CN1188346C - Preparing method particle active carbon with high decolorizing performance - Google Patents

Preparing method particle active carbon with high decolorizing performance Download PDF

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Publication number
CN1188346C
CN1188346C CNB031316514A CN03131651A CN1188346C CN 1188346 C CN1188346 C CN 1188346C CN B031316514 A CNB031316514 A CN B031316514A CN 03131651 A CN03131651 A CN 03131651A CN 1188346 C CN1188346 C CN 1188346C
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China
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active carbon
phosphoric acid
granulated active
preparation
decoloration performance
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CN1456499A (en
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蒋剑春
王志高
邓先伦
应浩
戴伟娣
张天健
刘汉超
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Institute of Chemical Industry of Forest Products of CAF
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Institute of Chemical Industry of Forest Products of CAF
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Abstract

The present invention discloses a method for preparing granular active carbon with high decolorizing performance, which comprises: lignin hydrolyzed by acid is arranged in phosphoric acid in which the ratio by weight of pure phosphoric acid to the lignin hydrolyzed by acid is 1.0 to 2.5: 1, evenly stirred, soaked at the temperature of 50DEG C to 250DEG C for more than 0.5 hour, and extruded into granules; the formed granules are hardened, activated at the temperature of 300DEG C to 500DEG C for more than 30 minutes, boiled with water, washed until the pH value of active carbon reaches 5 to 6, dewatered and dried to form the granular active carbon with high decolorizing performance. In the present invention, the lignin hydrolyzed by acid is pretreated by the phosphoric acid, especially the phosphoric acid with the concentration of 20% to 85%, so that the granular active carbon with high decolorizing performance, which is prepared by using the phosphoric acid method, is high in decolorizing performance, the decolorizing rate of caramel by using the method A is more than 120%, the methylene blue is more than 270 mg/g, the iodine value is more than 1285 mg/g, and the strength is more than 80%.

