CN102716767B - Preparation method of high-acid-content carbon-based solid acid - Google Patents
Preparation method of high-acid-content carbon-based solid acid Download PDFInfo
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- CN102716767B CN102716767B CN201210229347.4A CN201210229347A CN102716767B CN 102716767 B CN102716767 B CN 102716767B CN 201210229347 A CN201210229347 A CN 201210229347A CN 102716767 B CN102716767 B CN 102716767B
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Abstract
The invention relates to a preparation method of high-acid-content carbon-based solid acid, which comprises the steps of: firstly oxidizing coal tar pitch by using hydrogen peroxide under the effect of ultrasonic waves, using chloroacetic acid as chlorinating agent, introducing chlorine atoms in benzene ring structures of aromatic compounds through reaction and sulphonating the aromatic compounds to introduce more sulfonic acid groups, so as to increase carbon-based surface acid content, improve acid strength and enhance acid catalytic capability. Since the solid acid is prepared by introducing high-content sulfonic acid groups at more active sites which are provided by the chlorine atoms and can be substituted by the sulfonic acid groups and by fully using the characteristic that the major components, i.e. large ring aromatic compounds in the coal tar pitch are sulphonated, the esterification rate of ethanol and acetic acid esterification reaction can reach 87 percent, the esterification rate is not decreased after the solid acid is repetitively used for five times, the acid content of the solid acid is two times of the acid content of solid acid reported by open literature, and the solid acid has the characteristics of high acid content, acid and alkali resistance and high thermal stability.
Description
Technical field
The present invention relates to a kind of method of preparing carbon-based solid acid, especially a kind of taking coal tar pitch as raw material, by adding oxidant hydrogen peroxide to carry out oxidation pre-treatment under ultrasonic wave is auxiliary, then chlorination, makes chlorinity reach 18～20wt%, through pulverizing, sieve, then carry out the target product of sulfonation system.This method, by chlorination processing in advance, has improved sulfonation degree, has increased Surface acidity, and then has improved acid strength and heat endurance, has expanded the range of application of made solid acid.
Technical background
The exploitation of resources effective utilization and environmentally friendly catalyst becomes one of common important goal of pursuing of the numerous scientific workers in the world today.Acid is widely used as the catalyst of many reactions, as preparation, the producing hexanolactam from cyclohexanone-oxime etc. of alcoholic acid esterification, bio oil.Because liquid acid is as the easy etching apparatus of catalyst, be difficult to reclaim, and environment is caused to very large pollution, green chemical industry becomes target and the direction of transition and sustainable development.Because solid acid catalyst had both shown stronger acidity, there is again the recovery of being convenient to feature, and the advantage that equipment corrosion is reduced greatly, scientist has studied method and the catalytic property thereof of preparing various solid acids.Wherein, especially to prepare carbon-based solid acid because of raw materials used wide material sources and to enrich, have the feature such as catalyst that acid-fast alkali-proof and tool be easy to preparation and can be used for many reactions the concern that is subject to more scientists.As taking living beings and coal as raw material, be converted into amorphous carbon by heat treatment, then with concentrated sulfuric acid effect, and then reach and introduce sulfonic object.But this route can only utilize the limited surface hydroxyl and the concentrated sulfuric acid effect that produce through charing to introduce sulfonic acid group, i.e. acid amount is subject to the how many restriction of surface group.Carbonization temperature is higher, remains in surperficial number of hydroxyl groups fewer, and the solid acid Surface acidity making is lower, and acid strength is also just lower; Carbonization temperature is low, remains in surperficial hydroxyl quantity many, but the Carbon Materials poor heat stability obtaining.Solid acid is as catalyst, and Surface acidity is the principal element that affects its catalytic action.At present in disclosed bibliographical information; the various solid acid acid amounts of preparation are up to 5.0 mmol/L; the solid acid acid amount of preparing taking naphthalene as raw material as Japanese scholars Hara M etc. is 4.9 mmol/L (Angew Chem Int Ed, 2004,43 (22): 2955-2958); That prepare taking microcrystalline cellulose is 2.0mmol/L (Suganuma S etc., J Am Chem Soc, 2008,130,12787-12797).Surface acidity still needs further raising, to improve catalytic activity.Therefore, preparation have Surface acidity solid acid high and Heat stability is good be this class catalyst enter industrialization still need solve a subject matter.
Summary of the invention
The technical problem to be solved in the present invention is further to improve acid content and the stability thereof on existing solid acid surface, and a kind of preparation method of peracid amount carbon-based solid acid is provided.
