CN104941663A - Preparation method of high acid content solid acid catalyst - Google Patents
Preparation method of high acid content solid acid catalyst Download PDFInfo
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- CN104941663A CN104941663A CN201510286135.3A CN201510286135A CN104941663A CN 104941663 A CN104941663 A CN 104941663A CN 201510286135 A CN201510286135 A CN 201510286135A CN 104941663 A CN104941663 A CN 104941663A
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- 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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Abstract
The invention discloses a preparation method of a high acid content solid acid catalyst, which takes plant waste material as a raw material. The method comprises the following steps: drying plant waste material, crushing and sieving, adding into concentrated sulfuric acid while stirring, uniformly mixing, then dehydrating and carbonizing under room temperature for 10-24 hours, sulfonating for 15-30 hours under 100-200 hours to obtain a solid mixture; washing the mixture by hot water, removing residual liquid acid in the mixture, filtering the cleaned solids, drying and crushing to prepare the solid acid catalyst, wherein the acidity of solid acid is 3.5-5.0mmol/g, and the solid acid catalyst can be called GDUT-1. The preparation method is simple and feasible, the solid acid catalyst has the characteristics of high acid amount, good catalytic activity, cycle utilization, green environmental protection, low preparation cost, and is suitable for industrial production.
Description
Technical field
The invention belongs to solid acid catalyst technical field, be specifically related to a kind of preparation method of peracid amount solid acid catalyst.
Background technology
In modern chemical industry is produced, acid catalyst occupies very consequence, because having, catalytic performance is good, lower-price characteristic is widely used in Chemical Manufacture for liquid acid catalyst such as sulfuric acid, hydrochloric acid, phosphoric acid, hydrofluoric acid, p-methyl benzenesulfonic acid etc., but exist serious to equipment corrosion, be difficult to repetition regeneration, be separated with reactant and product difficulty, the shortcomings such as three wastes discharge amount is large, cause serious negative effect to the health of the mankind, work and living environment.
Along with the enhancing of people's environmental consciousness and the proposition of Green Chemistry concept, development benefit takes into account environment, realize the solid acid catalyst of chemical industrial product cleanly production has become the domestic demand impelling chemical industry sustainable development.Compared to liquid acid catalyst, it is easily separated that solid acid catalyst has catalyst and raw material and product, recyclable recycling, do not corrode consersion unit and the advantage such as free from environmental pollution.Wherein, because having, the advantages such as catalytic perfomance is good, with low cost, resource effectively utilizes become the study hotspot of field of catalyst preparation to biomass solid acid catalyst; but current this kind of catalyst is mainly obtained by high temperature cabonization sulfonation method; under high temperature (>350 DEG C), under inert atmosphere protection, carry out incomplete carbonization by raw material, then with the concentrated sulfuric acid or oleum, sulfonated process is carried out to it.This method operation more complicated, need the preparation condition such as high temperature, inert atmosphere, and obtained solid acid catalyst specific area is little, original structure destroys serious, and Surface acidity is low and be easy to run off simultaneously.Such as Chinese invention patent application CN104475127A report pineapple bran makes active carbon, then prepares solid acid catalyst with obtained active carbon, needs high-temperature activation at 450 ~ 500 DEG C.Can find out, existing biomass solid acid preparation technology is difficult to large-scale industrial production, therefore be badly in need of improving preparation technology, synthesize a kind of peracid amount, Stability Analysis of Structures and be applicable to the solid acid catalyst of suitability for industrialized production by easy method, thus realize the object this type of catalyst being really used for chemical industrial product cleanly production.
Summary of the invention
The technical problem that the present invention solves is the preparation method providing a kind of peracid amount solid acid catalyst, the solid acid surface acidity utilizing the method obtained is 3.5 ~ 5.0mmol/g, this solid acid catalyst is called GDUT-1, has the feature of low cost, peracid amount, simple and efficient, applicable suitability for industrialized production.
