CN1958150A - High surface-active adsorbing matter, and preparation method - Google Patents
High surface-active adsorbing matter, and preparation method Download PDFInfo
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- CN1958150A CN1958150A CN 200610022034 CN200610022034A CN1958150A CN 1958150 A CN1958150 A CN 1958150A CN 200610022034 CN200610022034 CN 200610022034 CN 200610022034 A CN200610022034 A CN 200610022034A CN 1958150 A CN1958150 A CN 1958150A
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Abstract
An adsorptive material with high surface activity, large specific surface area and uniform pore diameter is prepared from one or more of petroleum coke, asphalt coke, and fruit nut. Its preparing process is also disclosed.
Description
Technical field
The present invention relates to a kind of high surface-active adsorbing matter and preparation method thereof.
Background technology
Active adsorbing material with high surface and high absorption capacity has become the research and development focus of field of new, its purposes is very extensive, mainly comprise fields such as ultracapacitor, transformation absorption, absorption natural gas-storing, medical purification, air cleaning and absorption microwave, obtained tremendous economic and social benefit in fields such as ultracapacitor and transformation absorption at present.As active carbon and NACF etc. promptly is the high surface-active adsorbing matter of using always.But how to expand its market, downstream, enlarge its practical application area, key is to realize the industrialization of such material and significantly reduces its production cost.
More existing patents of invention have been introduced the preparation method of relevant sorbing material therewith.As:
CN 1411903 discloses rich micropore carbon adsorbent of a kind of natural gas-storing and preparation method thereof.This method is a raw material with petroleum coke, lignin, walnut shell, adopts composite activator method double-furnace two-step activation technology and clad forming process to prepare adsorbent.This adsorbent has flourishing especially micropore, its BET (be a kind of mensuration solid method for specific area based on the BET adsorption theory of multimolecular layers, BET is three founder Bo Lu Nao thats (Brunauer), Ai Mote (Emmett) and the Taylor's (Teller) of this theory a abbreviation) specific surface can reach 2500～3500m
2/ g, the pore volume of micropore reaches 1.5～1.8cm
3/ g is a kind of ideal material that adsorbs natural gas-storing, both can be used for the no pipe network storage transportation of natural gas-storing as motor vehicle fuel or domestic fuel and natural gas, can be used to again adsorb toxic and harmful and be used to inhale ripple, sound-absorbing material etc. as coating additive.The shortcoming of this method is complex forming technology, higher, the difficult realization industrialization of preparation cost.
CN 1617273 discloses a kind of double layer capacitor and preparation method thereof, this electrode material adopts composite activating agent, and the method that low temperature and high temperature activate respectively is prepared from, and its micro-pore diameter is distributed as 1～2nm, microporosity is more than 90%, BET specific surface 2500～3500m
2/ g, micropore pore volume 1.5～1.8cm
3/ g.The capacitance of this capacitor is 100～150F/g, electrode density 0.5～0.6g/cm
3, capacitance per unit volume amount 50～80F/cm
3
CN 1070846 and CN 1258638 disclose the preparation method of active carbon of a kind of natural gas adsorbent for store and manufacture method and a kind of absorbing and storing methane respectively, its common feature is to adopt infusion process mixed material and chemical activating agent, adopt single one step of stove activation method to prepare powdered absorbent, the bonding agent compression forming is adopted in the moulding of adsorbent.The obvious weak point of this technology is that priming reaction is inhomogeneous, and properties of product are still undesirable.
CN 1402280 provides a kind of preparation method with formed active carbon electrode of high specific capacitance.This method is the specific area＞3000m with load Mn, Co metal ion
2/ g powdered activated carbon makes carried metal high-specific surface area formed active carbon electrode.
But present high surfacing all in various degree existence activator level is bigger than normal in the preparation, the product pore size distribution is restive, complicated process of preparation, cost is than problems such as height.
Summary of the invention
The purpose of this invention is to provide a kind of new high surface-active adsorbing matter.The specific area height of this sorbing material, even aperture distribution, and production cost is low, more easily realize industrialization.
Another object of the present invention provides a kind of preparation method of above-mentioned high surface-active adsorbing matter.
