CN104801327A - Preparation method of solid acid catalyst - Google Patents
Preparation method of solid acid catalyst Download PDFInfo
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- CN104801327A CN104801327A CN201510154308.6A CN201510154308A CN104801327A CN 104801327 A CN104801327 A CN 104801327A CN 201510154308 A CN201510154308 A CN 201510154308A CN 104801327 A CN104801327 A CN 104801327A
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- acid catalyst
- solid acid
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- ammonium
- chloride
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Abstract
The invention particularly provides a preparation method of a solid acid catalyst. The method comprises the following steps: using metal chlorides as raw materials, performing hydrolysis, neutralization, aging, washing and drying, so as to obtain solid powder; fully grinding the solid powder, mixing the ground solid powder with ammonium salt, and roasting, so as to obtain the solid acid catalyst. According to the preparation method of the solid acid catalyst, the raw materials are low in cost and easy to obtain, the synthetic method is simple, and the analysis on a test result shows that the synthesized solid acid catalyst is high in acidity and excellent in heat stability, so that the preparation method has wide application prospect.
Description
Technical field
The invention belongs to chemical reagent synthesis technical field, be specifically related to a kind of preparation method of solid acid catalyst.
Background technology
Acid is the important catalyst of a class, can be used for catalytic esterification, Friedel-Crafts reaction and aldol reaction etc.The acid catalyst of current industrial application is liquid acid catalyst mostly, such as: sulfuric acid, phosphoric acid, nitric acid, hydrochloric acid, p-methyl benzenesulfonic acid etc.Because the acid catalyzed reaction of liquid belongs to homogeneous reaction, catalytic activity is high, but liquid acid catalyst exists etching apparatus, difficulty and product separation, is difficult to the difficult problems such as recycling.
Because solid acid has easily and the advantage such as product separation, recyclable recycling, be subject to the extensive concern of academia and industrial quarters in recent years.The solid acid catalyst reported at present comprises the heteropllyacids such as phosphomolybdic acid, silico-tungstic acid, the cationic ion-exchange resin classes such as Amberlyst-15, zeolite molecular sieve class etc., and wherein after the reaction of heteropllyacids compound, easily generating portion is dissolved, not easily recycling; Cationic ion-exchange resin class easily occurs swelling and broken in catalyse organic reaction process; Zeolite molecular sieve then there is acid strength and the drawbacks such as limited are measured in acid.
For above-mentioned existing solid acid catalyst synthesis Problems existing, the invention discloses a kind of is raw material with metal chloride, by hydrolysis, neutralization, ageing, washing, oven dry, obtain the method mixed with ammonium salt after pressed powder fully grinds, novel solid acid catalyst is prepared in roasting.
Summary of the invention
The object of the invention is to overcome existing solid acid catalyst easy generating portion in catalytic reaction dissolve, swelling and broken, not easily recycling, acid strength and the limited problem of acid amount.
For this reason, the invention provides a kind of preparation method of solid acid catalyst, comprise the steps:
Step 1) hydrolysis: by the ratio mixed dissolution of metal chloride and water 1:5 ~ 1:100 in mass ratio;
Step 2) neutralization: adopt concentration be 5% ~ 30% alkali lye by the metal chloride solutions after dissolving, to be adjusted to pH be 8 ~ 10;
Step 3) ageing, washing: by the liquid after still aging 10 ~ 30 hours after neutralization, adopt deionized water washing 3 ~ 10 times;
Step 4) to dry: the solid after washing is placed in baking oven and dries, bake out temperature is 80 ~ 120
oc, drying time is 10 ~ 30 hours;
Step 5) fully being pulverized by the solid after drying lastly mixes with ammonium salt, and ammonium salt quality is 5% ~ 50% of pressed powder quality;
Step 6) powder mixed in step 5) is placed in Muffle furnace roasting, obtain solid acid catalyst, wherein, sintering temperature is 300 ~ 600
oc, roasting time is 3 ~ 15 hours.
Above-mentioned metal chloride is two or more in butter of tin, titanium tetrachloride, zirconium chloride, zinc chloride, iron chloride, aluminium chloride.