For realizing above-mentioned technical goal, the technical solution used in the present invention is:
A preparation method for peracid amount solid acid catalyst, the method take plant waste as raw material, first add the concentrated sulfuric acid dehydration carbonization, after carry out sulfonation, comprise the following steps:
(1) plant waste of drying is pulverized also 20 ~ 80 orders to sieve;
(2) to join after sieving in the concentrated sulfuric acid and mechanical agitation, at room temperature dewater carbonization 10 ~ 24h, then sulfonation 15 ~ 30h at 100 ~ 200 DEG C in an oven, obtains solid mixture;
(3) this mixture is washed to pH in filtrate no longer to change, then filters, dry, pulverize the i.e. obtained solid acid catalyst and 20 ~ 80 orders sieve.
In described step (1) plant waste be peltate yam waste slag, coconut palm chaff, rice bran, wheat husk, peanut shell, bamboo bits, wood chip, stalk any one or a few.
Plant waste joins in the concentrated sulfuric acid by the ratio of mass ratio 1:1 ~ 10 in plant waste and the concentrated sulfuric acid in described step (2).
In described step (3), method for washing is add water in mixture than the ratio of 1:3 ~ 5 in the mass/volume of mixture with water, and be placed in the water-bath magnetic agitation of 60 ~ 80 DEG C, mixing time is 30 ~ 60min, washes 4 ~ 6 times.
The GDUT-1 solid acid catalyst that the present invention obtains with plant waste cheap and easy to get for raw material, the dehydration property of the concentrated sulfuric acid and highly acid is utilized at room temperature to be dewatered by raw material carbonization, obtain the solid carbon material with rock-steady structure, sulfonation is heated further again at 100 ~ 200 DEG C, thus the original architectural characteristic of living beings can be kept, formation Stability Analysis of Structures, the solid acid catalyst that specific area is large, acid amount is high.
The present invention, compared with existing biomass solid acid catalyst technology of preparing, has following beneficial effect:
(1) preparation technology is simple, and living beings original structure does not destroy.First at room temperature dewater carbonization, then sulfonation at 100 ~ 200 DEG C, without the need to high temperature and inert atmosphere, plant waste is with low cost, is applicable to suitability for industrialized production;
(2) obtained GDUT-1 solid acid catalyst acid amount is high, is 3.5 ~ 5.0mmol/g.Heat endurance is high, and heat decomposition temperature more than 200 DEG C, and has higher catalytic activity, and can recycled for multiple times, is a kind of efficient, stable, clean catalysis agent with wide application prospect.
Detailed description of the invention
Be described in detail technical scheme of the present invention below in conjunction with specific embodiment, following examples are in order to those skilled in the art understands the present invention better, and unrestricted technical scheme of the present invention.
Embodiment 1
The peltate yam waste slag of drying is pulverized also 80 orders to sieve; Taking 350g ginger ground-slag joins in the 350g concentrated sulfuric acid, mechanical agitation, and mixing time is 18h, then baking oven is placed in, 150 DEG C of 6h, 190 DEG C of 12h obtain mixture, add water in mixture in mixture quality and water volume ratio 1:3 ratio, be placed in 70 DEG C of water-bath magnetic agitation, mixing time is 60min, washes 4 times, filtering drying after washing, pulverize the i.e. obtained GDUT-1 solid acid catalyst and 80 orders sieve, acidity is 4.28mmol/g.
Embodiment 2
The coconut palm chaff of drying is pulverized also 60 orders to sieve; Taking 150g coconut palm chaff powder joins in the 450g concentrated sulfuric acid, mechanical agitation, and mixing time is 12h, then baking oven is placed in, 140 DEG C of 6h, 200 DEG C of 10h obtain mixture, add water in mixture in mixture quality and water volume ratio 1:5 ratio, be placed in 60 DEG C of water-bath magnetic agitation, mixing time is 50min, washes 5 times, filtering drying after washing, pulverize the i.e. obtained GDUT-1 solid acid catalyst and 60 orders sieve, acidity is 4.84mmol/g.
Embodiment 3
The rice bran of drying is pulverized also 20 orders to sieve; Taking 300g bran powder joins in the 1500g concentrated sulfuric acid, mechanical agitation, and mixing time is 20h, then baking oven is placed in, 130 DEG C of 8h, 180 DEG C of 16h obtain mixture, add water in mixture in mixture quality and water volume ratio 1:4 ratio, be placed in 80 DEG C of water-bath magnetic agitation, mixing time is 40min, washes 6 times, filtering drying after washing, pulverize the i.e. obtained GDUT-1 solid acid catalyst and 20 orders sieve, acidity is 4.25mmol/g.