For the problems referred to above and object, one aspect of the present invention considers to be applicable to as far as possible preparing solid acid to the raw material using from the Nomenclature Composition and Structure of Complexes, pass through on the other hand chemical reaction, in its structure, introduce some active groups, and then carry out sulfonating reaction, to improve the quantity of sulfonic acid group, increase its acid amount.
The measure that the present invention takes is a kind of preparation method's of peracid amount carbon-based solid acid technical scheme, and described in it, method is taking coal tar pitch as raw material, first to raw material chlorination processing, after carry out sulfonation; Concrete grammar step is as follows:
Getting the coal tar pitch of certain mass, is the xylene soluble of 2～4 times of coal tar pitch quality with volume milliliter number;
Adding quality is that solid monoxone and the volume milliliter number of 2～3 times of coal tar pitch quality is the H that 3～5 times of coal tar pitch quality, concentration are 30%
2o
2, be at 70～90 DEG C ultrasonic 40～60 minutes in temperature, rear suction filtration and dry after, obtain the chloride chlorination coal tar pitch at 18～20 wt%;
Chlorination coal tar pitch is pulverized, 200 orders sieve;
The concentrated sulfuric acid and chlorination coal tar pitch quality are added in chlorination coal tar pitch than for 5:1～7:1, and reaction temperature is 165 DEG C～180 DEG C, and the reaction time is 12h, after be cooled to room temperature;
Using sand core funnel suction filtration, is neutral with distilled water washing sulfonated product to filtrate pH, is placed in drying box, at 110 DEG C of temperature, dries 4h, makes Surface acidity and reach the solid acid of 7.5mmol/g.
Wherein, described coal tar pitch is medium temperature coal pitch, or coal tar pitch; Described monoxone is chloroacetic acid, dichloroacetic acid, or trichloroacetic acid.
Technique scheme of the present invention be taking coal chemical enterprise produce byproduct coal tar pitch as raw material, make full use of the feature that ingredient is mainly aromatic compound, adopt be different from open source literature report completely raw material is carried out to simple method of sulfonating, but according to aromatic compound design feature, first under ul-trasonic irradiation, utilize mild oxidizer H
2o
2to part radical oxidation, then chlorination in raw material.The carrying out of oxidizing process, is conducive to the charcoal particle that prepared sizes are little; The object of chlorination, is conducive to provide more active groups that can be replaced by sulfonic group, to increase Surface acidity, improves acid strength.Compare with the solid acid of preparing without coal tar pitch and other Carbon Materials of chlorination, Surface acidity increases by 1 times, heat endurance is also significantly improved, using prepared solid acid as ethanol with the catalyst of acid esterification reaction, result shows, can reach 87% to ethanol and acetic acidreaction esterification yield, through recycling 5 times, still have original catalytic effect, catalyst recovery yield can reach 99%.
The solid acid that adopts the invention described above method to prepare, can be used as the catalyst of various acid catalyzed reactions, change low value coal tar pitch into high value fine chemicals, greatly improve its use value, extend the industry chain (supply chain) of coal chemical enterprise downstream product, promoted the service efficiency of this disposable fossil resource.The present invention adopts that route device therefor is simple, process is easy to realize and operation, especially coal tar pitch deep processing belong to environmental protection and preferentially subsidize developing industry, has broad application prospects.
Detailed description of the invention
Below the specific embodiment of the present invention is made an explanation.
Implement a kind of preparation method of peracid amount carbon-based solid acid, the method is taking coal tar pitch as raw material, first to raw material chlorination processing, and then the process of carrying out sulfonation, concrete grammar step is: get certain mass coal tar pitch, be the xylene soluble of 2～4 times of coal tar pitch quality with volume milliliter number, then to add quality be that solid monoxone and the volume milliliter number of 2～3 times of coal tar pitch quality is the H of 3～5 times of coal tar pitch quality
2o
2, be at 70～90 DEG C ultrasonic 40～60 minutes in temperature, through suction filtration and dry after obtain the chloride chlorination coal tar pitch at 18～20 wt%, then the coal tar pitch of chlorination is pulverized, 200 orders (74 microns) sieve, the concentrated sulfuric acid is added in chlorination coal tar pitch than the mode that is 5:1～7:1 according to the concentrated sulfuric acid and chlorination coal tar pitch quality, control reaction temperature and react 12h 165 DEG C～180 DEG C scopes, after reaction finishes, be cooled to room temperature, use sand core funnel suction filtration, washing sulfonated product with distilled water is neutral to filtrate pH, be placed in drying box and dry 4h at 110 DEG C of temperature, obtain the solid acid that Surface acidity reaches 7.5mmol/g, compare with the solid acid of preparing without coal tar pitch and other Carbon Materials of chlorination, Surface acidity increases by 1 times, heat endurance is also significantly improved, preparing the restriction that raw materials used coal tar pitch is not subject to pitch kind, can be both medium temperature coal pitch, can be also coal tar pitch, is not subject to the place of production and process conditions to produce the restriction of coal tar pitch, the monoxone that its chlorination process uses can be chloroacetic acid, dichloroacetic acid or trichloroacetic acid.
