CN101147880A - Method for preparing condensing multi-kernel aromatic resin carbon based solid acid catalyst - Google Patents
Method for preparing condensing multi-kernel aromatic resin carbon based solid acid catalyst Download PDFInfo
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- CN101147880A CN101147880A CNA2007100446135A CN200710044613A CN101147880A CN 101147880 A CN101147880 A CN 101147880A CN A2007100446135 A CNA2007100446135 A CN A2007100446135A CN 200710044613 A CN200710044613 A CN 200710044613A CN 101147880 A CN101147880 A CN 101147880A
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Abstract
The present invention discloses a preparation method of new-type condensed polynuclear aromatic resin carbon base solid acid catalyst. Said preparation method includes the following steps: using polycyclic aromatic compound or its mixture as raw material, using aldehyde compound as cross-linking agent, using inorganic strong acid as catalyst, making condensation reaction to obtain B-stage condensed polynuclear aromatic resin; adding inorganic strong acid and aldehyde compound in the B-stage condensed polynuclear aromatic resin, making continuous reaction at high temperature to obtain C-stage condensed polyunuclear aromatic resin; then making the C-stage condensed polynuclear romatic resin undergo the processes of sulfonation, washing by using water, filtering, removing sulfonating agent and drying so as to obtain the invented target product.
Description
Technical field
The present invention relates to the preparation method of Preparation of catalysts method, particularly a kind of condensing multi-kernel aromatic resin carbon based solid acid catalyst.
Background technology
Today of crisis occurs in energy problem, environmental problem, seek with a spot of energy, do not produce unnecessary accessory substance, can generate the important goal that the purpose product is a modern chemical industry effectively.Acid catalyst is absolutely necessary in the modern chemistry industry, is widely used in the manufacturing of variety of products such as medicine, petro chemical industry product, macromolecule product, but the liquid acid that its most acid catalyst is hydrochloric acid, sulfuric acid and so on.The liquid catalyst that uses in the manufacturing process is neutralized by alkali, by removing the operation of the salt that is generated by neutralization, separates from product, reclaims.But the energy that consumes in the operation of removing of above-mentioned neutralization and salt accounts for quite a few that manufacturing process's integral body is used energy.In addition, the salt excess supply that on market, reclaims, it mostly is the little accessory substance of availability greatly, therefore is difficult to usually handle.
With respect to above-mentioned situation, because solid acid catalyst can not generate unnecessary accessory substance in the operation of removing of separating, do not need when reclaiming above-mentioned neutralization or salt, and energy-conservation ground manufacturing purpose product, therefore the research of this respect has been subjected to scientific worker's concern (Ishihara, K; Hasegawa, A; Yamamoto, H.Angew.Chem.Int.Ed.2001,40,4077).Aspect the research and development of solid acid catalyst, solid acid catalysts such as zeolite, silica-alumina, moisture niobium have become the huge achievement of chemical industry, bring very big contribution to society.The material that the polystyrene sulfonation obtains as the strong acid polymer, can be thought solid acid, in the past always as having acid cationic ion-exchange resin.In addition, the known Nafion (registration mark of E.I.Du Pont Company) that has sulfo group in the polytetrafluoroethylene (PTFE) skeleton also is the extremely strong solid acid of possess hydrophilic property (solid super-strong acid), and the super acids that their conducts have greater than the acid strength of liquid acid works.Yet the cationic ion-exchange resin of polystyrene sulfonation has pair thermally labile, selling at exorbitant prices during the industrial use of Nafion.Consider that from aspects such as performance and costs use solid acid catalyst than using liquid acid and more be difficult to design favourable industrial processes, in chemical industry, acid catalyzed reaction mostly depends on liquid acid catalyst now.In order to break this present situation, wish to appear at the solid acid catalyst that performance and cost aspect surpass liquid acid.
Summary of the invention
The objective of the invention is to provide the preparation method of the novel condensing multi-kernel aromatic resin carbon based solid acid catalyst of a kind of environmental friendliness and economy at the deficiencies in the prior art.