Embodiment 4
The wheat husk of drying is pulverized also 40 orders to sieve; Taking 200g wheat husk powder joins in the 1900g concentrated sulfuric acid, mechanical agitation, and mixing time is 24h, then baking oven is placed in, 140 DEG C of 12h, 180 DEG C of 14h obtain mixture, add water in mixture in mixture quality and water volume ratio 1:4 ratio, be placed in 70 DEG C of water-bath magnetic agitation, mixing time is 60min, washes 4 times, filtering drying after washing, pulverize the i.e. obtained GDUT-1 solid acid catalyst and 40 orders sieve, acidity is 4.90mmol/g.
Embodiment 5
The peanut shell of drying is pulverized also 20 orders to sieve; Taking 750g peanut hull meal joins in the 1500g concentrated sulfuric acid, mechanical agitation, and mixing time is 14h, then baking oven is placed in, 120 DEG C of 11h, 200 DEG C of 9h obtain mixture, add water in mixture in mixture quality and water volume ratio 1:3 ratio, be placed in 60 DEG C of water-bath magnetic agitation, mixing time is 50min, washes 5 times, filtering drying after washing, pulverize the i.e. obtained GDUT-1 solid acid catalyst and 20 orders sieve, acidity is 4.13mmol/g.
Embodiment 6
Broken for the bamboo powder of drying and 60 orders are sieved; Taking 200g bamboo powder joins in the 1200g concentrated sulfuric acid, mechanical agitation, and mixing time is 20h, then baking oven is placed in, 100 DEG C of 14h, 200 DEG C of 10h obtain mixture, add water in mixture in mixture quality and water volume ratio 1:4 ratio, be placed in 80 DEG C of water-bath magnetic agitation, mixing time is 40min, washes 6 times, filtering drying after washing, pulverize the i.e. obtained GDUT-1 solid acid catalyst and 60 orders sieve, acidity is 3.89mmol/g.
Embodiment 7
The wood chip of drying is pulverized also 40 orders to sieve; Taking 400g wood powder joins in the 1600g concentrated sulfuric acid, mechanical agitation, and mixing time is 18h, then baking oven is placed in, 130 DEG C of 8h, 180 DEG C of 16h obtain mixture, add water in mixture in mixture quality and water volume ratio 1:4 ratio, be placed in 70 DEG C of water-bath magnetic agitation, mixing time is 50min, washes 5 times, filtering drying after washing, pulverize the i.e. obtained GDUT-1 solid acid catalyst and 40 orders sieve, acidity is 4.77mmol/g.
Embodiment 8
The crushed stalk of drying 20 orders are sieved; Taking 500g powder of straw joins in the 3500g concentrated sulfuric acid, mechanical agitation, and mixing time is 16h, then baking oven is placed in, 150 DEG C of 6h, 190 DEG C of 13h obtain mixture, add water in mixture in mixture quality and water volume ratio 1:5 ratio, be placed in 80 DEG C of water-bath magnetic agitation, mixing time is 40min, washes 6 times, filtering drying after washing, pulverize the i.e. obtained GDUT-1 solid acid catalyst and 20 orders sieve, acidity is 4.19mmol/g.
Embodiment 9
The bamboo of drying bits and wood chip are pulverized also 60 orders sieve; Take 300g bamboo powder and 300g wood powder respectively, join in the 3600g concentrated sulfuric acid successively, mechanical agitation, mixing time is 12h, is then placed in baking oven, 130 DEG C of 10h, 180 DEG C of 15h obtain mixture, add water in mixture in mixture quality and water volume ratio 1:4 ratio, be placed in 70 DEG C of water-bath magnetic agitation, mixing time is 50min, wash 5 times, filtering drying after washing, pulverize the i.e. obtained GDUT-1 solid acid catalyst and 60 orders sieve, acidity is 4.62mmol/g.
It should be noted last that: above embodiment is only in order to explanation, and unrestricted technical scheme of the present invention, although with reference to above-described embodiment to invention has been detailed description, those of ordinary skill in the art is to be understood that: still can modify to the present invention or equivalent exchange, and not departing from any modification or partial replacement of the spirit and scope of the present invention, it all should be encompassed among right of the present invention.