Embodiment 1
Get 20g medium temperature coal pitch, add 40ml dimethylbenzene, stirring and dissolving, then add 50g trichloroacetic acid and 60ml, 30% H
2o
2, be under 80 DEG C of conditions ultrasonic 50 minutes in temperature, through suction filtration and dry after obtain the chlorination coal tar pitch of chloride 20 wt%; Then pulverize the coal tar pitch of chlorination, 200 orders that sieve (74 microns), put into beaker, add the 100g concentrated sulfuric acid, be placed in conduction oil bath, controlling reaction temperature is 165 DEG C, after reaction 12h, being cooled to room temperature, using sand core funnel suction filtration, is then neutral with distilled water washing sulfonated product to filtrate pH, be placed in drying box and dry 4h at 110 DEG C of temperature, obtain Surface acidity and reach the solid acid of 7.3 mmol/g.
Embodiment 2
Get 20g coal tar pitch, add 60ml dimethylbenzene, stirring and dissolving, then add 60g dichloroacetic acid and 80ml, 30% H
2o
2, be under 90 DEG C of conditions ultrasonic 60 minutes in temperature, through suction filtration and dry after obtain the chlorination coal tar pitch of chloride 18.6 wt%; Then pulverize the coal tar pitch of chlorination, 200 orders that sieve (74 microns), put into beaker, add the 172g concentrated sulfuric acid, be placed in conduction oil bath, controlling reaction temperature is 170 DEG C, after reaction 12h, being cooled to room temperature, using sand core funnel suction filtration, is then neutral with distilled water washing sulfonated product to filtrate pH, be placed in drying box and dry 4h at 110 DEG C of temperature, obtain Surface acidity and reach the solid acid of 7.5 mmol/g.
Embodiment 3
Get 20g coal tar pitch, add 80ml dimethylbenzene, stirring and dissolving, then add 50g chloroacetic acid and 100ml, 30% H
2o
2, be under 70 DEG C of conditions ultrasonic 40 minutes in temperature, through suction filtration and dry after obtain the chlorination coal tar pitch of chloride 19.5 wt%; Then pulverize the coal tar pitch of chlorination, 200 orders that sieve (74 microns), put into beaker, add the 149.0g concentrated sulfuric acid, be placed in conduction oil bath, controlling reaction temperature is 170 DEG C, after reaction 12h, being cooled to room temperature, using sand core funnel suction filtration, is then neutral with distilled water washing sulfonated product to filtrate pH, be placed in drying box and dry 4h at 110 DEG C of temperature, obtain Surface acidity and reach the solid acid of 7.3 mmol/g.
Embodiment 4
Get 20g medium temperature coal pitch, add 70ml dimethylbenzene, stirring and dissolving, then add 40g trichloroacetic acid and 90ml, 30% H
2o
2, be under 85 DEG C of conditions ultrasonic 45 minutes in temperature, through suction filtration and dry after obtain the chlorination coal tar pitch of chloride 18.0 wt%; Then pulverize the coal tar pitch of chlorination, 200 orders that sieve (74 microns), put into beaker, add the 170.7g concentrated sulfuric acid, be placed in conduction oil bath, controlling reaction temperature is 165 DEG C, after reaction 12h, being cooled to room temperature, using sand core funnel suction filtration, is then neutral with distilled water washing sulfonated product to filtrate pH, be placed in drying box and dry 4h at 110 DEG C of temperature, obtain Surface acidity and reach the solid acid of 7.5 mmol/g.
Embodiment 5
Get 20g medium temperature coal pitch, add 80ml dimethylbenzene, stirring and dissolving, then add 60g chloroacetic acid and 100ml, 30% H
2o
2, be under 80 DEG C of conditions ultrasonic 55 minutes in temperature, through suction filtration and dry after obtain the chlorination coal tar pitch of chloride 19.0 wt%; Then pulverize the coal tar pitch of chlorination, 200 orders that sieve (74 microns), put into beaker, add the 148.1g concentrated sulfuric acid, be placed in conduction oil bath, controlling reaction temperature is 180 DEG C, after reaction 12h, being cooled to room temperature, using sand core funnel suction filtration, is then neutral with distilled water washing sulfonated product to filtrate pH, be placed in drying box and dry 4h at 110 DEG C of temperature, obtain Surface acidity and reach the solid acid of 7.4 mmol/g.
