CN105688946B - A kind of solid acid catalyst and its preparation method and application - Google Patents
A kind of solid acid catalyst and its preparation method and application Download PDFInfo
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- CN105688946B CN105688946B CN201610115612.4A CN201610115612A CN105688946B CN 105688946 B CN105688946 B CN 105688946B CN 201610115612 A CN201610115612 A CN 201610115612A CN 105688946 B CN105688946 B CN 105688946B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/053—Sulfates
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/09—Preparation of ethers by dehydration of compounds containing hydroxy groups
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Abstract
The invention belongs to catalysis technical field, and in particular to a kind of solid acid catalyst and its preparation method and application.A kind of solid acid catalyst, it is characterised in that：The catalyst adds suitable rare earth sulfate in ferric sulfate, and composite inorganic salt catalyst is made, and then the complex inorganic salt catalyst is loaded using the multi-walled carbon nanotube of acidifying as carrier.The beneficial effects of the present invention are adding the catalyst after rare earth sulfate has the catalytic effect more excellent than one-component ferric sulfate, using multi-walled carbon nanotube as carrier, provides the specific surface area of bigger for the load of active component so that catalytic effect further improves.
Description
Technical field
The present invention relates to the catalyst of isopropanol dehydration synthesis diisopropyl ether, the preparation method of the catalyst is further related to.
Background technology
Isopropyl ether is widely used in many industries, such as a kind of important Organic Chemicals and industrial solvent:Make
Oil refinery gasoline octane number is improved for gasoline additive, reduces the volatility of gasoline;It is used to extract in tobacco as extractant
Tar and nicotine, extract vitamin A etc. from cod-liver oil.Due to the popularity of isopropyl ether application, many people are energetically
Required catalyst in its synthetic method and building-up process is in depth studied.
The reaction of isopropanol dehydration synthesis isopropyl ether is highly developed, and key is the preparation selection of catalyst, isopropyl
The catalyst of dehydration of alcohols synthesis isopropyl ether mainly has：The concentrated sulfuric acid, cover and ask soil, molecular sieve, cation exchange resin and solid to surpass
Strong acid etc..It is preferable that the concentrated sulfuric acid does catalyst activity, but to equipment corrosion than more serious, and environment is caused very big
Endanger patent；Cover support soil and molecular sieve to do catalyst activity poor, such as：（Publication number CN101757942）In with modification
Zeolite molecular sieve is catalyst, has propylene hydration to generate isopropyl ether, since reaction temperature is of a relatively high, generation at 160 DEG C
Isopropyl ether is selectively poor；Although cation exchange resin better catalytic activity, high temperature and for a long time use ,-SO3H
Easily come off, catalyst life is not grown.
Sulfate is had been applied in many acid catalyzed reactions as solid acid catalyst, but is synthesized for isopropanol dehydration
Isopropyl ether reacts there is not yet report, especially composite inorganic salt catalyst and its loaded catalyst.
For loaded catalyst, common carrier has aluminium oxide, silica and activated carbon etc., carbon nanotubes research
Then few, multi-walled carbon nanotube has more mesoporous compared with activated carbon, is very beneficial for the transmission of material, and with aluminium oxide and
Silica is compared, its surface area is larger；Meanwhile if catalyst inactivation can recycle the price phase of load by completely burned
To high active component.
The content of the invention
Deficiency existing for used catalyst, the present invention propose a kind of new solid acid in being synthesized for current isopropyl ether
Catalyst, adds suitable rare earth sulfate in ferric sulfate, and complex inorganic salt catalyst is made, then with the multi-walled carbon nanotube of acidifying
The complex inorganic salt catalyst is loaded for carrier, adds the catalyst after rare earth sulfate with more excellent than one-component ferric sulfate
Catalytic effect, using multi-walled carbon nanotube as carrier, the specific surface area of bigger is provided for the load of active component, have it is higher
Catalytic activity.
The present invention is achieved through the following technical solutions.
