CN103194100A - Method for producing carbon black by lignite semi-coke - Google Patents
Method for producing carbon black by lignite semi-coke Download PDFInfo
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- CN103194100A CN103194100A CN2013101128845A CN201310112884A CN103194100A CN 103194100 A CN103194100 A CN 103194100A CN 2013101128845 A CN2013101128845 A CN 2013101128845A CN 201310112884 A CN201310112884 A CN 201310112884A CN 103194100 A CN103194100 A CN 103194100A
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Abstract
The invention discloses a method for producing carbon black by lignite semi-coke. The method comprises the following steps of crushing the lignite semi-coke until the lignite semi-coke is less than 45 microns; removing impurities, and reducing a volatile matter of the lignite semi-coke to below 5%, and reducing ash content of the lignite semi-coke to below 2%, then adjusting the pH value of the lignite semi-coke to 6-8; modifying, and adding a coupling agent to modify. By adopting the method disclosed by the invention to produce the carbon black, the added value of the lignite semi-coke product can be improved; meanwhile, the material source for producing the carbon black can be expanded; dependence on natural gas, the lignite semi-coke and the like is reduced; and the method has important economic value and social value.
Description
Technical field
The present invention relates to a kind of method of the lignite semi-coke utilization of resources, particularly a kind of method of utilizing lignite semi-coke to produce carbon black.
Background technology
China's lignite resource is abundant, and the principal feature of brown coal is moisture content height, oxygen level height, and thermal value is low.Brown coal are carried out the pyrolysis upgrading can make the brown coal that quality is low, purposes is narrow obtain multiple use product widely, simultaneously, brown coal pyrolysis upgrading can become Poly-generation by technology or product deep processing optimum combination, improve overall economic efficiency, as " brown coal pyrolysis upgrading technology and Poly-generation conception " (Guan Jun etc., Coal Chemical Industry, the 6th phase of December in 2011) disclosed such.The described lignite semi-coke of the application, refer to one of main products that obtains after brown coal pyrolysis (destructive distillation) upgrading, its ash oontent is generally more than 5%, the main component of ash content is some water-fast silicate and other inorganic salts, volatile content is generally more than 10%, and the composition of volatile matter mainly is some organism and organo-functional group.Lignite semi-coke can be used as blast furnace blowing material, metallurgical with burnt, industrial fuel and gac raw material etc., but have the carbonization at low temperature composition is had relatively high expectations of these application, the economic worth that has is lower.
Carbon black is a kind of important chemical material, is that hydrocarbons generates through incomplete combustion or cracking.Carbon black mainly is made up of carbon, and its crystallite has the meta anthracite structure, is concentric orientation, and its particle is to be close to spherical nano particle.Because the raw material of production carbon black mainly is that Sweet natural gas, oil system and coal tar are product, along with energy problem's aggravation, Sweet natural gas, ethylene bottom oil and coal tar price rise and fluctuate bigger gradually, make that the production of carbon black cost of carbon black is higher, thereby cause carbon black to hold at high price.
Produce carbon black if utilize resourceful lignite semi-coke, to improve the added value of product of semicoke on the one hand, also can reduce carbon black on the other hand to the dependence of high price, low yield raw material, the coal-based energy utilization frontier of developing solid, for adopting lignite semi-coke to produce the method for carbon black, do not appear in the newspapers at present.
Summary of the invention
The purpose of this invention is to provide a kind of lignite semi-coke and produce the method for carbon black, developing production of carbon black novel method when being intended to improve the coproduction benefit of brown coal upgrading.
