CN107876088A - A kind of method that electrophilic substitution reaction prepares stability solid acid catalyst - Google Patents
A kind of method that electrophilic substitution reaction prepares stability solid acid catalyst Download PDFInfo
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- CN107876088A CN107876088A CN201711084915.5A CN201711084915A CN107876088A CN 107876088 A CN107876088 A CN 107876088A CN 201711084915 A CN201711084915 A CN 201711084915A CN 107876088 A CN107876088 A CN 107876088A
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- solid acid
- carrier
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- electrophilic substitution
- substitution reaction
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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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0215—Sulfur-containing compounds
- B01J31/0225—Sulfur-containing compounds comprising sulfonic acid groups or the corresponding salts
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/12—Oxidising
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Abstract
The invention discloses a kind of method that electrophilic substitution reaction prepares stability solid acid catalyst, comprise the following steps：1) pretreatment of carrier：From aromatic ring compounds of group as carrier, it is added to after carrier is carried out into activating pretreatment in deionized water；2) parental materials：Instill the sulfonate presoma containing carbon-carbon double bond or chloromethyl and be stirred reaction, filtered after stirring reaction, washing；Finally product is dried processing.Charcoal is modified makes it possible to receive more faintly acid positions first by the present invention, with (CH2)n‑SO3H groups instead of traditional SO3H groups, which not only improves the sour density of solid acid, and solve the problems, such as the leaching of solid acid, not only increase the catalytic efficiency of catalyst, and improve the purity of product.
Description
Technical field
The invention belongs to catalyst preparation technical field, and in particular to a kind of electrophilic substitution reaction prepares stability solid acid
The method of catalyst.
Background technology
With the development of mankind's technology, fossil fuel is increasingly exhausted, and people transfer to study recyclable fuel.Inedible
Biomass such as agricultural wastes and forestry waste are exactly good recyclable organism fuel.In order to convert biomass into biological combustion
Material is, it is necessary to be hydrolyzed and pyrolysis processing.It can be carried out during pyrolysis in the case of without catalyst, but in the hydrolysis phase
Between have to the participation of catalyst, and the upgrading of bio oil has to use acidic catalyst, thus acidic catalyst be must
An indispensable part.
Although existing solid acid widely applies in industrial production, many problems are remained.Such as
Amberlyst 70, the low about 2.55mmol/g of its sour density, operation temperature is low to be less than 190 DEG C, and its acidic leaching-
SO3H groups can be with H2SO 4Form leached in hot aqueous medium, mixed with product liquid, polluted product.Therefore, it is necessary to open
The synthetic route for sending out new, suppress the back reaction of sulfonating reaction, to prepare new catalyst.
The content of the invention
The present invention is intended to provide a kind of method that electrophilic substitution reaction prepares stability solid acid catalyst, the present invention is first
Aromatic compound such as charcoal is modified and makes it possible to receive more faintly acid positions, with-(CH2)n-SO3H groups instead of
Traditional-SO3H groups, which not only improves the sour density of solid acid, and solve the problems, such as the leaching of solid acid, not only carry
The high catalytic efficiency of catalyst, and improve the purity of product.
What the present invention realized by the following technical solutions, one aspect of the present invention provides a kind of electrophilic substitution reaction and prepared surely
The method of qualitative solid acid catalyst, comprises the following steps：
1) pretreatment of carrier：From aromatic ring compounds of group as carrier, it is added to after carrier is carried out into activating pretreatment
In deionized water；
2) parental materials：Instill the sulfonate presoma containing carbon-carbon double bond or chloromethyl and be stirred reaction, stirring is anti-
Should after filtered, washed with dilute acid soln；Finally product is dried processing.
Because sulfonation is high reversible, desulphurization reaction is inherently hydrolysis, in order to prevent-SO3H hydrolysis,
Need to be in aromatic ring and-SO3Hydrocarbon chain is inserted between H groups, to prepare stability solid acid catalyst, in aqueous phase, aromatic ring connects with carbon
The key connect is covalent bond, so be difficult to be destroyed, while aliphatic carbon chain does not possess pi bond to give-SO3H electrophilic additions, therefore
Carbochain and-SO3H groups are also difficult to decompose.
The present invention realizes-(CH by the reaction of alkyl introducing aromatic ring2)n-SO3The electrophilic substitution reaction of H groups, this
Individual reaction can be carried out under gentle reaction, and reacted and will not be stopped in single substitution reaction；Groups have supplied for electronic work
With multiple-(CH2)n-SO3H groups be directed into an aromatic ring, and which greatly enhances the sour close of solid acid catalyst
Degree.And in the sulfonating reaction of prior art, because-SO3H groups are electrophilic, therefore only a group is introduced into virtue
Ring, the sour density are low.