Reaction expression of the present invention is as follows:
B rank condensing multi-kernel aromatic resin:
C rank condensing multi-kernel aromatic resin:
Sulfonation:
The present invention is: with condensed-nuclei aromatics or its mixture is that raw material, aldehyde compound serve as that connection agent, inorganic acid are catalyst, carries out condensation reaction, gets B rank condensing multi-kernel aromatic resin; In the condensing multi-kernel aromatic resin of B rank, add inorganic acid and aldehyde compound again, at high temperature continue reaction, get C rank condensing multi-kernel aromatic resin; Then C rank condensing multi-kernel aromatic resin is carried out sulfonation, washing, filtration, removal sulfonating agent, products therefrom is drying to obtain target product in baking oven, and its concrete steps are as follows:
The 1st step made B rank condensing multi-kernel aromatic resin
In the three-necked bottle that has electromagnetic agitation, thermometer, reflux condensing tube, water knockout drum, add: condensed-nuclei aromatics or its mixture, with condensed-nuclei aromatics or its mixture mol ratio be that 1: 1～5 aldehyde compound, the molar percentage that accounts for condensed-nuclei aromatics or its mixture are 0.1～5% inorganic acid, add thermal agitation, carry out condensation reaction 8～72h under 120～180 ℃, the dope that gets black is B rank condensing multi-kernel aromatic resins.
The 2nd step made C rank condensing multi-kernel aromatic resin
In the above-mentioned black dope that obtains, add again: the molar percentage that accounts for above-mentioned condensed-nuclei aromatics or its mixture be 0.1～5% inorganic acid, with condensed-nuclei aromatics or its mixture mol ratio be 1～5 aldehyde compound, be heated to 200～400 ℃, be cured reaction 4～16h, get C rank condensing multi-kernel aromatic resin.
The 3rd step washing suction filtration and oven dry
After the above-mentioned C rank condensing multi-kernel aromatic resin that obtains is cooled to room temperature, add 80～100 ℃ hot water, wash, filter, till the filtrate clarification, not having inorganic acid to be detected, again product is placed 120 ℃ baking oven, dried 1～2 day.
The 4th step sulfonating reaction and washing suction filtration
In having the 100mL three-necked bottle of electromagnetic agitation, thermometer, reflux condensing tube, water knockout drum, add: the solid product that the 3rd step obtained, with described solid product mass ratio be 1: 2～10 sulfuric acid, add thermal agitation, behind reaction 8～48h under 80～200 ℃, after reactant liquor is cooled to room temperature, in the impouring cold water, carry out suction filtration, hot water with 80～100 ℃ washs, till the filtrate clarification, not having sulfuric acid to be detected, again product is placed 120 ℃ baking oven, dried 1～2 day, and got novel condensing multi-kernel aromatic resin carbon based solid acid catalyst.
Described condensed-nuclei aromatics or its mixture are methyl naphthalene, naphthalene, pitch or tar.
Described aldehyde compound is formaldehyde, paraformaldehyde or benzaldehyde.
Described inorganic acid is sulfuric acid, hydrochloric acid or nitric acid.
Compared with prior art, the advantage of products therefrom of the present invention is: (1) heat endurance height, and heat decomposition temperature is more than 160 ℃; (2) acid number height, general acid number is at 1～6mmol/g; (3) He Cheng cost is low; (4) excellent catalytic effect, to general acid catalyzed reaction as: esterification, condensation, alkylation, etherificate etc. have very high catalytic activity; (5) catalyst can repeat repeatedly to use; (6) be with a wide range of applications.
The specific embodiment
Below will the present invention is further elaborated by specific embodiment:
Embodiment 1
The 1st step made B rank condensing multi-kernel aromatic resin
Add in having the 100mL three-necked bottle of electromagnetic agitation, thermometer, reflux condensing tube, water knockout drum: 0.1mol naphthalene, 0.5mol paraformaldehyde, 0.1g sulfuric acid add thermal agitation, carry out condensation reaction 24h under 150 ℃, obtain the dope of black.
