CN102702801B - High-purity carbon black and production method thereof - Google Patents
High-purity carbon black and production method thereof Download PDFInfo
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Abstract
The invention discloses a method for producing high-purity carbon black. The method comprises the following steps of: adding the ordinary carbon black into a closed heating device, vacuumizing, introducing a purifying agent containing a chlorine element, heating to the temperature of between 900 and 3,500 DEG C, keeping the temperature for at least 5 minutes, and introducing inert gases into the heating device to obtain the high-purity carbon black, wherein the moisture content is low, ash content is below 100 ppm, and 45-micrometer screenings can reach below 20 ppm; the content of metal impurities is low, and particularly the content of Fe is below 50 ppm; and the requirement of batteries in the field of energy can be met, and the high-purity carbon black can be used for food and metallurgical products, improves the technical and economic content and competitive strength of relevant products in China and has significant economic value and social benefit.
Description
Technical field
The present invention relates to a kind of carbon black, particularly a kind of high-purity carbon black.
Background technology
Carbon black is that hydrocarbons generates through incomplete combustion or cracking.Carbon black is of many uses, except for the rubber item reinforcement, also can be used for other material, as coating, paint, printing ink, ink powder, electronic product, plastics, fiber, battery etc., gives goods required painted, conductivity.In addition, carbon black can also be as the important source material of metallurgical industry.
The purity of carbon black can be divided into physics purity and chemical pure cleanliness two classes.The physics purity refers to the impurity in carbon black, and burnt grain and other mechanical inclusion, content what comprise, usually adopts 45 μ m screeningss to measure.The rubber grade carbon black standard allows 45 μ m screeningss≤0.10%, namely≤1000 ppm, and common product reality is in 200 ppm left and right, i.e. the application's described " ordinary carbon black ".Improve physics purity main path and have two: one is to start with from production technique, and the equipment and the higher stock oil of purity that adopt anticorrosive to manufacture are strengthened raw material oil throwing and micrometer crusher process, to produce the lower carbon black of screenings; Another is that carbon black products is carried out to superfine grinding and stage treatment.The chemical pure cleanliness refers in carbon black products, what of sulphur, metal, polycyclic aromatic hydrocarbons and benzopyrene content.The carbon black of high chemical pure cleanliness, can be by carrying out the chemical liquid phase purifying to carbon black, i.e. pickling obtains, but the method needs follow-up drying treatment, and production cost is very high, but also pollution problem easily occurs.
Along with the development of science and technology and improving constantly of human's demand, more and more higher for the purity requirement of carbon black.
In field of batteries, the high purity graphitized carbon black is the indispensable additive of power lithium-ion battery, and its performance is directly connected to the development of power lithium-ion battery performance and technology.The raising in power lithium-ion battery specific storage and life-span and the internal resistance of cell and negative material activity have direct relation, and the size of the internal resistance of cell directly is decided by the conductive agent that adopts---the performance of carbon black.Power cell adopts repeatedly in application, the high current charge-discharge mode of rapid charge is worked.Impurity in carbon black, as the material of inorganic salt one class, can be from solving metal ion in electrolytic solution.The reaction that occurs in battery is very complicated, and metal ion can resolve to metal after repeated charge.The existence of these metals can reduce the capacity of secondary cell on the one hand, and the metal of separating out simultaneously can form " dendrite " and puncture that barrier film causes instantaneous short circuit and to produce amount of heat explosion caused.Therefore, high-purity graphitized carbon black is to determine the safe reliability of power cell and the important factor in work-ing life.
At present, the Timcal(Te Migao on Switzerland uncle ground difficult to understand) graphite and C.-Chem AG adopt special technique, control gasdynamics and thermodynamic condition in production of carbon black: lower flow velocity, do not add quenched water extinguishing and additive-free, the ENSACO that produces and SUPER P series graphitized carbon black product have high purity, and (its metals content impurity is lower than 50ppm, ash content is lower than 0.1%), be widely used in lithium cell.But this production technique is all high especially to the requirement of raw materials for production, equipment, technique, makes production cost high.
