CN1104175A - Method for preparation of active carbon - Google Patents
Method for preparation of active carbon Download PDFInfo
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- CN1104175A CN1104175A CN93120925A CN93120925A CN1104175A CN 1104175 A CN1104175 A CN 1104175A CN 93120925 A CN93120925 A CN 93120925A CN 93120925 A CN93120925 A CN 93120925A CN 1104175 A CN1104175 A CN 1104175A
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Abstract
The present invention recommends a method for preparing active carbon, in particular by using bitumen as raw material. Its main technique is characterized by that the pulverized bitumen is passed through the process of anti-melting treatment, and then is uniformly mixed with extrusion accelerator and adhesive, etc. and formed, and then passed through such proceses of carburizing and activating, so that the invented product ca be obtained. As compared with existent techniques it has the advantages of simple process, low contamination, easily forming, good anti-melting effect and easily making regeneration treatment, and is high in strength, good in adsorptive power and low in ash content.
Description
The present invention relates to a kind of preparation method of active carbon, particularly is the feedstock production process of active carbon with pitch.
As everyone knows, gac has purposes widely in industrial and agricultural production and daily life.The preparation of traditional gac normally with the shell of fruit, is made for raw material as Exocarpium cocois (Cocos nucifera L), apricot shell etc.Because the restriction of this type of shell resource, therefore make the raw material of Activated Carbon Production comparatively lack, thereby cause the price of gac more expensive, had a strong impact on its range of application, such as in environment-friendly engineering, active carbon adsorption since its to have a facility investment few, the advantage that effect is good, and usually be used to remove objectionable impurities, reduce aspects such as COD value of waste water, but because it costs an arm and a leg, cause the operational cost in the treating processes to increase greatly, thereby have to adopt other method,, brought scale of investment excessive to manufacturer virtually as biochemical process etc., the trouble of maintenance of the equipment and complicated operation.Therefore,, improve its performance, in recent years, carried out a large amount of research work both at home and abroad in order to reduce the production cost of gac.
It is that raw material is made cylindrical process of active carbon with weakly caking coal that CN86107847 discloses a kind of, and this method makes that owing to being raw material with the coal gac specific surface of making is less, and intensity is relatively poor, the ash height.
It is feedstock production ball-type process of active carbon that U.S. Pat P3917806, USP4228037, the clear 56-5313 of Japanese Patent have introduced a class petroleum pitch.Because these class methods adopt heating and melting to disperse spherical container shaping method, in preparation process, need to add aromatic hydrocarbon solvent, be scattered in then in the solution that contains tensio-active agent, and the high-speed stirring balling-up, again the aromatic solvent in the bitumen ball is carried out extracting with the lighter hydrocarbons solvent afterwards, obtain activated carbon product.By said process as can be seen, this method has shortcomings such as complex process equipment, operation inconvenience, activated carbon product intensity difference, simultaneously, also can produce comparatively serious environmental pollution aborning.
It is the feedstock production process of active carbon with petroleum pitch that FR2467177 discloses a kind of, adopts the fusion spherical container shaping method equally.Though the not mentioned aromatic solvent of using of the document need add pore-forming material in process of production, also need then this pore-forming material is carried out extracting; In addition, must add the anti-fusing of chemistry agent, in the hope of reaching anti-fusing effect.Therefore, this method has shortcomings such as equipment complexity, operation inconvenience and contaminate environment equally.
The objective of the invention is to overcome the shortcoming of prior art, provide a kind of technology simple, easy to operate, pollute little, activated carbon product excellent property and can require produce the preparation method of active carbon of different shape again according to difference.
Technical characterictic of the present invention is:
(1) be that 150～370 ℃ pitch is broken into powdery with softening temperature; Then with this asphalt powder under oxidizing atmosphere, be warming up to 200～350 ℃, carry out 6～72 hours anti-melt processed, product A.
(2) product A and extrusion aid, tackiness agent and water are mixed, moulding and dry gets product B according to a conventional method.