The technical solution adopted for the present invention to solve the technical problems is: a kind of high surface-active adsorbing matter, this material with in petroleum coke, pitch coke and the shell any one or multiple be that feedstock production forms.
Above-mentioned high surface-active adsorbing matter has flourishing microcellular structure, and its BET specific surface can reach 2000～3000m
2/ g, the pore volume of micropore reaches 1.2～1.5cm
3/ g accounts for more than 90% of total pore volume, and its hole skeleton structure which floor carbon atom lamella flexural deformation is made of, and the carbon atom on the interface mainly forms multiple oxygen-containing functional group such as C-O-C, C-OH, C=O, O-C-O and COOH etc.
Above-mentioned high surface-active adsorbing matter can prepare by the method that mainly may further comprise the steps:
(1) one section charing: with described raw material pulverizing, sieve into 200～500 order powder, through 700～900 ℃ of charings 1.5～3 hours;
(2) three stage activations: the raw material after the charing is directly mixed with 1: 1～1: 3 ratio with KOH, in 150～550 ℃ low-temp reaction stove, reacted 1～2 hour; Material behind the low-temp reaction enters high temperature reaction stove, reacts 1～2 hour down at 650～850 ℃ earlier, reacts 1～3 hour down at 950～1050 ℃ again;
(3) cleaning, drying: the material behind the priming reaction is extremely neutral through washing and pickling, make the powdery high surface-active adsorbing matter through abundant drying again.
The carbonization temperature of raw material is preferably 800 ℃ in above-mentioned (1) step, and carbonization time is preferably 2 hours.
Used sour available watery hydrochloric acid or dilute sulfuric acid etc. in above-mentioned (3) step; Be preferably watery hydrochloric acid.
In above-mentioned one section charing and three stage activation processes, can realize the heat integration and the material associating of charing and activation process, effectively to reduce production costs.And, the activation process of charing and different temperatures reaches the efficient utilization of heat energy by heat-exchange network, and the oxygen enrichment process of activation and the oxygen process of charing are coupled, and carry out in same activation furnace, can realize whole material balance and thermal balance, environment does not pollute to external world.
The high surface-active adsorbing matter that adopts above-mentioned technology to make has higher specific surface area and good adsorption performance, can be used for fields such as ultracapacitor, transformation absorption purifying hydrogen of hydrogen, absorption natural gas-storing and absorption microwave.It can reach 40～50F/g at the apparent specific capacitance of organic system bipolar electrode at normal temperatures when being used for ultracapacitor.
Compared with prior art, the invention has the beneficial effects as follows: the specific area height of high surface-active adsorbing matter of the present invention, even aperture distribution, and raw material is easy to get, and production cost is low.On the other hand, the preparation method of high surface-active adsorbing matter of the present invention is simple to operate, more easily realizes industrialization; And by the heat integration and the material associating of realization charing of PROCESS COUPLING technology and activation process, can control specific area, the pore-size distribution of product, be beneficial to the energy optimization utilization, can significantly reduce production costs, and this method help developing accessory substance K
2CO
3Recovery and utilization technology and the reaction flue gas utilize technology, can accomplish " zero " pollution substantially.
The specific embodiment
The present invention is described in further detail below in conjunction with the specific embodiment.
But this should be interpreted as that the scope of the above-mentioned theme of the present invention only limits to following embodiment.Do not breaking away under the above-mentioned technological thought situation of the present invention, various replacements or change according to ordinary skill knowledge and customary means are made include within the scope of the invention.
Embodiment 1
(1) one section charing: described raw material petroleum coke, pitch coke and shell are mixed, pulverize with any arbitrary proportion, sieve into 200～300 order powder, through 800 ℃ of charings 2 hours;
(2) three stage activations: the raw material after the charing is directly mixed with 1: 2 ratio with KOH, and reaction is 2 hours in 300 ℃ low-temp reaction stove; Material behind the low-temp reaction enters high temperature reaction stove, 750 ℃ of down reactions 1 hour, after enter high temperature section, 1000 ℃ of activation 2 hours down;
(3) cleaning, drying: the material behind the priming reaction is washed till neutrality through washing and watery hydrochloric acid, and fully drying makes the powdery high surface-active adsorbing matter.
