CN101497027A - Method for preparing adsorption material using modified coal-tar pitch - Google Patents
Method for preparing adsorption material using modified coal-tar pitch Download PDFInfo
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- CN101497027A CN101497027A CNA200910073671XA CN200910073671A CN101497027A CN 101497027 A CN101497027 A CN 101497027A CN A200910073671X A CNA200910073671X A CN A200910073671XA CN 200910073671 A CN200910073671 A CN 200910073671A CN 101497027 A CN101497027 A CN 101497027A
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Abstract
The invention provides a method for preparing an adsorption material from modified coal tar asphalt, and aims at lowering production cost. The method comprises that: after the coal tar is continuously fractionated, the medium-temperature asphalt on the bottom part of a second-segment evaporator is placed in a reaction kettle, by filled with compressed air, the medium-temperature asphalt is forced to be oxidized for 3 to 6 hours to become the modified asphalt, and the softening point of the modified asphalt is rised to be 100 to 120 DEG C; the modified asphalt is cooled down and ground into the modified asphalt powder with the size of between 50 and 100mu m; the unmodified medium-temperature asphalt is ground into powder to be used as a bonding agent, quaternary amination cation fulvic acid is added to be used as a chemical activation additive, and silanization fulvic acid is added to be used as a thinning agent; at a temperature of between 75 and 90 DEG C, the modified asphalt powder is subjected to strip-extrusion by an extrusion pelletizer, cutting, rounding and granulation; the obtain particle is sent to a carbonized oven, filled with nitrogen gas for protection and subjected to infusible carbonization through three phases, and filled with vapor for activation for 5 hours when the final temperature reaches 900 DEG C; and after reaction, the heating stops, the nitrogen gas is continuously filled until the sample is cooled down to the room temperature, and the formed asphalt active carbon is taken out.
Description
Technical field
The present invention relates to a kind of method of utilizing modified coal tar pitch to prepare sorbing material.
Technical background
The range of application of sorbing material is very wide, and the present preparation method of active carbon class sorbing material mainly is physical activation method and chemical activation method.Physical activation method is carbon and the CO2 that utilizes in the modified coal tar pitch,, gas activation agent effect such as H2O, produce the big sorbing materials of porosity such as micropore, mesopore.Chemical activation then generally adds KOH, ZnCl2 or H2PO4 and modified coal tar pitch reaction generating structure compound thing and takes up space, and forms hole by clearing up reaction (wash-out) again, is the big sorbing material of surface area.These two kinds of preparation methods' production cost is all than higher.And coal tar pitch is the residue behind coal tar distillation extraction light oil, carbolic oil, naphtalene oil, washing oil and the carbolineum.Domestic existing coal tar pitch is mid temperature pitch mostly, because the unsaturated aromatic hydrocarbon that contains in the mid temperature pitch, ager process is fast than asphalt under the effect of oxygen, daylight temperature, ultraviolet ray and precipitation in air, and the harmful composition that contains is many than asphalt, and therefore the application in urban construction such as high-grade highway is restricted.If can utilize coal tar pitch to produce sorbing material, will help enlarging the use approach of coal tar pitch, reduce the production cost of sorbing material simultaneously.
Summary of the invention
The present invention seeks to overcome the deficiency of above-mentioned prior art, the modified coal-tar pitch that utilizes that to provide a kind of be raw material with the coal tar pitch, can reduce production costs prepares the method for sorbing material.
The present invention is by the forced oxidation to the part mid temperature pitch, extract part photo-thermal unstability compounds such as the pitch pyrene that cracking produces in oxidizing process, firefly anthracene, make the modified coal tar pitch softening point rise to 100～120 ℃, then with its cooling, wear into asphalt powder, coexist mixing under the effect of additives such as quaternary ammoniated cation fulvic acid, silanization fulvic acid, thinner with upgrading mid temperature pitch powder one not, extrusion, cutting, rounding, granulation obtain the big active carbon class sorbing material of specific area through charing, activation etc. again in the extruding pelletizer.