Preferably, the mol ratio of each material is：Carrier：Sulfonate presoma=1 of carbon-carbon double bond or chloromethyl:
2~1:6.
Preferably, in step 1), the aromatic ring compounds of group selects charcoal, and activating pretreatment step is：By biology
Charcoal is added in the beaker equipped with strong acid and stirred, and is then slow added into strong oxidizer, backflow, is washed with deionized, and filters.
Charcoal is the joint product of biomass pyrolytic, has a high surface specific surface area, unique pore structure and multiple
Surface functional group, the hydrophilic radical such as hydroxyl and carboxyl of biological carbon surface can be with avtive spots, to keep biomass such as (to form hydrogen
Key) as reactant so that acidic site close to be easier；Hydroxyl can be introduced by acid treatment, and carboxyl can pass through
Strong oxidizer (hydrogen peroxide, KMnO4Deng) oxidation introduce.
Preferably, in step 1), the strong oxidizer is from one kind in hydrogen peroxide and potassium permanganate.
Preferably, in step 1), the strong acid selects concentrated nitric acid or the concentrated sulfuric acid.
Preferably, in step 2), the stirring reaction of the carrier and carbon-carbon double bond or the sulfonate presoma of chloromethyl
Temperature be 20-90 DEG C, stir the time as 2~6 hours.
Filtered, washed preferably, adding dilute hydrochloric acid solution in step 2), after stirring reaction.
The present invention compared with prior art, has following good effect：
Aromatic compound such as charcoal is modified makes it possible to receive more faintly acid positions first by the present invention, with-
(CH2)n-SO3H groups instead of traditional-SO3H groups, which not only improves the sour density of solid acid, and solves solid
The leaching problem of acid, not only increases the catalytic efficiency of catalyst, and improve the purity of product.
Brief description of the drawings
In order to illustrate more clearly about the embodiment of the present invention or technical scheme of the prior art, below will be to embodiment or existing
There is the required accompanying drawing used in technology description to be briefly described, it should be apparent that, drawings in the following description are only this
Some embodiments of invention, for those of ordinary skill in the art, on the premise of not paying creative work, can be with
Other accompanying drawings are obtained according to these accompanying drawings.
Fig. 1 is the synthesis path of prior art solid acid；
Fig. 2 is the synthesis path of solid acid of the present invention；
Fig. 3 is Amberlyst 70 and using solid acid made from methylpropene sodium sulfonate as presoma in hydrothermal condition (210
DEG C) lower surface acid density changes over time curve.
Embodiment
In order to make the purpose , technical scheme and advantage of the present invention be clearer, with reference to embodiments, to the present invention
It is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, it is not used to
Limit the present invention.
The application principle of the present invention is further described with reference to specific embodiment.
Embodiment 1, as shown in Fig. 2 a kind of method that electrophilic substitution reaction prepares stability solid acid catalyst, including with
Lower step：
1) pretreatment of carrier：It is carrier from charcoal, charcoal is added in the beaker equipped with concentrated nitric acid and stirred, so
After be slow added into potassium permanganate strong oxidizer, flow back 8-12h at a temperature of 80 to 90 DEG C, is washed with deionized, filter, then
It is added in deionized water；
2) parental materials：Instillation contains methylpropene sodium sulfonate presoma, according to charcoal：Methylpropene sodium sulfonate forerunner
Body=1:2 ratio is stirred reaction, and the temperature of stirring reaction is 40 DEG C, the time is stirred as 5 hours, with dilute salt after stirring reaction
Acid solution is filtered, washed；Finally product is dried processing.
Embodiment 2, as shown in Fig. 2 a kind of method that electrophilic substitution reaction prepares stability solid acid catalyst, including with
Lower step：
1) pretreatment of carrier：It is carrier from charcoal, charcoal is added in the beaker equipped with concentrated nitric acid and stirred, so
After be slow added into hydrogen peroxide oxidant, flow back 8-12h at a temperature of 80 to 90 DEG C, is washed with deionized, filter, then add
Into deionized water；
2) parental materials：Instillation contains methylpropene sodium sulfonate presoma, according to charcoal：Methylpropene sodium sulfonate forerunner
Body=1:6 ratio is stirred reaction, and the temperature of stirring reaction is 40 DEG C, the time is stirred as 6 hours, with dilute salt after stirring reaction
Acid solution is filtered, washed；Finally product is dried processing.