Apparent specific capacitance at the organic system bipolar electrode under the material normal temperature of gained is 45F/g.
Embodiment 2
(1) one section charing: described raw material petroleum coke, pitch coke and shell are mixed, pulverize with any arbitrary proportion, sieve into 400～500 order powder, through 800 ℃ of charings 2 hours;
(2) three stage activations: the raw material after the charing is directly mixed with 1: 1 ratio with KOH, and reaction is 1 hour in 200 ℃ low-temp reaction stove; Material behind the low-temp reaction enters high temperature reaction stove, reacts 2 hours down at 850 ℃ earlier, reacts 1 hour down at 950 ℃ again;
(3) cleaning, drying: the material behind the priming reaction is washed till neutrality through washing and watery hydrochloric acid, makes the powdery high surface-active adsorbing matter through abundant drying again.
Apparent specific capacitance at the organic system bipolar electrode under the material normal temperature of gained is 49F/g.
Embodiment 3
(1) one section charing: described material asphalt coke powder is broken, sieve into 200～300 order powder, through 700 ℃ of charings 3 hours;
(2) three stage activations: the raw material after the charing is directly mixed with 1: 3 ratio with KOH, and reaction is 2 hours in 550 ℃ low-temp reaction stove; Material behind the low-temp reaction enters high temperature reaction stove, reacts 1 hour down at 700 ℃ earlier, reacts 2 hours down at 1050 ℃ again;
(3) cleaning, drying: the material behind the priming reaction is washed till neutrality through washing and watery hydrochloric acid, makes the powdery high surface-active adsorbing matter through abundant drying again.
Apparent specific capacitance at the organic system bipolar electrode under the material normal temperature of gained is 41F/g.
Embodiment 4
(1) one section charing: described raw material petroleum coke is pulverized, sieved into 300～500 order powder, through 900 ℃ of charings 1.5 hours;
(2) three stage activations: the raw material after the charing is directly mixed with 1: 2 ratio with KOH, and reaction is 1 hour in 400 ℃ low-temp reaction stove; Material behind the low-temp reaction enters high temperature reaction stove, reacts 2 hours down at 800 ℃ earlier, reacts 3 hours down at 950 ℃ again;
(3) cleaning, drying: the material behind the priming reaction is washed till neutrality through washing and watery hydrochloric acid, makes the powdery high surface-active adsorbing matter through abundant drying again.
Apparent specific capacitance at the organic system bipolar electrode under the material normal temperature of gained is 40F/g.
Embodiment 5
(1) one section charing: described material asphalt Jiao and shell are mixed, pulverize with any arbitrary proportion, sieve into 300～400 order powder, through 800 ℃ of charings 2 hours;
(2) three stage activations: the raw material after the charing is directly mixed with 1: 3 ratio with KOH, and reaction is 2 hours in 150 ℃ low-temp reaction stove; Material behind the low-temp reaction enters high temperature reaction stove, reacts 2 hours down at 650 ℃ earlier, reacts 3 hours down at 1050 ℃ again;
(3) cleaning, drying: the material behind the priming reaction is extremely neutral through washing and dilute sulfuric acid dip, make the powdery high surface-active adsorbing matter through abundant drying again.
Apparent specific capacitance at the organic system bipolar electrode under the material normal temperature of gained is 47F/g.
Claims (6)
1. high surface-active adsorbing matter is characterized in that: this material with in petroleum coke, pitch coke and the shell any one or multiple be that feedstock production forms.
2. high surface-active adsorbing matter according to claim 1 is characterized in that: described high surface-active adsorbing matter has flourishing microcellular structure, and its BET specific surface reaches 2000～3000m
2/ g, the pore volume of micropore reaches 1.2～1.5cm
3/ g accounts for more than 90% of total pore volume, and its hole skeleton structure which floor carbon atom lamella flexural deformation is made of, and the carbon atom on the interface mainly forms multiple oxygen-containing functional group.
3. high surface-active adsorbing matter according to claim 2 is characterized in that: described oxygen-containing functional group mainly is C-O-C, C-OH, C=O, O-C-O and COOH.