The inventive method is:
(1) mid temperature pitch at the bottom of the flash evaporator still after the continuous fractionation of coal tar is placed reactor, under 385～425 ℃ of conditions of temperature, feeding pressure by mid temperature pitch and compressed air volume ratio 1:1～2 is the compressed air of 0.02-0.5MPa, forced oxidation 3～6 hours, become modified coal tar pitch, its softening point rises to 100～120 ℃;
(2) wear into the modified coal tar pitch powder of 50～100 μ m after the cooling;
(3) the mid temperature pitch of upgrading is not clayed into power as binding agent, is that mix 1:1～3 according to binding agent and modified coal tar pitch powder weight ratio, becomes the mix asphalt powder;
(4) be that the ratio of 1:0.001～0.05 adds quaternary ammoniated cation fulvic acid and makes the chemical activation additive according to mix asphalt powder and cation fulvic acid weight ratio, the fulvic acid (FA) that adds silanization in same ratio is made thinner again;
(5) under 75～90 ℃ of temperature, by extruding pelletizer extrusion, granulation behind cutting, rounding;
(6) retort is sent in granulation, charge into the nitrogen protection that flow is 12ml/ming, divide 320～400 ℃ with 3 ℃/min, 4 ℃/min, the speed of 5 ℃/min, 400～750 ℃, 750～900 ℃ of three stage do not melted charing, when treating that temperature reaches three phase temperature of charing, each constant temperature 15min time, continue then to heat up; When reaching whole warm 900 ℃, fed steam activation 5 hours; Stop heating after the end, the nitrogen that continues to feed 3 ℃/min takes out the pitch active carbon of moulding up to the sample cool to room temperature.
Ordinary circumstance by pushing the vertical bar that pelletizer is extruded into diameter 1～5mm, causes diameter 1～5mm particle behind cutting, rounding.Part light, thermal instability compounds such as the pyrene that cracking produces to the reinforcement oxidizing process, firefly anthracene can pass through outer destilling tower of reactor and aerial cooler cooling, recovery.
The present invention is applicable to and utilizes modified coal-tar pitch to prepare sorbing material.The present invention utilizes the advantage that the coal tar pitch ash content is low, phosphorus content is high, both improved the softening point of modified coal tar pitch by forced oxidation, make the big sorbing material of specific area, can reclaim part light, thermal instability compounds such as the pyrene that produces in the original and oxicracking process in the coal tar pitch, firefly anthracene, improved the input-output ratio that coal tar is produced, enlarge the approach that utilizes of coal tar pitch, also reduced the production cost of sorbing material simultaneously.Utilize the interaction of modification fulvic acid and asphalt surface functional group, make active carbon material adsorbing material not only have big specific area, and have chemisorption, can improve its adsorption capacity specific pollutants.
Description of drawings
Fig. 1 is the infrared absorpting light spectra of medium temperature coal pitch behind the upgrading of the present invention.
The specific embodiment
Get softening point and be 81 ℃ mid temperature pitch 1000g, at 395 ℃ of temperature, pressure 0.05MPa, charged into compressed air in 1: 2 by volume in the reactor of 10000ml, constant temperature forced oxidation 6 hours, press the GB2294-1997 method and detect, the modified coal tar pitch softening point rises to 112 ℃ (infrared spectrum analysis behind its upgrading as shown in Figure 1); Simultaneously, the fluorenes that recovery is cooled off by the cracking of reactor top, pyrene, firefly anthracene etc., other is GC-MS and analyzes (wherein, except that naphthalene, a, B methyl naphthalene, anthracene, phenanthrene, carbazole, main component fluorenes 2.26%, pyrene 12.32%, firefly anthracene 1.67%), the pitch glue that takes out the transformation of the way in the still is at last worn into the asphalt powder of 100 μ m.
Get fusing point and be 110 ℃ modified coal tar pitch 1000g, fusing point is 81 ℃ of mid temperature pitch 500g, under 85 ℃ of extruding pelletizer temperature, carry out swelling, shearing, and add the fulvic acid thinner of rotten acid additive of quaternary ammoniated cationic yellow and silanization simultaneously according to identical weight, the ratio that two kinds of fulvic acids mix back weight and pitch material weight is 0.05:1, and time of staying 20min extrudes the vertical bar of diameter 2mm, cutting, rounding obtain the pitch carbon granule of diameter 2mm.
The pitch carbon granule is sent into retort; charge under the nitrogen protection that flow is 12ml/ming with 3 ℃/min, 4 ℃/min, the speed of 5 ℃/min and divide 320～400 ℃; 400～750 ℃; 750～900 ℃ of three stage do not melt, charing; when treating that temperature reaches three phase temperature of charing; each constant temperature 15min time; continue then to heat up; when reaching whole warm 900 ℃; feed 0.11～0.13Mpa steam, activate 5 hours, stop heating after the end; the nitrogen that continues to feed 3 ℃/min takes out the pitch active carbon of moulding up to the sample cool to room temperature.