The 2nd step made C rank condensing multi-kernel aromatic resin
Add 0.5g sulfuric acid again in the above-mentioned dope that obtains, the 0.1mol paraformaldehyde is heated to 250 ℃, is cured reaction 16h;
The 3rd step washing suction filtration and oven dry
After the above-mentioned C rank condensing multi-kernel aromatic resin that obtains was cooled to room temperature, the hot water that adds 80 ℃ washed, and filters, until the filtrate clarification, there is no sulfuric acid and detect till, again product is placed 120 ℃ baking oven, dried 1 day.
The 4th step sulfonating reaction and washing suction filtration
Add in having the 100mL three-necked bottle of electromagnetic agitation, thermometer, reflux condensing tube, water knockout drum: solid product, 20g sulfuric acid that the 3rd step of 2g obtains add thermal agitation, behind reaction 28h under 120 ℃; Behind the reactant liquor cool to room temperature, in the impouring cold water, carry out suction filtration, wash with 90 ℃ hot water, until filtrate clarification, till there is no sulfuric acid and detecting, again product is placed 120 ℃ baking oven, dried 1 day, obtain target product, its acid number is 1.6mmol/g, and heat decomposition temperature is 220 ℃.
Embodiment 2-4
Except for the following differences, all the other are identical with embodiment 1, and paraformaldehyde the results are shown in Table 1 in the ratio consumption of table 1
Table 1
| Embodiment | Paraformaldehyde (mol) | Acid number/mmol/g | Heat decomposition temperature/℃ |
| 2 3 4 | 0.1 1 1.8 | 1.0 1.2 2.1 | 180 210 220 |
Embodiment 5-7
Except for the following differences, all the other are identical with embodiment 1, and the sulfonating reaction time provides by table 2 respectively.
Table 2
| Embodiment | Reaction time/h | Acid number/mmol/g | Heat decomposition temperature/℃ |
| 5 6 7 | 12 24 30 | 1.0 1.3 1.8 | 180 220 210 |
Embodiment 8-15
Except for the following differences, all the other are identical with embodiment 1, and the influence of differential responses thing the results are shown in Table 3.
Table 3
| Embodiment | Condensed-nuclei aromatics or its mixture | Aldehydes | Acid number/mmol/g | Heat decomposition temperature/℃ |
| 8 9 10 11 12 13 14 15 | Naphthalene menaphthyl menaphthyl menaphthyl naphthalene pitch pitch pitch | Formaldehyde benzaldehyde paraformaldehyde formaldehyde benzaldehyde paraformaldehyde formaldehyde benzaldehyde | 1.0 1.2 1.5 1.6 1.8 1.0 1.1 1.2 | 180 200 210 220 230 210 210 230 |
Embodiment 16
Catalytic esterification: adding 0.1mol citric acid, 0.45mol n-butanol add thermal agitation in having the 100mL three-necked bottle of electromagnetic agitation, thermometer, reflux condensing tube, water knockout drum, treat the complete molten back of citric acid sampling and measuring acidity, the product of the present invention that adds 0.5g then, adding hot reflux stirs, the water that reaction is produced is told from water knockout drum, reaction 4h, calculated yield is 98.2%.
Embodiment 17-21
Except for the following differences, all the other are identical with embodiment 16, and after reaction finished, product of the present invention carried out filtered and recycled, after the acetone washing, place 100 ℃ of baking oven dryings after, continue reaction, the results are shown in Table 4.
Table 4
| Embodiment | The reuse number of times | Yield/% |
| 17 18 19 20 21 | 0 1 2 3 4 | 98.2 97.9 96.0 98.7 98.7 |
Embodiment 22
Catalyzing and condensing reaction: in having the 100mL three-necked bottle of electromagnetic agitation, reflux condensing tube, water knockout drum, add 0.1mol cyclohexanone, 0.15mol ethylene glycol, 10ml cyclohexane and 0.1g product of the present invention, adding the hot reflux stirring steams the water and the entrainer azeotropic of reaction generation, about reaction 2h, yield is 99%.Product of the present invention is reused 5 times, and catalytic activity does not change.