4. the preparation method of the described high surface-active adsorbing matter of claim 1 may further comprise the steps:
(1) one section charing: with described raw material pulverizing, sieve into 200～500 order powder, through 700～900 ℃ of charings 1.5～3 hours;
(2) three stage activations: the raw material after the charing is directly mixed with 1: 1～1: 3 ratio with KOH, in 150～550 ℃ low-temp reaction stove, reacted 1～2 hour; Material behind the low-temp reaction enters high temperature reaction stove, reacts 1～2 hour down at 650～850 ℃ earlier, reacts 1～3 hour down at 950～1050 ℃ again;
(3) cleaning, drying: the material behind the priming reaction is extremely neutral through washing and pickling, make the powdery high surface-active adsorbing matter through abundant drying again.
5. the preparation method of high surface-active adsorbing matter according to claim 4 is characterized in that: the carbonization temperature of raw material is 800 ℃ in described (1) step, and carbonization time is 2 hours.
6. the preparation method of high surface-active adsorbing matter according to claim 4 is characterized in that: the used acid of pickling is watery hydrochloric acid in described (3) step.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101844069A (en) * | 2010-04-23 | 2010-09-29 | 成都益盛环境工程科技有限责任公司 | Method for preparing high surface-activity adsorbing carbon material through catalysis and activation synchronous process |
| CN106587050A (en) * | 2016-12-28 | 2017-04-26 | 中国石油大学(华东) | Preparing method of biomass-residual oil co-coking activated carbon |
| CN106582529A (en) * | 2016-12-28 | 2017-04-26 | 中国石油大学(华东) | Application of biomass-residual oil co-coked activated carbon in adsorption desulfurization of crude oil |
-
2006
- 2006-10-13 CN CNB2006100220346A patent/CN100479914C/en active Active
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101844069A (en) * | 2010-04-23 | 2010-09-29 | 成都益盛环境工程科技有限责任公司 | Method for preparing high surface-activity adsorbing carbon material through catalysis and activation synchronous process |
| CN101844069B (en) * | 2010-04-23 | 2013-03-27 | 成都益盛环境工程科技有限责任公司 | Method for preparing high surface-activity adsorbing carbon material through catalysis and activation synchronous process |
| CN106587050A (en) * | 2016-12-28 | 2017-04-26 | 中国石油大学(华东) | Preparing method of biomass-residual oil co-coking activated carbon |
| CN106582529A (en) * | 2016-12-28 | 2017-04-26 | 中国石油大学(华东) | Application of biomass-residual oil co-coked activated carbon in adsorption desulfurization of crude oil |
| CN106582529B (en) * | 2016-12-28 | 2019-01-22 | 中国石油大学(华东) | A kind of biomass-residual oil is total to application of the coking active carbon in crude oil absorption desulfurization |
| CN106587050B (en) * | 2016-12-28 | 2019-02-26 | 中国石油大学(华东) | A kind of biomass-residual oil is total to the preparation method of coking active carbon |
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| CN100479914C (en) | 2009-04-22 |
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Assignee: Daying Juneng Science and Technology Development Co., Ltd Assignor: Yisheng Environment Engineering Tech Co., Ltd., Chengdu Contract fulfillment period: 2007.1.8 to 2016.12.20 contract change Contract record no.: 2009510000026 Denomination of invention: High surface-active adsorbing matter, and preparation method Granted publication date: 20090422 License type: Exclusive license Record date: 2009.9.10 |
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Free format text: EXCLUSIVE LICENSE; TIME LIMIT OF IMPLEMENTING CONTACT: 2007.1.8 TO 2016.12.20; CHANGE OF CONTRACT Name of requester: DAYING JUNENG SCIENCE AND TECHNOLOGY DEVELOPMENT C Effective date: 20090910 |
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Effective date of registration: 20160721 Address after: 629300 Suining Industrial Development Zone, Daying County, Sichuan, China Patentee after: Daying Juneng Science and Technology Development Co., Ltd Address before: 8 No. 64, No. 610041, KELONG North Road, Sichuan, Chengdu, No. 4 Patentee before: Yisheng Environment Engineering Tech Co., Ltd., Chengdu |