In the mixture of two or more metal chloride above-mentioned, metal molar percentage is respectively tin 1 ~ 20%, titanium 20 ~ 80%, zirconium 20 ~ 80%, zinc 0 ~ 15%, iron 0 ~ 20%, aluminium 0 ~ 15%.
Above-mentioned alkali lye is the one in NaOH, potassium hydroxide, ammoniacal liquor.
Above-mentioned concentration of lye is 2 ~ 20%.
Above-mentioned ammonium salt is one or more in ammonium chloride, ammonium sulfate, ammonium hydrogen sulfate, ammonium phosphate, ammonium hydrogen phosphate, ammonium dihydrogen phosphate (ADP), ammonium nitrate.
Above-mentioned steps 5) in ammonium salt quality to account for pressed powder optimal quality be 10% ~ 25%.
Beneficial effect of the present invention:
(1) this solid acid catalyst that obtains of the present invention is compared with the solid acid catalyst of existing synthesis, and cheaper starting materials is easy to get, simple synthetic method is easy.
(2) solid acid catalyst for preparing of the preparation method of this solid acid catalyst provided by the invention acid strong, to recycle performance good, have broad application prospects.
Below with reference to accompanying drawing, the present invention is described in further details.
Accompanying drawing explanation
Fig. 1 is the infrared figure of pyridine of the solid acid catalyst that embodiment 1 is synthesized.
Fig. 2 is the infrared figure of pyridine of the solid acid catalyst of the 2-in-1 one-tenth of embodiment.
Fig. 3 is the NH of the solid acid catalyst that embodiment 1 is synthesized
3-TPD schemes.
Fig. 4 is the NH of the solid acid catalyst of the 2-in-1 one-tenth of embodiment
3-TPD schemes.
Fig. 5 is the TG-DTA figure of the solid acid catalyst of the 2-in-1 one-tenth of embodiment.
Detailed description of the invention
Embodiment 1:
Dissolve to overcome existing solid acid catalyst easy generating portion in catalytic reaction, swelling and broken, not easily recycling, limited problem is measured in acid strength and calculation, present embodiments provides a kind of preparation method of solid acid catalyst, comprises the steps:
Step 1) hydrolysis: take 7.012 g SnCl
45H
2o, 13.280 g TiCl
4, 2.414 g AlCl
36H
2o(metal molar percentage is 20%:70%:10%), be dissolved in 500 mL water, fully stir and make it all dissolve.
Step 2) neutralization: add in above-mentioned solution concentration be 10% sodium hydroxide solution be adjusted to pH=10.
Step 3) ageing, washing: by the solution left standstill ageing after 15 hours after neutralization, adopt deionized water to wash 3 times.
Step 4) dry: the solid after above-mentioned washing is placed in baking oven 100
oCdry 15 hours.
Step 5) pressed powder after drying fully is ground, crosses 200 mesh sieves, take a certain amount of ammonium hydrogen sulfate (quality is 10% of pressed powder), the powder after it being sieved with ground solid fully mixes.
Step 6) mixed pressed powder is placed in Muffle furnace, 500
oc roasting 10 h, obtains solid acid catalyst.
Infrared and the NH by pyridine
3-TPD characterizes the solid acid catalyst that the present embodiment obtains, and as shown in figures 1 and 3, shows that the solid acid catalyst synthesized is simultaneously containing Lewis acid position and Br nsted acid position, and contains a large amount of Br nsted strong acidic sites and super acids position.
Embodiment 2:
Take 7.012 g SnCl
45H
2o, 15.177 g TiCl
4, 1.363 g ZnCl
2(metal molar percentage is 10%:80%:10%), is dissolved in 450 mL water, abundant stirring and dissolving, add in solution concentration be 10% ammoniacal liquor be adjusted to pH=9; By the solution left standstill ageing after neutralization after 20 hours, adopt deionized water to wash 5 times, the solid after washing is placed in baking oven 90
oCdry 20 hours; Pressed powder after oven dry fully grinds, cross 100 mesh sieves, and take a certain amount of ammonium sulfate (quality is 20% of pressed powder), the powder after it being sieved with ground solid fully mixes; Mixed pressed powder is placed in Muffle furnace, 450
oc roasting 15 h, obtains solid acid catalyst.