(3) product B is carried out carbonization, activation treatment according to a conventional method, can obtain described activated carbon product.
The granularity of asphalt powder recited above should better be less than 100 orders, preferably less than 200 orders less than 20 orders.The granularity of asphalt powder is excessive, with increasing the difficulty of anti-melt processed, easily causes the adverse consequences of not exclusively bringing the quality of activated carbon variation because of anti-melt processed.
Described anti-melt processed process is meant under oxidizing atmosphere and higher temperature condition, the process that material A is handled.Described oxidizing atmosphere can be gas mixture, the N of air, oxygen, oxygen and nitrogen
2O
4Gas, NO gas etc.Due to economic considerations, air preferably.Preferably 220～300 ℃ of the temperature of anti-melt processed, preferably 8～16 hours treatment time.In the actually operating, as follows material A is carried out anti-melt processed usually: material A is placed container, feed oxidizing gas, as air etc., begin slow intensification from room temperature, heat-up rate is controlled at 0.1～1 ℃/minute usually.When temperature is raised to required temperature, can finish in constant temperature 8-16 hour.This process can be carried out in plurality of devices such as fixed bed, ebullated bed, converter, activation furnace.
Extrusion aid recited above is the starch based flour, as being starch, sesbania powder etc.Described tackiness agent is enol polymkeric substance or cellulose family, preferably polyvinyl alcohol, methylcellulose gum or carboxymethyl cellulose etc.
Described extrusion aid adds with dry powder form, and its effect is to improve structure of activated carbon, when the material extrusion moulding that mixes, can guarantee to extrude smoothly simultaneously.The effect of tackiness agent then mainly is pulverulent material is bonded together effectively, and this agent is that the form with the aqueous solution joins in the powder, and powder is modulated into paste, thereby can easily it be squeezed into different shape, therefore requires its water-soluble will getting well.The mixing of asphalt powder, extrusion aid, tackiness agent and water must be even, otherwise will influence quality product.In addition, the blending ratio of asphalt powder, extrusion aid, tackiness agent and water should be controlled at suitable scope, normally they are mixed by 100: 1～25: 0.8～10: 35～55 weight ratio, preferably pressed 100: 2～15: 0.8～8.0: 38～45 mixed.Surpass this scope, will cause that quality of activated carbon descends or causes inconvenience in the production.Too big as the extrusion aid add-on, not only can increase production cost, can cause also that simultaneously product strength descends; Too small as the extrusion aid add-on, will bring difficulty to extrusion moulding, also can make mixing moulding after material be difficult to carry out fully anti-melt processed.Similarly, too big as the tackiness agent add-on, can increase considerably production cost, and this agent add-on is too little, product strength is descended.Described conventional forming method, be meant modal forming method in catalyst preparation process, as compressing tablet, extrusion, balling-up etc., wherein for the ease of the production process of serialization, preferably adopt the method for extrusion moulding, the plaster material that is about to mix is put into the hopper of banded extruder, makes material pass through the cold-forming process of orifice plate by squeezing action.The drying of material can adopt natural air drying, air blast to dry up or method such as heating, drying after the moulding.
Above describedly according to a conventional method material B is carried out carbonizing treatment, be meant and adopt USP3,917, disclosed method is carried out the carbonizing treatment process in 806, promptly at the material that will resist melt processed (material B), under temperature, carry out the process of carbonizing treatment under the inert gas atmosphere greater than 600 ℃ (600～700 ℃).Activation method is conventional water vapor/nitrogen or CO
2/ N
2Method, temperature are 800～1000 ℃.
Adopt the activated carbon product of the method for the invention preparation, its specification is as follows: specific surface area is 719～1870m
2/ g, pore volume 0.34～0.97ml/g, crushing strength is 8.4～26.6N/mm, ash content＜0.35%.