The technical scheme that the present invention addresses the above problem handles to obtain carbon black products through modification again after lignite semi-coke is pulverized.Mainly may further comprise the steps:
A kind of method of utilizing lignite semi-coke to produce carbon black is characterized in that: may further comprise the steps successively,
(1) pulverizes, lignite semi-coke is crushed to below the 45 μ m; Adopt breaking methods such as mechanical ball milling, comminution by gas stream, the lignite semi-coke size be crushed to 45 μ m(325 orders) below; Because according to the reinforcing effect of carbon black in rubber, greater than 45 μ m(325 orders) carbon black particle in sizing material, be equivalent to impurity, in sizing material, form physical imperfection, reduce the mechanical property of sizing material, so national standard " GB 3778-2011 rubber grade carbon black " is stipulated also greater than 45 μ m(325 orders) carbon black screenings content≤1000mg/kg;
(2) removal of impurities, it is below 5% that the fugitive constituent of lignite semi-coke is down to mass percent, it is below 2% that the ash content of lignite semi-coke is down to mass percent, then lignite semi-coke pH value is transferred to 6～8;
(3) modification, the interpolation weight percent is 0.5～10% coupling agent in the lignite semi-coke after regulating the pH value, after described lignite semi-coke and the even mixing of coupling agent, namely.In the process of mixing, because lignite semi-coke contains free radical and organo-functional group, as carboxyl, phenolic group, anhydride group, lactone group, carbonyl, quinonyl, ring-type peroxy etc., these functional groups can with coupling agent generation crosslinking reaction, improve the dispersiveness of lignite semi-coke powder and improve physical properties of rubber compound.
As preferably: the method that reduces fugitive constituent in the step (2) is the organic solvent extracting or heat-treats under protection of inert gas.The composition of fugitive constituent mainly is some organism and organo-functional group, and thermal treatment is that fugitive constituent heating is made its volatilization, toluene extracting is with organism and organo-functional group dissolving, to reduce fugitive constituent.Thermal treatment needs protection of inert gas, and preventing high temperature oxidation or to burn, and heat treated temperature is not higher than 900 ℃.
As preferably: the method that reduces ash in the step (2) is pickling or the gas that contains the chlorine element 300～900 ℃ of feedings.
Ash content mainly is some water-fast silicate and other inorganic salts, and pickling mainly is to make water-fast silicate and acid-respons in the ash content, generates behind the water-soluble material to reduce ash oontent.Kind and concentration to acid do not have particular requirement.Because pH causes pH lower during pickling, so need the pH value be transferred to 6-8 with alkali lye, is equivalent to transfer to neutral range.
As preferably: step also is added with the carbon-based material that is no more than lignite semi-coke quality 70% in (3), and mixes with lignite semi-coke and coupling agent.Certain functional group is contained on the carbon-based material surface, as carboxyl, phenolic group, anhydride group, lactone group, carbonyl, quinonyl, ring-type peroxy etc., chemical reaction takes place in coupling agent and these functional groups, can play the dispersiveness of improving carbon-based material, thereby the crosslinked action that increases between carbon-based material and the rubber improves reinforcing property; Under the situation of functional group's deficiency of lignite semi-coke itself, add carbon-based material, more crosslinking reaction can take place, add that the performance of carbon-based material is better than semi-coke powder, namely adding carbon-based material can adjust the performance of lignite semi-coke, to reach the carbon black index that various national standards require.
Further: described carbon-based material is at least a in carbon nanotube, carbon fiber, Graphene, the carbon black.
Further: the coupling agent described in the step (3) is at least a in silane coupling agent, titanate coupling agent, the aluminate coupling agent.
Adopt present method to produce carbon black, production technique is simple, and strong operability can be applied rapidly.
In sum, owing to adopted technique scheme, the invention has the beneficial effects as follows: adopt method of the present invention to produce carbon black, both can improve the added value of product of lignite semi-coke, simultaneously also can enlarge the production of carbon black raw material sources, minimizing has great economic worth and social benefit to the dependence of Sweet natural gas, coal tar wet goods.
Embodiment
Below the present invention is done detailed explanation.
In order to make purpose of the present invention, technical scheme and advantage clearer, below in conjunction with embodiment, the present invention is further elaborated.Should be appreciated that specific embodiment described herein only in order to explaining the present invention, and be not used in restriction the present invention.