Claims (5)
1. a preparation method for peracid amount solid acid catalyst, described method take plant waste as raw material, first add the concentrated sulfuric acid dehydration carbonization, after carry out sulfonation, it is characterized in that comprising the steps:
(1) plant waste of drying is pulverized also 20 ~ 80 orders to sieve;
(2) to join after sieving in the concentrated sulfuric acid and mechanical agitation, at room temperature dewater carbonization 10 ~ 24h, then sulfonation 15 ~ 30h at 100 ~ 200 DEG C in an oven, obtains solid mixture;
(3) this mixture is washed to pH in solution no longer to change, then filters, dry, pulverize the i.e. obtained solid acid catalyst and 20 ~ 80 orders sieve.
2. the preparation method of peracid amount solid acid catalyst according to claim 1, is characterized in that: in described step (1) plant waste be peltate yam waste slag, coconut palm chaff, rice bran, wheat husk, peanut shell, bamboo bits, wood chip, stalk any one or a few.
3. the preparation method of peracid amount solid acid catalyst according to claim 1, is characterized in that: plant waste joins in the concentrated sulfuric acid by the ratio of mass ratio 1:1 ~ 10 in plant waste and the concentrated sulfuric acid in described step (2).
4. the preparation method of peracid amount solid acid catalyst according to claim 1, it is characterized in that: in described step (3), method for washing is add water in mixture than the ratio of 1:3 ~ 5 in the mass/volume of mixture with water, be placed in the water-bath magnetic agitation of 60 ~ 80 DEG C, mixing time is 30 ~ 60min, washes 4 ~ 6 times.
5. the preparation method of peracid amount solid acid catalyst according to claim 1, is characterized in that: gained solid acid surface acidity is 3.5 ~ 5.0mmol/g, and this solid acid catalyst is called GDUT-1.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
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| CN201510286135.3A CN104941663A (en) | 2015-04-09 | 2015-05-29 | Preparation method of high acid content solid acid catalyst |
| PCT/CN2015/083776 WO2016192175A1 (en) | 2015-05-29 | 2015-07-10 | Method for preparing solid acid catalyst with high acid content |
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| CN201510165200 | 2015-04-09 | ||
| CN2015101652007 | 2015-04-09 | ||
| CN201510286135.3A CN104941663A (en) | 2015-04-09 | 2015-05-29 | Preparation method of high acid content solid acid catalyst |
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Cited By (4)
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| CN108855159A (en) * | 2018-06-27 | 2018-11-23 | 广东工业大学 | A kind of phosphatization cobalt and its preparation method and application with the synthesis of Prussian blue derivative |
| CN109225275A (en) * | 2018-11-06 | 2019-01-18 | 绍兴文理学院 | A kind of preparation method of carbon-based solid acid |
| CN112191257A (en) * | 2020-10-29 | 2021-01-08 | 广西大学 | Preparation method of solid acid catalyst and application of catalyst |
| CN113617332A (en) * | 2021-08-27 | 2021-11-09 | 郑子渝洋 | Sulfonated biochar for treating heavy metal waste liquid |
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| CN110846194A (en) * | 2019-11-21 | 2020-02-28 | 广西民族大学 | Method for improving quality of white spirit by using carbon-based solid acid |
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- 2015-05-29 CN CN201510286135.3A patent/CN104941663A/en active Pending
- 2015-07-10 WO PCT/CN2015/083776 patent/WO2016192175A1/en active Application Filing
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Cited By (4)
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| CN108855159A (en) * | 2018-06-27 | 2018-11-23 | 广东工业大学 | A kind of phosphatization cobalt and its preparation method and application with the synthesis of Prussian blue derivative |
| CN109225275A (en) * | 2018-11-06 | 2019-01-18 | 绍兴文理学院 | A kind of preparation method of carbon-based solid acid |
| CN112191257A (en) * | 2020-10-29 | 2021-01-08 | 广西大学 | Preparation method of solid acid catalyst and application of catalyst |
| CN113617332A (en) * | 2021-08-27 | 2021-11-09 | 郑子渝洋 | Sulfonated biochar for treating heavy metal waste liquid |
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| WO2016192175A1 (en) | 2016-12-08 |
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Application publication date: 20150930 |