The present invention adds a small amount of rare earth sulfate in ferric sulfate, prepares composite inorganic salt catalyst, has than one pack system
The catalytic activity of ferric sulfate higher, the rare earth sulfate is cerous sulfate, in lanthanum sulfate, praseodymium sulfate, Dineodymium trisulfate, samarium sulphate
Any one.
Preferably, the sulfate is cerous sulfate and lanthanum sulfate.
The additive amount of above-mentioned rare earth sulfate accounts for the 1%-10% of sulfuric acid weight of iron, preferably 5%.
It is carrier that the present invention, which selects multi-walled carbon nanotube when being loaded to complex inorganic salt catalyst, is the load of active component
Provide larger specific surface area.Its step is as follows when being loaded：
（1）A certain amount of multi-walled carbon nanotube is taken, is 1 according to solid-liquid mass ratio：2-1：4 addition mass fractions are 20%-
40% salpeter solution, soaks 1-3h at 70-90 DEG C, deionized water is washed to cleaning solution be in neutrality after it is dry；
（2）Be 0.4-0.6 according to complex inorganic salt catalyst and multi-walled carbon nanotube amount ratio, take complex inorganic salt catalyst and（1）In consolidate
Body, adds absolute ethyl alcohol and makees solvent, added solvent absolute ethyl alcohol is with solid total mass ratio：8-10, flows back at 80-100 DEG C
2-4h, solvent evaporated at identical temperature, obtains solid acid catalyst.
Wherein, step（1）Middle solid-liquid mass ratio preferably 1：3, the mass fraction preferably 30% of nitric acid, soaking temperature and time
It is preferred that 80 DEG C, 2h；Step（2）In complex inorganic salt catalyst and carrier quality ratio preferably 0.5, absolute ethyl alcohol and solid total mass ratio are excellent
Select 9, preferably 90 DEG C of temperature and time, 2h during load.
A kind of application of the solid acid catalyst of the present invention in isopropanol dehydration synthesis isopropyl ether reaction, its specific practice
It is as follows：Using the solid acid catalyst, at 130-150 DEG C 3-5h is reacted using isopropanol as raw material, cooled down after reaction
To room temperature, catalyst is centrifuged out, gas chromatography surveys isopropyl ether content.Catalyst is post-treated, reuses, wherein instead
Answer preferably 140 DEG C of temperature and time, 4h.
The present invention another important feature be：Solid acid catalyst dosage is the 1%-8% of isopropanol mass fraction in reaction,
It is preferred that 6%.
Embodiment
Embodiment one
10gFe is weighed respectively2(SO4)3 With 0.1g Ce2(SO4)3It is fully finely ground after in evaporating dish in mortar, add
Absolute ethyl alcohol submerges mixture, and the lower heating of 90 DEG C of stirrings is evaporated, and obtains complex inorganic salt catalyst catalyst Fe2(SO4)3- Ce2(SO4)3, note
For A1.
Embodiment two
10gFe is weighed respectively2(SO4)3 With 0.1g La2(SO4)3It is fully finely ground after in evaporating dish in mortar, add
Absolute ethyl alcohol submerges mixture, and the lower heating of 90 DEG C of stirrings is evaporated, and obtains complex inorganic salt catalyst catalyst Fe2(SO4)3- La2(SO4)3, note
For A2.
Embodiment three
6gFe is weighed respectively2(SO4)3 With 0.06g Ce2(SO4)3It is fully finely ground after in evaporating dish in mortar, add
Absolute ethyl alcohol submerges mixture, and the lower heating of 90 DEG C of stirrings is evaporated, and obtains complex inorganic salt catalyst catalyst Fe2(SO4)3- Ce2(SO4)3, note
For A3；
10g multi-walled carbon nanotubes are weighed, add 20g mass fractions as 20% salpeter solution, magnetic agitation 1h at 70 DEG C,
Then a period of time is stood, is filtered, deionized water is washed to neutrality, 100 DEG C of dryings to constant weight.Dried carrier 10g is in three
In mouth bottle, 4gA3 is added, adds 70ml absolute ethyl alcohols, 2h is refluxed at 80 DEG C, solvent evaporated is up to load at identical temperature
Type catalyst, is denoted as B1.