Measure gained sorbing material iodine sorption value 〉=950mg/g, methylene basket value 〉=120mg/g, specific area 1700m2/g by analysis.
Claims (3)
1, a kind of method of utilizing modified coal-tar pitch to prepare sorbing material is characterized in that:
(1) mid temperature pitch at the bottom of the flash evaporator still after the continuous fractionation of coal tar is placed reactor, under 385～425 ℃ of conditions of temperature, feeding pressure by mid temperature pitch and compressed air volume ratio 1:1～2 is the compressed air of 0.02-0.5MPa, forced oxidation 3～6 hours, become modified coal tar pitch, its softening point rises to 100～120 ℃;
(2) wear into the modified coal tar pitch powder of 50～100 μ m after the cooling;
(3) the mid temperature pitch of upgrading is not clayed into power as binding agent, is that mix 1:1～3 according to binding agent and modified coal tar pitch powder weight ratio, becomes the mix asphalt powder;
(4) be that the ratio of 1:0.001～0.05 adds quaternary ammoniated cation fulvic acid and makes the chemical activation additive according to mix asphalt powder and cation fulvic acid weight ratio, the fulvic acid (FA) that adds silanization in same ratio is made thinner again;
(5) under 75～90 ℃ of temperature, by extruding pelletizer extrusion, granulation behind cutting, rounding;
(6) retort is sent in granulation, charge into the nitrogen protection that flow is 12ml/ming, divide 320～400 ℃ with 3 ℃/min, 4 ℃/min, the speed of 5 ℃/min, 400～750 ℃, 750～900 ℃ of three stage do not melted charing, when treating that temperature reaches three phase temperature of charing, each constant temperature 15min time, continue then to heat up; When reaching whole warm 900 ℃, fed steam activation 5 hours; Stop heating after the end, the nitrogen that continues to feed 3 ℃/min takes out the pitch active carbon of moulding up to the sample cool to room temperature.
2, the method for utilizing modified coal-tar pitch to prepare sorbing material as claimed in claim 1 is characterized in that causing diameter 1～5mm particle by pushing the vertical bar that pelletizer is extruded into diameter 1～5mm behind cutting, rounding.
3, the method for utilizing modified coal-tar pitch to prepare sorbing material as claimed in claim 1 is characterized in that granulation is sent into when reaching eventually 900 ℃ of temperature behind the retort, feeds 0.11～0.13Mpa steam activation 5 hours.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101705355B (en) * | 2009-12-23 | 2011-06-29 | 任瑞刚 | Technique for producing metallurgical pellets |
| CN110272764A (en) * | 2019-06-04 | 2019-09-24 | 新奥科技发展有限公司 | A kind of preparation method of semicoke flying dust modifying agent and the utilization method of semicoke flying dust |
| CN111263731A (en) * | 2017-10-26 | 2020-06-09 | 浦项化学株式会社 | Preparation method of porous carbon material by using coal tar generated in COG (chemical oxygen demand) process |
-
2009
- 2009-01-16 CN CN200910073671XA patent/CN101497027B/en active Active
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101705355B (en) * | 2009-12-23 | 2011-06-29 | 任瑞刚 | Technique for producing metallurgical pellets |
| CN111263731A (en) * | 2017-10-26 | 2020-06-09 | 浦项化学株式会社 | Preparation method of porous carbon material by using coal tar generated in COG (chemical oxygen demand) process |
| US11369941B2 (en) | 2017-10-26 | 2022-06-28 | Posco Chemical Co., Ltd. | Method for preparing porous carbon material by using coal tar generated in COG process |
| CN111263731B (en) * | 2017-10-26 | 2022-12-23 | 浦项化学株式会社 | Preparation method of porous carbon material by using coal tar generated in COG (chemical oxygen demand) process |
| CN110272764A (en) * | 2019-06-04 | 2019-09-24 | 新奥科技发展有限公司 | A kind of preparation method of semicoke flying dust modifying agent and the utilization method of semicoke flying dust |
| CN110272764B (en) * | 2019-06-04 | 2020-12-29 | 新奥科技发展有限公司 | Preparation method of semicoke fly ash modifier and utilization method of semicoke fly ash |
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