Embodiment 3, as shown in Fig. 2 a kind of method that electrophilic substitution reaction prepares stability solid acid catalyst, including with
Lower step：
1) pretreatment of carrier：It is carrier from charcoal, charcoal is added in the beaker equipped with concentrated nitric acid and stirred, so
After be slow added into potassium permanganate strong oxidizer, flow back 8-12h at a temperature of 80 to 90 DEG C, is washed with deionized, filter, then
It is added in deionized water；
2) parental materials：Instillation contains methylpropene sodium sulfonate presoma, according to charcoal：Methylpropene sodium sulfonate forerunner
Body=1:4 ratio is stirred reaction, and the temperature of stirring reaction is 80 DEG C, the time is stirred as 4 hours, with dilute salt after stirring reaction
Acid solution is filtered, washed；Finally product is dried processing.
Charcoal is the joint product of biomass pyrolytic, has a high surface specific surface area, unique pore structure and multiple
Surface functional group, the hydrophilic radical such as hydroxyl and carboxyl of biological carbon surface can be with avtive spots, to keep biomass such as (to form hydrogen
Key) as reactant so that acidic site close to be easier；Hydroxyl can be introduced by acid treatment, and carboxyl can pass through
Strong oxidizer (hydrogen peroxide, KMnO4Deng) oxidation introduce.
Because sulfonation is high reversible, desulphurization reaction is inherently hydrolysis, in order to prevent-SO3H hydrolysis,
Need to be in aromatic ring and-SO3Hydrocarbon chain is inserted between H groups, to prepare stability solid acid catalyst, in aqueous phase, aromatic ring connects with carbon
The key connect is covalent bond, so be difficult to be destroyed, while aliphatic carbon chain does not possess pi bond to give-SO3H electrophilic additions, therefore
Carbochain and-SO3H groups are also difficult to decompose.
The present invention realizes-(CH by the reaction of alkyl introducing aromatic ring2)n-SO3The electrophilic substitution reaction of H groups, this
Individual reaction can be carried out under gentle reaction, and reacted and will not be stopped in single substitution reaction；Groups have supplied for electronic work
With multiple-(CH2)n-SO3H groups be directed into an aromatic ring, and which greatly enhances the sour close of solid acid catalyst
Degree.And in the sulfonating reaction of prior art, because-SO3H groups are electrophilic, therefore only a group is introduced into virtue
Ring, the sour density are low.
Above-described embodiment 1~3 and comparison of the prior art in terms of stability：
Prior art：Amberlyst 70 highest uses temperature in the Amberlyst series solid acids of DOW Chemical at present
Spend for 190 DEG C；
The present invention：The sulfonic acid type solid acid prepared by the electrophilic substitution reaction of vinylsulfonate and aromatic ring uses temperature
>=230 DEG C of degree.Experiment proves：(>=230 DEG C) can be stablized 200 hours catalyst under hydrothermal conditions, its acidic site removal efficiency<
5%.Table 1 is the stability data of embodiment 1~3.
Table 1
As shown in figure 3, it is Amberlyst 70 and using solid acid made from methylpropene sodium sulfonate as presoma in hydro-thermal
Condition (210 DEG C) lower surface acid density changes over time curve；As can be seen from Figure 3：Using methylpropene sodium sulfonate as forerunner
Solid acid made from body is under hydrothermal condition (210 DEG C), and the surface acid density in 150min is still above 3.5mmol/g；And
For Amberlyst 70 under hydrothermal condition (210 DEG C), the surface acid density in 150min is only 1.6mmol/g.
Certainly, described above is also not limited to the example above, the technical characteristic of the invention without description can by or
Realized, will not be repeated here using prior art；Above example and accompanying drawing are merely to illustrate technical scheme
It is limitation of the present invention, the present invention is described in detail with reference to preferred embodiment, the ordinary skill people of this area
Member is it should be appreciated that change, remodeling, the addition that those skilled in the art are made in the essential scope of the present invention
Or replace the claims that without departure from spirit of the invention, should also belong to the present invention.
Claims (7)
1. a kind of method that electrophilic substitution reaction prepares stability solid acid catalyst, it is characterised in that：Comprise the following steps：
1) pretreatment of carrier：From aromatic ring compounds of group as carrier, carrier is carried out be added to after activating pretreatment from
In sub- water；
2) parental materials：Instill the sulfonate presoma containing carbon-carbon double bond or chloromethyl and be stirred reaction, after stirring reaction
Filtered, washed with dilute acid soln；Finally product is dried processing.