Embodiment 6
Performance: use institute of the present invention controlling catalyst, according to ethanol and quality of acetic acid than for 3:1, to add the amount of catalyst be that 5%(is with ethanol quality note), reaction duration 60 minutes, its esterification yield is 87%, after reusing five times, esterification yield is still higher than 85%, catalyst recovery yield is 99%, and heat decomposition temperature is 360 DEG C.
Claims (3)
1. a preparation method for peracid amount carbon-based solid acid, described method is taking coal tar pitch as raw material, first to raw material chlorination processing, after carry out sulfonation; Concrete grammar step is as follows:
Getting the coal tar pitch of certain mass, is the xylene soluble of 2～4 times of coal tar pitch quality with volume milliliter number;
Adding quality is that solid monoxone and the volume milliliter number of 2～3 times of coal tar pitch quality is the H that 3～5 times of coal tar pitch quality, concentration are 30%
2o
2, be at 70～90 DEG C ultrasonic 40～60 minutes in temperature, rear suction filtration and dry after, obtain the chloride chlorination coal tar pitch at 18～20 wt%;
Chlorination coal tar pitch is pulverized, 200 orders sieve;
The concentrated sulfuric acid and chlorination coal tar pitch quality are added in chlorination coal tar pitch than for 5:1～7:1, and reaction temperature is 165 DEG C～180 DEG C, and the reaction time is 12h, after be cooled to room temperature;
Using sand core funnel suction filtration, is neutral with distilled water washing sulfonated product to filtrate pH, is placed in drying box, at 110 DEG C of temperature, dries 4h, makes Surface acidity and reach the solid acid of 7.5mmol/g.
2. the preparation method of peracid amount carbon-based solid acid according to claim 1, described coal tar pitch is medium temperature coal pitch, or coal tar pitch.
3. according to the preparation method of the peracid amount carbon-based solid acid described in claim 1, described monoxone is chloroacetic acid, dichloroacetic acid, or trichloroacetic acid.
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| CN103599814B (en) * | 2013-10-22 | 2015-07-29 | 太原理工大学 | A kind of high temperature resistant preparation with the superpower solid acid of the asphaltic base of hydrolysis |
| CN105879905B (en) * | 2014-09-17 | 2018-12-18 | 南开大学 | A kind of polyfunctional group chirality phosphine catalyst, preparation method and applications |
| CN104815690B (en) * | 2015-04-14 | 2018-03-23 | 贵州大学 | A kind of more sulfonic acid funtionalized mesoporous polymer solid acid catalysts and its preparation method and application |
| CN105879911B (en) * | 2016-04-07 | 2019-02-12 | 大连理工大学 | A kind of high temperature resistant solid acid catalyst and its preparation method and application based on organic point of DCL/Direct coal liquefaction heavy |
| CN113368899B (en) * | 2021-07-03 | 2022-05-10 | 太原理工大学 | Preparation method of high-acid-density cellulase-like resin solid acid catalyst |
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| CN101245254A (en) * | 2008-03-28 | 2008-08-20 | 华东师范大学 | Method for producing biological diesel oil with carbon-based solid acid as catalyst |
| CN101396669A (en) * | 2008-10-23 | 2009-04-01 | 福建师范大学 | Preparation method of asphalt base solid catalyst for producing biology diesel oil |
| CN101612587A (en) * | 2008-06-23 | 2009-12-30 | 汉能科技有限公司 | A kind of composite solid-acid catalyst and preparation method thereof |
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Patent Citations (6)
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| JP2741233B2 (en) * | 1989-02-13 | 1998-04-15 | チッソ株式会社 | Solid acid catalyst and method of using the same |
| CN1741991A (en) * | 2003-02-05 | 2006-03-01 | 独立行政法人科学技术振兴机构 | Polycyclic aromatic carbon based solid strong acid |
| CN101147880A (en) * | 2007-08-07 | 2008-03-26 | 华东师范大学 | Method for preparing condensing multi-kernel aromatic resin carbon based solid acid catalyst |
| CN101245254A (en) * | 2008-03-28 | 2008-08-20 | 华东师范大学 | Method for producing biological diesel oil with carbon-based solid acid as catalyst |
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Inventor after: Cao Qing Inventor after: Jie Xiaoling Inventor after: Jin Lie Inventor after: Yu Hui Inventor after: Zhang Huaiping Inventor before: Cao Qing Inventor before: Jin Lie Inventor before: Jie Xiaoling Inventor before: Zhang Huaiping Inventor before: Yu Hui |
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