Embodiment 1
Be 12.8% with lignite semi-coke A1(fugitive constituent mass content, the ash content mass content is 7.6%) ball milling 5 hours on ball mill, then that ball milling is good semi-coke powder is crossed 325 orders (45 μ m) screen cloth, and the powder that extracts by screen cloth carries out removal of impurities; Under nitrogen protection, feed carbon tetrachloride gas and at 800 ℃ semi-coke powder was heat-treated 2 hours, to reduce its fugitive constituent to 4.5%; Ash content to the ash oontent that then adopts 5% dilute hydrochloric acid to remove in the semi-coke powder is 0.5%, with 5% KOH solution its pH value is transferred to 7 again, obtains product A after adding the titanate coupling agent TM-139 reacting drying of 50% N330 carbon black and 0.5% then.Product A is tested according to national standard " GB 3778-2011 rubber grade carbon black ", and it the results are shown in Table 1.As seen from Table 1, the product A physicals has reached the performance requriements of Sweet natural gas semi-reinforcing hydrocarbon black.
Embodiment 2
Be 15.1% with lignite semi-coke B1(fugitive constituent mass content, the ash content mass content is 7.5%) put into micronizer mill, the semi-coke powder that the micronizer mill discharge port is collected is crossed 325 orders (45 μ m) screen cloth then, and the powder that extracts by screen cloth carries out removal of impurities; At first semi-coke powder is poured into and carried out extracting in the toluene, to reduce its fugitive constituent to 1.9%; Ash content to the ash oontent that adopts 10% dilute sulphuric acid to remove in the semi-coke powder then is 0.4%, with 10% NaOH solution its pH value is transferred to 8 again, then adds 30% carbon nanotube and 10% aluminate coupling agent DL-411, obtains product B after being dried.Product B is tested according to national standard " GB 3778-2011 rubber grade carbon black ", and it the results are shown in Table 1.As seen from Table 1, the product B physicals has reached the performance requriements of N660 carbon black.
Embodiment 3
Be 11.6% with lignite semi-coke C1(fugitive constituent mass content, the ash content mass content is 9.2%) put into micronizer mill, the semi-coke powder that the micronizer mill discharge port is collected is crossed 325 orders (45 μ m) screen cloth then, and the powder that extracts by screen cloth carries out removal of impurities; At first semi-coke powder is poured into and carried out extracting in the toluene, to reduce its fugitive constituent to 1.2%; Ash content to the ash oontent that then adopts rare nitric acid of 15% to remove in the semi-coke powder is 0.5%, with 5% KOH solution its pH value is transferred to 6 again, adds 2% silane coupling agent Si69 then, obtains products C after being dried.Obtain products C after being dried.Products C is tested according to national standard " GB 3778-2011 rubber grade carbon black ", and it the results are shown in Table 2.As seen from Table 2, the products C physicals has reached the performance requriements of N326 carbon black.
Embodiment 4
Be 13.5% with lignite semi-coke D1(fugitive constituent mass content, the ash content mass content is 11.9%) put into superfine mill, the semi-coke powder that the pulverizing mill discharge port is collected is crossed 325 orders (45 μ m) screen cloth then, and the powder that extracts by screen cloth carries out removal of impurities; Under nitrogen protection, feed chlorine and at 600 ℃ semi-coke powder was heat-treated 3 hours, to reduce its fugitive constituent to 0.5%; Ash content to the ash oontent that then adopts 20% acetic acid solution to remove in the semi-coke powder is 0.5%, with 15% NaOH solution its pH value is transferred to 7 again, adds 70% N234 carbon black and 1% silane resin acceptor kh-550 then, obtains product D after being dried.Obtain product D after being dried.Product D is tested according to national standard " GB 3778-2011 rubber grade carbon black ", and it the results are shown in Table 2.As seen from Table 2, product D physicals has reached the performance requriements of N220 carbon black.
The performance of the carbon black that table 1 lignite semi-coke is produced
The performance of the carbon black that table 2 lignite semi-coke is produced
Claims (6)
1. method of utilizing lignite semi-coke to produce carbon black is characterized in that: may further comprise the steps successively,
(1) pulverizes, lignite semi-coke is crushed to below the 45 μ m;
(2) removal of impurities, it is below 5% that the fugitive constituent of lignite semi-coke is down to mass percent, it is below 2% that the ash content of lignite semi-coke is down to mass percent, then lignite semi-coke pH value is transferred to 6～8;
(3) 0.5～10% coupling agent is added weight percent and is in modification in the lignite semi-coke after regulating pH value, with described lignite semi-coke and coupling agent evenly after the mixing namely.