2. the method that a kind of electrophilic substitution reaction according to claim 1 prepares stability solid acid catalyst, its feature
It is：The mol ratio of each material is：Carrier：Sulfonate presoma=1 of carbon-carbon double bond or chloromethyl:2~1:6.
3. the method that a kind of electrophilic substitution reaction according to claim 1 prepares stability solid acid catalyst, its feature
It is：In step 1), the aromatic ring compounds of group selects charcoal, and activating pretreatment step is：Charcoal is added to equipped with strong
Stirred in the beaker of acid, be then slow added into strong oxidizer, flowed back, be washed with deionized, filtered.
4. the method that a kind of dipping-carbonizatin method according to claim 3 prepares peracid density solid catalyst, its feature exist
In：In step 1), the strong oxidizer is from one kind in hydrogen peroxide and potassium permanganate.
5. the method that a kind of dipping-carbonizatin method according to claim 3 prepares peracid density solid catalyst, its feature exist
In：In step 1), the strong acid selects concentrated nitric acid or the concentrated sulfuric acid.
6. the method that a kind of electrophilic substitution reaction according to claim 1 prepares stability solid acid catalyst, its feature
It is：In step 2), the temperature of the carrier and carbon-carbon double bond or the stirring reaction of the sulfonate presoma of chloromethyl is 20-90
DEG C, the time is stirred as 2~6 hours.
7. the method that a kind of electrophilic substitution reaction according to claim 1 prepares stability solid acid catalyst, its feature
It is：Dilute hydrochloric acid solution is added in step 2), after stirring reaction to be filtered, washed.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201711084915.5A CN107876088B (en) | 2017-11-07 | 2017-11-07 | Method for preparing stable solid acid catalyst by electrophilic substitution reaction |
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| CN201711084915.5A CN107876088B (en) | 2017-11-07 | 2017-11-07 | Method for preparing stable solid acid catalyst by electrophilic substitution reaction |
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| CN107876088B CN107876088B (en) | 2020-06-19 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111346673A (en) * | 2020-03-19 | 2020-06-30 | 济南大学 | Preparation method and application of high-acid-density solid acid catalyst |
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| CN101773860A (en) * | 2010-02-05 | 2010-07-14 | 绍兴文理学院 | Carbon-based solid acid catalyst synthesized by one-step hydrothermal carbonization process |
| CN102218342A (en) * | 2011-04-02 | 2011-10-19 | 华东理工大学 | Preparation method of high efficient sulfonated carbon solid acid catalyst |
| CN103691483A (en) * | 2013-12-16 | 2014-04-02 | 太原理工大学 | Carbon-based solid acid catalyst and preparation method thereof |
| CN104028307A (en) * | 2014-06-25 | 2014-09-10 | 中国矿业大学 | Magnetic solid super acidic catalyst and preparation method thereof |
| CN104815690A (en) * | 2015-04-14 | 2015-08-05 | 贵州大学 | Multi-sulfonic acid funtionalized mesoporous polymeric solid acid catalyst and preparation method and application thereof |
| CN106345491A (en) * | 2016-07-29 | 2017-01-25 | 中国科学院广州能源研究所 | Grafted solid acid catalyst, preparation method thereof and application of grafted solid acid catalyst in saccharification process of lignocellulose |
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2017
- 2017-11-07 CN CN201711084915.5A patent/CN107876088B/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101773860A (en) * | 2010-02-05 | 2010-07-14 | 绍兴文理学院 | Carbon-based solid acid catalyst synthesized by one-step hydrothermal carbonization process |
| CN102218342A (en) * | 2011-04-02 | 2011-10-19 | 华东理工大学 | Preparation method of high efficient sulfonated carbon solid acid catalyst |
| CN103691483A (en) * | 2013-12-16 | 2014-04-02 | 太原理工大学 | Carbon-based solid acid catalyst and preparation method thereof |
| CN104028307A (en) * | 2014-06-25 | 2014-09-10 | 中国矿业大学 | Magnetic solid super acidic catalyst and preparation method thereof |
| CN104815690A (en) * | 2015-04-14 | 2015-08-05 | 贵州大学 | Multi-sulfonic acid funtionalized mesoporous polymeric solid acid catalyst and preparation method and application thereof |
| CN106345491A (en) * | 2016-07-29 | 2017-01-25 | 中国科学院广州能源研究所 | Grafted solid acid catalyst, preparation method thereof and application of grafted solid acid catalyst in saccharification process of lignocellulose |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111346673A (en) * | 2020-03-19 | 2020-06-30 | 济南大学 | Preparation method and application of high-acid-density solid acid catalyst |
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