Description

The preparation method of high decoloration performance granulated active carbon
One, technical field
The present invention relates to a kind of technology of preparing of high decoloration performance granulated active carbon, especially relate to a kind of method of utilizing the high decoloration performance granulated active carbon of acid hydrolysis lignin system.
Two, background technology
At present, be that raw material is produced granulated active carbon and mostly adopted the physics method with the hydrolytic lignin.People such as Li Yun are raw material with the hydrolytic lignin; control moisture is 40~50%; rely on the cohesive action of lignin self; select the screw extruder extrusion molding for use; and after drying, charing (400 ℃ of following 15min), the activation (850 ℃ of following steam activation 50min); the intensity of resulting granules gac is 94.6%, benzene absorption 41.2%, iodine number 1083.5mg/g.Though the prepared granulated active carbon intensity of this method height, absorption property is not high, does not more have the caramel decoloring ability.And other are raw material with the lignin, adopt chemical method to prepare the burgy that is all with caramel percent of decolourization.Adopt the two stage activation method as people such as Yan Shanghua, with the ZnCl of 50~60Be ' 2Be activator, successively at 200 ℃ of following charing 20min and 600 ℃ of following activation 90min, the adsorptive value of prepared its methylene blue of gac of result is 153.75~156.45mg/g, and A method caramel percent of decolourization is greater than 100%.People such as Zhang Yun's night are raw material with the hydrolytic lignin, adopt 95%H 2SO 4Soak, activate 45min down at 240 ℃, obtained the methylene blue adsorptive value at 165~225mg/g, A method caramel percent of decolourization reaches 80~95%.But the employed chemical substance of above method or be the serious material of environmental pollution, or be the very strong material of corrodibility, embarrass actual industrial process to use.
Three, technology contents
Technical problem the invention provides the preparation method of the little and high decoloration performance granulated active carbon that can reduce production costs of a kind of environmental pollution, and this method can also alleviate the corrosion to equipment.
The preparation method of a kind of high decoloration performance granulated active carbon of technical scheme is that the ratio (weight ratio) according to pure phosphoric acid and acid hydrolysis lignin is (1.0~2.5): 1 ratio; place phosphoric acid to stir evenly the back after 50 ℃ of-250 ℃ of following pre-treatment are more than 0.5 hour the acid hydrolysis lignin; be squeezed into particle; down harden 1 hour or more at 100~200 ℃ shaped granule; then; activate more than 30 minutes down at 300 ℃-500 ℃; at last; use water boil; through wash be 5-6 to the pH value of gac after; dehydration, oven dry become high decoloration performance granulated active carbon.
Beneficial effect (1) the present invention has carried out pre-treatment, sclerosis, activatory operation to the acid hydrolysis lignin; the granulated active carbon that it is prepared; absorption property is higher; not only methylene blue is more than 270mg/g; iodine sorption value is more than 1285mg/g, and its A method caramel percent of decolourization is more than 120%.(2) the present invention's pre-treatment that places phosphoric acid that the acid hydrolysis lignin is done; make the pyrolysis under the effect of phosphoric acid of acid hydrolysis lignin produce tar as binding agent; under the situation of not adding other binding agents; make lignin from moulding; prepared high decoloration performance granulated active carbon has the high advantage of intensity, and its intensity is more than 80%.(3) the present invention adopts phosphoric acid to produce high decoloration performance granulated active carbon, and adopts sulfuric acid particularly to adopt the vitriol oil to prepare gac to compare, and is lighter to the corrosion of equipment, just can produce thus to help the advantage that reduces production costs.Particularly phosphoric acid can be realized recycling, therefore, not only helps further to reduce production costs, and can reduce environmental pollution.(3) the present invention be that activator production process of active carbon is compared with the zinc chloride, have the little advantage of environmental pollution.(4) the present invention takes in the pre-treatment that the acid hydrolysis lignin is carried out, and the heat while stirring technical measures of mediating and 120~200 ℃ of following hardening technique measures more than 2 hours all helps guaranteeing or improving the intensity of high decoloration performance granulated active carbon.In sum, it is little that the present invention has an environmental pollution, light to the equipment corrosion degree, the advantage that helps production cost to reduce; Have good decoloring performance, advantage that intensity is high by the prepared granulated active carbon of the present invention.
Four, specific embodiments
The preparation method of 1 one kinds of high decoloration performance granulated active carbons of embodiment; be that ratio (weight ratio) according to pure phosphoric acid and acid hydrolysis lignin is (1.0~2.5): 1 ratio; place phosphoric acid to stir evenly the back after 50 ℃ of-250 ℃ of following pre-treatment are more than 0.5 hour the acid hydrolysis lignin; be squeezed into particle; down harden 1 hour or more at 100~200 ℃ shaped granule; then; activate more than 30 minutes down at 300 ℃-500 ℃; at last; use water boil; through wash be 5-6 to the pH value of gac after, dehydration, oven dry become high decoloration performance granulated active carbon.In the present embodiment, in preprocessing process, carrying out pretreatment time with phosphoric acid is 0.5 hour-12 hours, and the kneading of taking to heat while stirring, being loose condition (of surface) until mixture, material is easy to the technical measures of moulding, used concentration of phosphoric acid is 20%-85%, setting time is more than 2 hours, 120~200 ℃ of temperature, and the soak time of acid hydrolysis lignin is 30 minutes~150 minutes.
The preparation method of 2 one kinds of high decoloration performance granulated active carbons of embodiment; be that ratio (weight ratio) according to pure phosphoric acid and acid hydrolysis lignin is 1: 1 a ratio; it is that the phosphoric acid of 50%-85% stirs evenly the back after 50 ℃ of following pre-treatment are more than 8 hours that the acid hydrolysis lignin is placed concentration; be squeezed into particle; shaped granule was hardened 8 hours down at 100 ℃; then; activate 0.5 hour down at 400 ℃; at last; use water boil; after the pH value of gac was 5-6, dehydration, oven dry can obtain high decoloration performance granulated active carbon through washing.
The preparation method of 3 one kinds of high decoloration performance granulated active carbons of embodiment; be that ratio (weight ratio) according to pure phosphoric acid and acid hydrolysis lignin is 1.3: 1 a ratio, place phosphoric acid to stir evenly the back after 95 ℃ of following pre-treatment are more than 6 hours the acid hydrolysis lignin, be squeezed into particle; shaped granule was hardened 6 hours down at 120 ℃; then, activate 1 hour down at 450 ℃, last; use water boil; after the pH value of gac was 5-6, dehydration, oven dry can obtain high decoloration performance granulated active carbon through washing.
The preparation method of 4 one kinds of high decoloration performance granulated active carbons of embodiment; be that ratio (weight ratio) according to pure phosphoric acid and acid hydrolysis lignin is 1.8: 1 a ratio; place phosphoric acid to stir evenly the back after 130 ℃ of following pre-treatment are more than 3 hours the acid hydrolysis lignin; be squeezed into particle; shaped granule was hardened 3 hours down at 150 ℃; then; activate 2.5 hours down at 320 ℃; at last; use water boil; after the pH value of gac was 5-6, dehydration, oven dry can obtain high decoloration performance granulated active carbon through washing.
The preparation method of 5 one kinds of high decoloration performance granulated active carbons of embodiment; be that ratio (weight ratio) according to pure phosphoric acid and acid hydrolysis lignin is 2.5: 1 a ratio, place phosphoric acid to stir evenly the back after 165 ℃ of following pre-treatment are more than 1 hour the acid hydrolysis lignin, be squeezed into particle; shaped granule was hardened 2 hours down at 180 ℃; then, activate 1 hour down at 490 ℃, last; use water boil; after the pH value of gac was 5-6, dehydration, oven dry can obtain high decoloration performance granulated active carbon through washing.
The preparation method of 6 one kinds of high decoloration performance granulated active carbons of embodiment; be that ratio (weight ratio) according to pure phosphoric acid and acid hydrolysis lignin is 2.2: 1 a ratio, with the acid hydrolysis lignin place phosphoric acid stir evenly the back in 200 ℃ soak more than 0.5 hour down after, be squeezed into particle; shaped granule was hardened 1 hour down at 200 ℃; then, activate 2 hours down at 350 ℃, last; use water boil; after the pH value of gac was 5-6, dehydration, oven dry can obtain high decoloration performance granulated active carbon through washing.