Example IV
6gFe is weighed respectively2(SO4)3 With 0.3g La2(SO4)3It is fully finely ground after in evaporating dish in mortar, add nothing
Water-ethanol submerges mixture, and the lower heating of 90 DEG C of stirrings is evaporated, and obtains complex inorganic salt catalyst catalyst Fe2(SO4)3- La2(SO4)3, it is denoted as
A4；
10g multi-walled carbon nanotubes are weighed, add 30g mass fractions as 20% salpeter solution, magnetic agitation 2h at 80 DEG C,
Then a period of time is stood, is filtered, deionized water is washed to neutrality, 100 DEG C of dryings to constant weight.Dried carrier 10g is in three
In mouth bottle, 5gA4 is added, adds 85ml absolute ethyl alcohols, 3h is refluxed at 90 DEG C, solvent evaporated is up to load at identical temperature
Type catalyst, is denoted as B2.
Embodiment five
6gFe is weighed respectively2(SO4)3 With 0.6g Ce2(SO4)3It is fully finely ground after in evaporating dish in mortar, add nothing
Water-ethanol submerges mixture, and the lower heating of 90 DEG C of stirrings is evaporated, and obtains complex inorganic salt catalyst catalyst Fe2(SO4)3- Ce2(SO4)3, it is denoted as
A5；
10g multi-walled carbon nanotubes are weighed, add 40g mass fractions as 20% salpeter solution, magnetic agitation 3h at 90 DEG C,
Then a period of time is stood, is filtered, deionized water is washed to neutrality, 100 DEG C of dryings to constant weight.Dried carrier 10g is in three
In mouth bottle, 6gA5 is added, adds 100ml absolute ethyl alcohols, 4h is refluxed at 100 DEG C, solvent evaporated is up to negative at identical temperature
Supported catalyst, is denoted as B3.
Embodiment six
6gFe is weighed respectively2(SO4)3 With 0.6g La2(SO4)3It is fully finely ground after in evaporating dish in mortar, add nothing
Water-ethanol submerges mixture, and the lower heating of 90 DEG C of stirrings is evaporated, and obtains complex inorganic salt catalyst catalyst Fe2(SO4)3- La2(SO4)3, it is denoted as
A6；
10g multi-walled carbon nanotubes are weighed, add 40g mass fractions as 20% salpeter solution, magnetic agitation 3h at 90 DEG C,
Then a period of time is stood, is filtered, deionized water is washed to neutrality, 100 DEG C of dryings to constant weight.Dried carrier 10g is in three
In mouth bottle, 6gA6 is added, adds 100ml absolute ethyl alcohols, 4h is refluxed at 100 DEG C, solvent evaporated is up to negative at identical temperature
Supported catalyst, is denoted as B4.
Embodiment seven
19 15ml reaction kettles are taken, are separately added into 10ml isopropanols, catalyst is added and is reacted under specified conditions.Reaction knot
Shu Hou, Filtration of catalyst, the content of isopropyl ether see the table below in gas chromatographic detection product：
Claims (7)
1. a kind of solid acid catalyst, it is characterized in that, which is that appropriate rare earth sulfate is added in ferric sulfate,
Complex inorganic salt catalyst is prepared into, and the complex inorganic salt catalyst is loaded as carrier using being acidified multi-walled carbon nanotube, the catalysis
Agent is used in the reaction of isopropanol dehydration synthesis diisopropyl ether.
2. a kind of solid acid catalyst as claimed in claim 1, it is characterized in that, the rare earth sulfate is cerous sulfate, sulfuric acid
Any one in lanthanum, praseodymium sulfate, Dineodymium trisulfate, samarium sulphate.