The present invention will be because employing will be broken into powdered pitch, after anti-melt processed, with mixing moulding such as extrusion aid, tackiness agents; Carry out the technology that carbonization and activation treatment prepare gac then, make its compared with prior art have technology simple, pollute that low, anti-fusing is effective, convenient formation and be easy to advantage such as manipulation of regeneration; The present invention is owing to adopt above-mentioned technology, simultaneously with asphalt powder and extrusion aid, tackiness agent (and water) rational allocation good with its compatibleness, advantage such as make that the activated carbon product make compared with prior art has the physical strength height, absorption property is good and ash is low, the adsorption cleaning process of the gas phase that is specially adapted to have relatively high expectations, liquid-phase system also can be used for simultaneously other adsorption cleaning process or as siccative, catalyzer and the support of the catalyst of oil, chemical field.
Further describe technical characterstic of the present invention below in conjunction with example.
Example 1
100 gram pitches (264 ℃ of softening temperatures, Yanshan Petrochemical company product is by obtaining after the distillation of cracking of ethylene residual oil) are crushed to below 100 orders, be placed in the loft drier, be warming up to 250 ℃ with 0.2 ℃/minute heat-up rate, constant temperature is 2 hours under the air, obtains material A.
In material A, add 3 gram sesbania powder (Shanghai local products company product) mixings.Get 8 gram polyvinyl alcohol (the new Photochemical agents in Beijing factory product) and it be dissolved in the 92 gram water, treat that it fully dissolves after, get this solution 40 grams, join in the mixture of asphalt powder and sesbania powder, fully mix pinch even.And then put it into extrusion moulding in the banded extruder; 120 ℃ were descended dry 2 hours after the moulding, got material B.
Material B 700 ℃ of charings under nitrogen were handled 1 hour, and activation can obtain activated carbon product HA in 1 hour under 900 ℃ of water vapors then, and its performance sees Table 1.
Example 2
100 gram pitches (231 ℃ of softening temperatures, Yanshan Petrochemical company product is by obtaining after the distillation of cracking of ethylene residual oil) are crushed to below 30 orders, are placed in the loft drier, be warming up to 210 ℃ with 0.2 ℃/minute heat-up rate, constant temperature is 4 hours under the air, obtains material A.
In material A, add 13 gram sesbania powder (Shanghai local products company product) mixings.Get 6 gram polyvinyl alcohol (the new Photochemical agents in Beijing factory product) and it be dissolved in the 92 gram water, treat that it fully dissolves after, get this solution 40 grams, join in the mixture of asphalt powder and sesbania powder, fully mix pinch even.And then put it into extrusion moulding in the banded extruder; 120 ℃ were descended dry 2 hours after the moulding, got material B.
Material B 700 ℃ of charings under nitrogen were handled 1 hour, and activation can obtain activated carbon product HB in 1 hour under 900 ℃ of water vapor/nitrogen then, and its performance sees Table 1.
Example 3
100 gram pitches (224 ℃ of softening temperatures, Yanshan Petrochemical company product is by obtaining after the distillation of cracking of ethylene residual oil) are crushed to below 200 orders, be placed in the loft drier, be warming up to 340 ℃ with 0.8 ℃/minute heat-up rate, constant temperature is 1 hour under the air, obtains material A.
In material A, add 5 gram sesbania powder (Shanghai local products company product) mixings.Get 8 gram polyvinyl alcohol (the new Photochemical agents in Beijing factory product) and it be dissolved in the 92 gram water, treat that it fully dissolves after, get this solution 40 grams, join in the mixture of asphalt powder and sesbania powder, fully mix pinch even.And then put it into extrusion moulding in the banded extruder; 120 ℃ were descended dry 2 hours after the moulding, got material B.
Material B 700 ℃ of charings under nitrogen were handled 2 hours, and activation can obtain activated carbon product HC in 1 hour under 900 ℃ of water vapor/nitrogen then, and its performance sees Table 1.
Example 4
100 gram pitches (334 ℃ of softening temperatures, Yanshan Petrochemical company product is by obtaining after the distillation of cracking of ethylene residual oil) are crushed to below 100 orders, be placed in the loft drier, be warming up to 200 ℃ with 0.2 ℃/minute heat-up rate, constant temperature is 12 hours under the air, obtains material A.
