2osO
41%5～10 parts of solution weight concentration.
2. method according to claim 1, it is characterized in that, in step (2), at 20 DEG C～30 DEG C, described A solution and described B solution are added drop-wise in C solution simultaneously, dropwised in 20 minutes at 10 minutes, stir 2～3 hours, then be warming up to 70 DEG C～80 DEG C, continue to stir 2～3 hours, be down to normal temperature, after static 5～10 hours, suction filtration, collecting precipitation thing, washing, is dried to moisture at 100 DEG C～120 DEG C and all evaporates, 1150 DEG C～1250 DEG C roastings after 3～4 hours, by calcining matter grounds travel powder.
3. method according to claim 1, is characterized in that, in step (3), by the powder of step (2), adds K
2cO
3and AuCl
3after solution mixes, roasting after 1～2 hour at 950 DEG C～1150 DEG C, then by calcining matter grounds travel powder.
4. method according to claim 1, is characterized in that, described nanometer SrCO
3particle diameter be 20～30 nanometers.
5. the compound brilliant solid base carried catalyst of preparing according to the method described in claim 1～4 any one.
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| CN104014338B (en) * | 2014-06-12 | 2016-03-02 | 上海东升新材料有限公司 | Solid base carrier thallium catalyst and preparation method |
| CN111876597B (en) * | 2020-08-03 | 2022-02-22 | 国家地质实验测试中心 | Extraction of radioactive cause from molybdenite187Methods for Os |
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