3. a kind of solid acid catalyst as claimed in claim 1, it is characterized in that, the rare earth sulfate is cerous sulfate, sulfuric acid
Lanthanum.
4. a kind of solid acid catalyst as claimed in claim 1, it is characterized in that, sulphur in the preparation process of the solid acid catalyst
Sour cerium, the additive amount of lanthanum sulfate account for the 1%-10% of sulfuric acid weight of iron.
5. a kind of solid acid catalyst as claimed in claim 1, it is characterized in that, the acidifying multi-walled carbon nanotube, carries out acid
Used acid is nitric acid during change, and the mass fraction of nitric acid is：20%-40%, when immersion, take the solid-liquid mass ratio to be：1:2-1:4,
Soaking time is：1-3h, temperature are：70-90℃.
6. a kind of preparation method of solid acid catalyst as claimed in claim 1, its specific preparation process are as follows：
（1）The preparation of complex inorganic salt catalyst：It is abundant in mortar that ferric sulfate and cerous sulfate, lanthanum sulfate solid are weighed according to a certain percentage
Finely ground after in evaporating dish, addition absolute ethyl alcohol submerges mixture, stirs lower heating and is evaporated；
（2）A certain amount of multi-walled carbon nanotube is weighed to soak in the salpeter solution of certain mass fraction, deionized water wash to
Cleaning solution is in neutrality, spare after dry；
（3）It is 0.4-0.6 according to complex inorganic salt catalyst and multi-walled carbon nanotube mass ratio, takes（1）With（2）In solid, add nothing
Water-ethanol makees solvent, and added solvent absolute ethyl alcohol is with solid total mass ratio：8-10, flow back 2-4h at 80-100 DEG C, identical
At a temperature of solvent evaporated.
A kind of 7. application of solid acid catalyst as claimed in claim 1, it is characterized in that anti-in isopropanol dehydration synthesis isopropyl ether
Application in answering, its specific practice are as follows：It is anti-at 130-150 DEG C using isopropanol as raw material using the solid acid catalyst
3-5h is answered, catalyst amount is the 1-8% of isopropanol quality；It is cooled to room temperature after reaction, Filtration of catalyst, obtains slightly
Product isopropyl ether；Crude product isopropyl ether surveys isopropyl ether content through distilling to obtain product isopropyl ether, gas chromatography.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1368493A (en) * | 2001-02-07 | 2002-09-11 | 北京燕山石油化工公司研究院 | Process for preparing bimethyl ether by catalytic dewatering of methanol |
| CN1919451A (en) * | 2006-07-21 | 2007-02-28 | 新奥新能(北京)科技有限公司 | Catalyst for preparing dimethyl ether by methanol dehydration and its preparation method |
| CN101176847A (en) * | 2007-11-27 | 2008-05-14 | 浙江大学 | Complex vitriolate dehydration catalyst as well as method for preparing propenoic acid and methyl ester using the same |
-
2016
- 2016-03-02 CN CN201610115612.4A patent/CN105688946B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1368493A (en) * | 2001-02-07 | 2002-09-11 | 北京燕山石油化工公司研究院 | Process for preparing bimethyl ether by catalytic dewatering of methanol |
| CN1919451A (en) * | 2006-07-21 | 2007-02-28 | 新奥新能(北京)科技有限公司 | Catalyst for preparing dimethyl ether by methanol dehydration and its preparation method |
| CN101176847A (en) * | 2007-11-27 | 2008-05-14 | 浙江大学 | Complex vitriolate dehydration catalyst as well as method for preparing propenoic acid and methyl ester using the same |
Non-Patent Citations (2)
| Title |
|---|
| 丙烯醚化合成二异丙醚催化剂研究;张淑梅等;《燃料化学学报》;20050228;第33卷(第1期);107-111 * |
| 催化合成异丙醚的研究进展;冯文国等;《石油化工》;19981231;第27卷(第9期);695-699 * |
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