In material A, add 3 gram sesbania powder (Shanghai local products company product) mixings.Get 8 gram polyvinyl alcohol (the new Photochemical agents in Beijing factory product) and it be dissolved in the 42 gram water, treat that it fully dissolves after, join in the mixture of asphalt powder and sesbania powder, fully mix pinch even.And then put it into extrusion moulding in the banded extruder; 120 ℃ were descended dry 2 hours after the moulding, got material B.
Material B 700 ℃ of charings under nitrogen were handled 2 hours, and activation can obtain activated carbon product HD in 1 hour under 900 ℃ of water vapor/nitrogen then, and its performance sees Table 1.
Example 5
100 gram pitches (174 ℃ of softening temperatures, Yanshan Petrochemical company product is by obtaining after the distillation of cracking of ethylene residual oil) are crushed to below 30 orders, are placed in the loft drier, be warming up to 240 ℃ with 0.2 ℃/minute heat-up rate, constant temperature is 8 hours under the air, obtains material A.
In material A, add 23 gram sesbania powder (Shanghai local products company product) mixings.Get 1 gram polyvinyl alcohol (the new Photochemical agents in Beijing factory product) and it be dissolved in the 35 gram water, treat that it fully dissolves after, join in the mixture of asphalt powder and sesbania powder, fully mix pinch even.And then put it into extrusion moulding in the banded extruder; 120 ℃ were descended dry 2 hours after the moulding, got material B.
Material B 700 ℃ of charings under nitrogen were handled 2 hours, and activation can obtain activated carbon product HE in 1 hour under 900 ℃ of water vapor/nitrogen then, and its performance sees Table 1.
The Properties of Activated Carbon test comprises specific surface area, pore volume, crushing strength (being called for short intensity in the table 1), ash, iodine number and methylene blue adsorption value (being called for short adsorptive value in the table 1) etc.
Specific surface area and pore volume adopt the B E T Brunauer Emett Teller method of nitrogen adsorption at low temperature test; Ash adopts the test of the standard LY 217-80 of Ministry of Forestry method; Methylene blue adsorption value adopts the test of the standard LY216-79 of Ministry of Forestry method; Iodine number adopts international liquid phase decoloring method test; Crushing strength adopts the method test of introducing among the CN92109335.7.
Table 1
| Numbering | Specific surface area m 2/g | Pore volume ml/g | Intensity N/mm | Ash m% | Adsorptive value mg/g | Iodine number mg/g |
| HA | 1064 | 0.62 | 12.3 | 0.31 | 221 | 1166 |
| HB | 1091 | 0.54 | 11.5 | 0.22 | 148 | 1139 |
| HC | 1100 | 0.58 | 15.8 | 0.11 | 214 | 1114 |
| HD | 1110 | 0.55 | 9.7 | 0.15 | 232 | 1232 |
| HE | 1341 | 0.49 | 11.8 | 0.24 | 119 | 1011 |
Claims (5)
1, a kind of is the feedstock production process of active carbon with pitch, it is characterized in that:
(1) be that 150～370 ℃ pitch is broken into powdery with softening temperature; Then with this asphalt powder under oxidizing atmosphere, be warming up to 200～350 ℃, carry out 6～72 hours anti-melt processed, product A;
(2) product A and extrusion aid, tackiness agent and water are mixed, moulding and dry gets product B according to a conventional method;
(3) product B is carried out carbonization, activation treatment according to a conventional method, can obtain described activated carbon product.
2, in accordance with the method for claim 1, it is characterized in that 1(1) granularity of described asphalt powder should be less than 20 orders; Described oxidizing atmosphere is meant the mixed gas or the N of air or oxygen or oxygen and nitrogen
2O
4Gas or NO gas; Preferably 220～300 ℃ of anti-melt processed temperature, preferably 8～16 hours treatment time.
3, in accordance with the method for claim 2, the granularity that it is characterized in that described asphalt powder better is less than 100 orders; Be preferably less than 200 orders; Described oxidizing atmosphere, preferably air.