Infrared and the NH by pyridine
3-TPD characterizes the solid acid catalyst that the present embodiment obtains, and result as shown in Figure 2 and Figure 4, shows that the solid acid catalyst synthesized is simultaneously containing Lewis acid position and Br nsted acid position, and contains a large amount of Br nsted strong acidic sites and super acids position.As shown in Figure 5, analyzed by TG-DTA, show that the solid acid catalyst synthesized has excellent heat endurance.
Embodiment 3:
Take 3.506 g SnCl
45H
2o, 18.656 g ZrCl
4, 1.363 g ZnCl
2, 1.207 g AlCl
36H
2o(metal molar percentage is 5%:80%:10%:5%), be dissolved in 750 mL water, abundant stirring and dissolving, add in solution concentration be 5% potassium hydroxide be adjusted to pH=8; By the solution left standstill ageing after neutralization after 10 hours, deionized water is adopted to wash 3 times; Solid after washing is placed in baking oven 80
oCdry 10 hours; Pressed powder after oven dry fully grinds, cross 100 mesh sieves, and take the mixture of a certain amount of ammonium sulfate and ammonium chloride, its gross mass is 5% of pressed powder, and the powder after it being sieved with ground solid fully mixes; Mixed pressed powder is placed in Muffle furnace, 300
oc roasting 3 h, obtains solid acid catalyst.
By characterizing, show that the solid acid catalyst that the present embodiment synthesizes contains Lewis acid position and Br nsted acid position simultaneously, and containing Br nsted strong acidic site and super acids position, and there is excellent heat endurance.
Embodiment 4:
Take 5.25 g SnCl
45H
2o, 18.656 g ZrCl
4, 1.352 g FeCl
36H
2o(metal molar percentage is 15%:80%:5%), be dissolved in 1000 mL water, abundant stirring and dissolving, add in solution concentration be 30% NaOH be adjusted to pH=10; By the solution left standstill ageing after neutralization after 30 hours, deionized water is adopted to wash 10 times; Solid after washing is placed in baking oven 120
oCdry 30 hours; Pressed powder after oven dry fully grinds, cross 100 mesh sieves, and take a certain amount of ammonium sulfate and ammonium hydrogen sulfate mixture (quality is 20% of pressed powder), the powder after it being sieved with ground solid fully mixes; Mixed pressed powder is placed in Muffle furnace, 600
oc roasting 15 h, obtains solid acid catalyst.
By characterizing, show that the solid acid catalyst synthesized is simultaneously containing Lewis acid position and Br nsted acid position, and containing Br nsted strong acidic site and super acids position, and there is excellent heat endurance.
Ammonium salt in above-described embodiment can also be one or more in ammonium phosphate, ammonium hydrogen phosphate, ammonium dihydrogen phosphate (ADP), ammonium nitrate.
In sum, the preparation method of this solid acid catalyst provided by the invention take metal chloride as raw material, by hydrolysis, neutralization, ageing, washing, oven dry, obtain the method mixed with ammonium salt after pressed powder fully grinds, novel solid acid catalyst is prepared in roasting, compared with the solid acid catalyst of existing synthesis, cheaper starting materials of the present invention is easy to get, simple synthetic method is easy, characterization result shows, the solid acid catalyst of synthesis is acid strong, it is good to recycle performance, has broad application prospects.
More than exemplifying is only illustrate of the present invention, does not form the restriction to protection scope of the present invention, everyly all belongs within protection scope of the present invention with the same or analogous design of the present invention.
Claims (7)
1. a preparation method for solid acid catalyst, is characterized in that: comprise the steps:
Step 1) hydrolysis: by the ratio mixed dissolution of metal chloride and water 1:5 ~ 1:100 in mass ratio;
Step 2) neutralization: adopt concentration be 5% ~ 30% alkali lye by the metal chloride solutions after dissolving, to be adjusted to pH be 8 ~ 10;
Step 3) ageing, washing: by the liquid after still aging 10 ~ 30 hours after neutralization, adopt deionized water washing 3 ~ 10 times;
Step 4) to dry: the solid after washing is placed in baking oven and dries, bake out temperature is 80 ~ 120
oc, drying time is 10 ~ 30 hours;
Step 5) fully being pulverized by the solid after drying lastly mixes with ammonium salt, and ammonium salt quality is 5% ~ 50% of pressed powder quality;
Step 6) powder mixed in step 5) is placed in Muffle furnace roasting, obtain solid acid catalyst, wherein, sintering temperature is 300 ~ 600
oc, roasting time is 3 ~ 15 hours.