Claims (5)

1, a kind of preparation method of high decoloration performance granulated active carbon; it is characterized in that being (1.0~2.5): 1 ratio according to the ratio (weight ratio) of pure phosphoric acid and acid hydrolysis lignin; place phosphoric acid to stir evenly the back after 50 ℃ of-250 ℃ of following pre-treatment are more than 0.5 hour the acid hydrolysis lignin; be squeezed into particle; with shaped granule 100~200 ℃ the sclerosis more than 1 hour after; activate more than 30 minutes down at 300 ℃-500 ℃; at last; use water boil; through wash be 5-6 to the pH value of gac after; dehydration, oven dry become high decoloration performance granulated active carbon.
2, the preparation method of high decoloration performance granulated active carbon according to claim 1 is characterized in that in preprocessing process, and the kneading that heats while stirring is loose condition (of surface) until mixture, and material is easy to moulding.
3, the preparation method of high decoloration performance granulated active carbon according to claim 1 is characterized in that setting time more than 2 hours, 120~200 ℃ of temperature.
4, the preparation method of high decoloration performance granulated active carbon according to claim 1, the phosphoric acid concentration that it is characterized in that handling the acid hydrolysis lignin is 20%-85%.
5, according to the preparation method of claim 1,2,3 or 4 described high decoloration performance granulated active carbons, the soak time that it is characterized in that the acid hydrolysis lignin is 30 minutes~150 minutes.
CNB031316514A 2003-05-30 2003-05-30 Preparing method particle active carbon with high decolorizing performance Expired - Fee Related CN1188346C (en)

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Publication number Priority date Publication date Assignee Title
CN100371245C (en) * 2006-01-24 2008-02-27 朝阳森塬活性炭有限公司 Preparation method of granular active carbon for sugar decoloration
CN1994555B (en) * 2006-12-15 2010-06-23 四川省林业科学研究院 Impregnated active carbon and preparation method thereof
CN106744938A (en) * 2016-12-17 2017-05-31 段清 A kind of method that utilization bagasse produces decoloration active carbon high
CN107537440A (en) * 2017-09-15 2018-01-05 江苏科力特环保科技有限公司 A kind of preparation method of organic matter absorption granular activated carbon

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