Embodiment 23
Catalytic alkylation reaction: add 0.1mol catechol, the 0.15mol tert-butyl alcohol and 0.1g product of the present invention in having the 100mL three-necked bottle of electromagnetic agitation, reflux condensing tube, water knockout drum, add hot reflux and stir, about reaction 4h, yield is 90%.Product of the present invention is reused 5 times, and catalytic activity does not change.
Embodiment 24
The catalyst etherifying reaction: add 0.1mol2-naphthols, 0.15mol methyl alcohol and 0.1g product of the present invention in having the 100mL three-necked bottle of electromagnetic agitation, reflux condensing tube, water knockout drum, add hot reflux and stir, about reaction 6h, yield is 96%.Product of the present invention is reused 5 times, and catalytic activity does not change.
Claims (4)
1. the preparation method of a condensing multi-kernel aromatic resin carbon based solid acid catalyst, it is characterized in that: with condensed-nuclei aromatics or its mixture is that raw material, aldehyde compound serve as that connection agent, inorganic acid are catalyst, carry out condensation reaction, get B rank condensing multi-kernel aromatic resin; In the condensing multi-kernel aromatic resin of B rank, add inorganic acid and aldehyde compound again, at high temperature continue reaction, get C rank condensing multi-kernel aromatic resin; Then C rank condensing multi-kernel aromatic resin is carried out sulfonation, washing, filtration, removal sulfonating agent, products therefrom is drying to obtain target product in baking oven, and its concrete steps are as follows:
The 1st step made B rank condensing multi-kernel aromatic resin
In the three-necked bottle that has electromagnetic agitation, thermometer, reflux condensing tube, water knockout drum, add: condensed-nuclei aromatics, with the condensed-nuclei aromatics mol ratio be that 1～5 aldehyde compound, the molar percentage that accounts for condensed-nuclei aromatics are 0.1～5% inorganic acid, add thermal agitation, carry out condensation reaction 8～72h under 120～180 ℃, the dope that gets black is B rank condensing multi-kernel aromatic resins;
The 2nd step made C rank condensing multi-kernel aromatic resin
In the above-mentioned black dope that obtains, add again: the molar percentage that accounts for above-mentioned condensed-nuclei aromatics be 0.1～5% inorganic acid, with the condensed-nuclei aromatics mol ratio be 1～5 aldehyde compound, be heated to 200～400 ℃, be cured reaction 4～16h, get C rank condensing multi-kernel aromatic resin;
The 3rd step washing suction filtration and oven dry
After the above-mentioned C rank condensing multi-kernel aromatic resin that obtains is cooled to room temperature, add 80～100 ℃ hot water, wash, filter, till the filtrate clarification, not having inorganic acid to be detected, again product is placed 120 ℃ baking oven, dried 1～2 day;
The 4th step sulfonating reaction and washing suction filtration
In having the 100mL three-necked bottle of electromagnetic agitation, thermometer, reflux condensing tube, water knockout drum, add: the solid product that the 3rd step obtained, with described solid product mass ratio be 1: 2～10 sulfuric acid, add thermal agitation, behind reaction 8～48h under 80～200 ℃, after reactant liquor is cooled to room temperature, in the impouring cold water, carry out suction filtration, hot water with 80～100 ℃ washs, till the filtrate clarification, not having sulfuric acid to be detected, again product is placed 120 ℃ baking oven, dried 1～2 day, and got novel condensing multi-kernel aromatic resin carbon based solid acid catalyst.
2. preparation method according to claim 1 is characterized in that described condensed-nuclei aromatics or its mixture are methyl naphthalene, naphthalene, pitch or tar.
3. preparation method according to claim 1 is characterized in that described aldehyde compound is formaldehyde, paraformaldehyde or benzaldehyde.