2. the preparation method of solid acid catalyst as claimed in claim 1, is characterized in that: described metal chloride is two or more in butter of tin, titanium tetrachloride, zirconium chloride, zinc chloride, iron chloride, aluminium chloride.
3. the preparation method of solid acid catalyst as claimed in claim 2, is characterized in that: in the mixture of two or more metal chloride described, metal molar percentage is respectively tin 1 ~ 20%, titanium 20 ~ 80%, zirconium 20 ~ 80%, zinc 0 ~ 15%, iron 0 ~ 20%, aluminium 0 ~ 15%.
4. the preparation method of solid acid catalyst as claimed in claim 1, is characterized in that: described alkali lye is the one in NaOH, potassium hydroxide, ammoniacal liquor.
5. the preparation method of solid acid catalyst as claimed in claim 4, is characterized in that: described concentration of lye is 2 ~ 20%.
6. the preparation method of solid acid catalyst as claimed in claim 1, is characterized in that: described ammonium salt is one or more in ammonium chloride, ammonium sulfate, ammonium hydrogen sulfate, ammonium phosphate, ammonium hydrogen phosphate, ammonium dihydrogen phosphate (ADP), ammonium nitrate.
7. the preparation method of solid acid catalyst as claimed in claim 1, is characterized in that: described step 5) in ammonium salt quality to account for pressed powder optimal quality be 10% ~ 25%.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106513024A (en) * | 2016-10-20 | 2017-03-22 | 陕西延长石油（集团）有限责任公司炼化公司 | Solid acid catalyst, and preparation method and application thereof |
| CN106554277A (en) * | 2016-10-20 | 2017-04-05 | 陕西延长石油（集团）有限责任公司炼化公司 | A kind of solid acid catalysis synthesize the method for Isosorbide-5-Nitrae butylene glycol aerylate |
| CN112973663A (en) * | 2021-03-12 | 2021-06-18 | 盐城工学院 | Solid acid catalyst for catalyzing esterification reaction of pentaerythritol and stearic acid and preparation method thereof |
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| CN102921399A (en) * | 2012-10-30 | 2013-02-13 | 陕西启源科技发展有限责任公司 | Method for preparing solid catalyst |
| EP2612878A1 (en) * | 2010-08-31 | 2013-07-10 | Toray Industries, Inc. | Polylactic acid block copolymer |
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2015
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Patent Citations (4)
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| CN101708470A (en) * | 2009-11-18 | 2010-05-19 | 广西科学院 | Method for preparing magnetic solid acid catalyst for production of biodiesel |
| EP2612878A1 (en) * | 2010-08-31 | 2013-07-10 | Toray Industries, Inc. | Polylactic acid block copolymer |
| CN102921399A (en) * | 2012-10-30 | 2013-02-13 | 陕西启源科技发展有限责任公司 | Method for preparing solid catalyst |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106513024A (en) * | 2016-10-20 | 2017-03-22 | 陕西延长石油（集团）有限责任公司炼化公司 | Solid acid catalyst, and preparation method and application thereof |
| CN106554277A (en) * | 2016-10-20 | 2017-04-05 | 陕西延长石油（集团）有限责任公司炼化公司 | A kind of solid acid catalysis synthesize the method for Isosorbide-5-Nitrae butylene glycol aerylate |
| CN112973663A (en) * | 2021-03-12 | 2021-06-18 | 盐城工学院 | Solid acid catalyst for catalyzing esterification reaction of pentaerythritol and stearic acid and preparation method thereof |
| CN112973663B (en) * | 2021-03-12 | 2023-03-10 | 盐城工学院 | Solid acid catalyst for catalyzing esterification reaction of pentaerythritol and stearic acid and preparation method thereof |
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