2. a kind of method of utilizing lignite semi-coke to produce carbon black according to claim 1, it is characterized in that: the method that reduces fugitive constituent in the step (2) is the organic solvent extracting or heat-treats under protection of inert gas.
3. a kind of method of utilizing lignite semi-coke to produce carbon black according to claim 1, it is characterized in that: the method that reduces ash in the step (2) is pickling or the gas that contains the chlorine element 300～900 ℃ of feedings.
4. a kind of method of utilizing lignite semi-coke to produce carbon black according to claim 1 is characterized in that: also be added with 70% the carbon-based material that is no more than the lignite semi-coke quality in the step (3), and mix with lignite semi-coke and coupling agent.
5. a kind of method of utilizing lignite semi-coke to produce carbon black according to claim 4 is characterized in that: described carbon-based material is at least a in carbon nanotube, carbon fiber, Graphene, the carbon black.
6. a kind of method of utilizing lignite semi-coke to produce carbon black according to claim 1 is characterized in that: the coupling agent described in the step (3) is at least a in silane coupling agent, titanate coupling agent, the aluminate coupling agent.
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Cited By (6)
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| CN103540172A (en) * | 2013-10-31 | 2014-01-29 | 王兢 | Method and system for preparing regenerative carbon black by deashing and modifying pyrolytic carbon of waste rubber and plastic products |
| CN106276908A (en) * | 2015-12-02 | 2017-01-04 | 临泉县泉河纳米植物新材料有限公司 | A kind of nanometer plant white carbon black and preparation method thereof |
| CN106497152A (en) * | 2016-10-19 | 2017-03-15 | 拜城县中碳科技有限责任公司 | A kind of production technology of the colour carbon black for improving dispersibility and blackness |
| CN110694614A (en) * | 2019-09-04 | 2020-01-17 | 重庆大学 | Preparation method of active semicoke carrier suitable for low-temperature SCR denitration catalyst |
| CN110980932A (en) * | 2019-11-26 | 2020-04-10 | 兰州交通大学 | Oil shale semicoke/polyvinyl alcohol composite immobilized carrier and preparation method thereof |
| CN112194913A (en) * | 2020-11-04 | 2021-01-08 | 中南大学 | Method for preparing carbon black |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103540172A (en) * | 2013-10-31 | 2014-01-29 | 王兢 | Method and system for preparing regenerative carbon black by deashing and modifying pyrolytic carbon of waste rubber and plastic products |
| CN106276908A (en) * | 2015-12-02 | 2017-01-04 | 临泉县泉河纳米植物新材料有限公司 | A kind of nanometer plant white carbon black and preparation method thereof |
| CN106276908B (en) * | 2015-12-02 | 2018-02-06 | 临泉县泉河纳米植物新材料有限公司 | A kind of nanometer plant carbon black and preparation method thereof |
| CN106497152A (en) * | 2016-10-19 | 2017-03-15 | 拜城县中碳科技有限责任公司 | A kind of production technology of the colour carbon black for improving dispersibility and blackness |
| CN110694614A (en) * | 2019-09-04 | 2020-01-17 | 重庆大学 | Preparation method of active semicoke carrier suitable for low-temperature SCR denitration catalyst |
| CN110980932A (en) * | 2019-11-26 | 2020-04-10 | 兰州交通大学 | Oil shale semicoke/polyvinyl alcohol composite immobilized carrier and preparation method thereof |
| CN110980932B (en) * | 2019-11-26 | 2022-06-03 | 兰州交通大学 | Oil shale semicoke/polyvinyl alcohol composite immobilized carrier and preparation method thereof |
| CN112194913A (en) * | 2020-11-04 | 2021-01-08 | 中南大学 | Method for preparing carbon black |
| CN112194913B (en) * | 2020-11-04 | 2021-11-02 | 中南大学 | Method for preparing carbon black |
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Address after: 643000 Zigong city of Sichuan Province, Ziliujing District Hing Road No. 168 Patentee after: Hao Yuan black Research & Design Institute of Chemical Industry Co. Ltd. Address before: 643000, 568, Hui Xing Road, Huili Eastern Road, Sichuan, Zigong Patentee before: China Rubber Group Carbon Black Research & Design Institute |