4. preparation method according to claim 1 is characterized in that described inorganic acid is sulfuric acid, hydrochloric acid or nitric acid.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102453227A (en) * | 2010-10-26 | 2012-05-16 | 武汉保华石化新材料开发有限公司 | Preparation method for polycyclic aromatic hydrocarbon resin |
| CN102574963A (en) * | 2009-09-15 | 2012-07-11 | 三菱瓦斯化学株式会社 | Aromatic hydrocarbon resin and composition for forming underlayer film for lithograph |
| CN102716767A (en) * | 2012-07-04 | 2012-10-10 | 太原理工大学 | Preparation method of high-acid-content carbon-based solid acid |
| CN102728404A (en) * | 2012-06-27 | 2012-10-17 | 南京工业大学 | Preparation method for carbon-base solid sulfonic acid catalyst for hydrolysis |
| CN102040727B (en) * | 2009-10-13 | 2013-07-17 | 中国石油化工股份有限公司 | Novel process for utilizing catalytic cracked heavy oil and condensed multinuclear anime prepared with same |
| CN112851893A (en) * | 2021-01-07 | 2021-05-28 | 浙江万里新材料科技有限公司 | Irradiation crosslinking polyethylene foam material and preparation method thereof |
| CN113527639A (en) * | 2021-08-02 | 2021-10-22 | 武汉科技大学 | Method for preparing spinnable asphalt with high softening point from naphthalene and product thereof |
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- 2007-08-07 CN CNB2007100446135A patent/CN100560206C/en not_active Expired - Fee Related
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| EP2479198A4 (en) * | 2009-09-15 | 2013-12-25 | Mitsubishi Gas Chemical Co | Aromatic hydrocarbon resin and composition for forming underlayer film for lithography |
| CN102574963A (en) * | 2009-09-15 | 2012-07-11 | 三菱瓦斯化学株式会社 | Aromatic hydrocarbon resin and composition for forming underlayer film for lithograph |
| EP2479198A1 (en) * | 2009-09-15 | 2012-07-25 | Mitsubishi Gas Chemical Company, Inc. | Aromatic hydrocarbon resin and composition for forming underlayer film for lithography |
| CN102040727B (en) * | 2009-10-13 | 2013-07-17 | 中国石油化工股份有限公司 | Novel process for utilizing catalytic cracked heavy oil and condensed multinuclear anime prepared with same |
| CN102453227A (en) * | 2010-10-26 | 2012-05-16 | 武汉保华石化新材料开发有限公司 | Preparation method for polycyclic aromatic hydrocarbon resin |
| CN102453227B (en) * | 2010-10-26 | 2013-05-22 | 武汉保华石化新材料开发有限公司 | Preparation method for polycyclic aromatic hydrocarbon resin |
| CN102728404A (en) * | 2012-06-27 | 2012-10-17 | 南京工业大学 | Preparation method for carbon-base solid sulfonic acid catalyst for hydrolysis |
| CN102716767A (en) * | 2012-07-04 | 2012-10-10 | 太原理工大学 | Preparation method of high-acid-content carbon-based solid acid |
| CN102716767B (en) * | 2012-07-04 | 2014-06-04 | 太原理工大学 | Preparation method of high-acid-content carbon-based solid acid |
| CN112851893A (en) * | 2021-01-07 | 2021-05-28 | 浙江万里新材料科技有限公司 | Irradiation crosslinking polyethylene foam material and preparation method thereof |
| CN112851893B (en) * | 2021-01-07 | 2022-09-02 | 浙江万里新材料科技有限公司 | Irradiation crosslinking polyethylene foam material and preparation method thereof |
| CN113527639A (en) * | 2021-08-02 | 2021-10-22 | 武汉科技大学 | Method for preparing spinnable asphalt with high softening point from naphthalene and product thereof |
| CN113527639B (en) * | 2021-08-02 | 2022-08-02 | 武汉科技大学 | Method for preparing spinnable asphalt with high softening point from naphthalene and product thereof |
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