4, in accordance with the method for claim 1, it is characterized in that 1(2) blending ratio (weight) of described asphalt powder and extrusion aid, tackiness agent and water is 100: 1～25: 0.8～10: 35～55; Described extrusion aid is the starch based meal, and tackiness agent is enol polymkeric substance or Mierocrystalline cellulose.
5, in accordance with the method for claim 4, it is characterized in that described blending ratio (weight) preferably 100: 2～15: 0.8～8.0: 38～45; Described extrusion aid is sesbania powder or starch preferably, and tackiness agent is polyvinyl alcohol, methylcellulose gum or carboxymethyl cellulose preferably.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN93120925A CN1036333C (en) | 1993-12-21 | 1993-12-21 | Method for preparation of active carbon |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN93120925A CN1036333C (en) | 1993-12-21 | 1993-12-21 | Method for preparation of active carbon |
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| Publication Number | Publication Date |
|---|---|
| CN1104175A true CN1104175A (en) | 1995-06-28 |
| CN1036333C CN1036333C (en) | 1997-11-05 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN93120925A Expired - Fee Related CN1036333C (en) | 1993-12-21 | 1993-12-21 | Method for preparation of active carbon |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1076006C (en) * | 1997-01-28 | 2001-12-12 | 新疆石油管理局独山子石油化工总厂 | Petroleum asphalt based active carbon and its prepn. method |
| CN1089097C (en) * | 1998-01-23 | 2002-08-14 | 中国科学院山西煤炭化学研究所 | Method for preparing asphalt based spherical active carbon by adding inorganic metal salt |
| CN101306815B (en) * | 2007-05-17 | 2011-02-16 | 林建屏 | Process for preparing high adsorbing active carbon by using petroleum coke as raw material |
| CN102218297A (en) * | 2011-04-28 | 2011-10-19 | 孔亦周 | Preparation method of asphalt based spherical active carbon without infusibility processing technology |
| CN110237814A (en) * | 2019-06-21 | 2019-09-17 | 一重集团大连工程建设有限公司 | A kind of preparation method for the active carbon handling marine oil spill |
| CN112125306A (en) * | 2020-09-28 | 2020-12-25 | 烟台中科恩吉科创新产业园管理有限公司 | Activated carbon and preparation method thereof |
-
1993
- 1993-12-21 CN CN93120925A patent/CN1036333C/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1076006C (en) * | 1997-01-28 | 2001-12-12 | 新疆石油管理局独山子石油化工总厂 | Petroleum asphalt based active carbon and its prepn. method |
| CN1089097C (en) * | 1998-01-23 | 2002-08-14 | 中国科学院山西煤炭化学研究所 | Method for preparing asphalt based spherical active carbon by adding inorganic metal salt |
| CN101306815B (en) * | 2007-05-17 | 2011-02-16 | 林建屏 | Process for preparing high adsorbing active carbon by using petroleum coke as raw material |
| CN102218297A (en) * | 2011-04-28 | 2011-10-19 | 孔亦周 | Preparation method of asphalt based spherical active carbon without infusibility processing technology |
| WO2012146048A1 (en) * | 2011-04-28 | 2012-11-01 | 深圳市芭田生态工程股份有限公司 | Preparation method for asphalt-based spherical active carbon with no need for non-melting process |
| CN110237814A (en) * | 2019-06-21 | 2019-09-17 | 一重集团大连工程建设有限公司 | A kind of preparation method for the active carbon handling marine oil spill |
| CN110237814B (en) * | 2019-06-21 | 2022-05-13 | 一重集团大连工程建设有限公司 | Preparation method of activated carbon for treating ocean oil spill |
| CN112125306A (en) * | 2020-09-28 | 2020-12-25 | 烟台中科恩吉科创新产业园管理有限公司 | Activated carbon and preparation method thereof |
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| Publication number | Publication date |
|---|---|
| CN1036333C (en) | 1997-11-05 |
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