Domestic graphitized carbon black product mainly contains three classes.One class is the heavy oil gasification by product carbon, has good electroconductibility, but owing to being by product, purity is not high, output is limited.Equations of The Second Kind is acetylene black, acetylene black is the carbon black of the good conductivity take acetylene gas as raw material production, but energy consumption is high, pollution is large, and this class particle size carbon black is excessive, microtexture with porous, in the charging and discharging lithium battery process, can produce larger expansion or contraction, cause lithium salts to come off and cell container is decayed rapidly.The 3rd class is the Audit For Process graphitized carbon black, and the Audit For Process graphitized carbon black has good electroconductibility and dispersiveness, but is subjected to the restriction of raw material and production technique, and product purity is low, can not meet the requirement of dynamic lithium battery conductive agent.
In food service industry, with the coloring plastic of Food Contact, toy for children, plastic dinner dish, cookware etc., require to adopt the food-grade high-purity colour carbon black.U.S. food and drug administration (FDA) past regulation only allows to use thermally oxidized black with the tinting material of the plastics of Food Contact, has allowed now to use the high purity furnace treated black.Its purity requirement is in carbon black: polycyclic aromatic hydrocarbons (PAHs)≤0.5 ppm; Benzopyrene≤5.0 ppb; Addition in plastics≤2.5 %(quality).The food grade carbon black mainly contains Black Pearls 4350 and the Monarch 4750 that U.S. Cabot Co.,Ltd produces, Pure black 100 Carbon and 115 Carbon of Columbia Co., Ltd's exploitation, the PRINTEX F alpha of Germany's goldschmidt chemical corporation exploitation etc., the domestic report that yet there are no oven process food grade production of carbon black.
At metallurgy industries such as Wimet, also require carbon black purity high (carbon content >=99%), sulphur content is low, and ash content and other detrimental impurity content are atomic.Normally take the Sweet natural gas after desulfurization as raw material production, production unit mainly adopts stainless steel to metallurgy with carbon black at present, and the production technique water requires, through purifying treatment, to make production cost higher.
Therefore, the simple controlled highly purified carbon black of low, the production method of a kind of production cost of exploitation is all a kind of urgent demand for the fields such as field of batteries, field of food or Wimet.
Summary of the invention
One of goal of the invention purpose of the present invention is: for the problem of above-mentioned existence, provide the production method of the high-purity carbon black that a kind of production cost is low, production method is simply controlled.
The technical solution used in the present invention is such: a kind of production method of high-purity carbon black is characterized in that: comprise the following steps successively,
(1) ordinary carbon black is put into to airtight heating unit; Airtight heating unit can adopt the devices such as high-temperature heater;
(2) after heating unit is vacuumized, then pass into the purifying agent that contains the chlorine element, be warming up to 900～3500 ℃; In order to prevent in the situation that there is the air carbon black oxidized, so before carrying out purification reaction, make reaction unit keep vacuum state, to prevent the introducing of new impurity;
(3), under 900～3500 ℃, be incubated at least 5 minutes;
(4) in heating unit, pass into rare gas element again; For the haloid element of eliminating system introducing, so pass into rare gas element;
(5) heating unit is cooled to room temperature, closes aforesaid purifying agent and rare gas element, obtains.
As preferably: in (2) step, be evacuated to 100Pa or below 100Pa.Air is removed more thorough, carbon black oxidized probability and ratio in the vapor phase purification reaction process is less, be conducive to reduce the loss of carbon black in purge process, improve carbon yield and quality, but vacuum tightness more greatly more can increase production time and cost, the contriver is by great many of experiments, determine vacuum tightness be 100Pa and following be optimal balance between purification effect and cost.
As preferably: purifying agent described in (2) step is at least a in chlorine, Refrigerant 12, tetracol phenixin.
As preferably: described in (4) step, rare gas element is argon gas or nitrogen.
In the present invention, the gas chemistry purifying treatment is the key that obtains high-purity carbon black.Off the beaten track magnet purifying or chemical liquid phase purifying process, high-temperature stability according to carbon black, by controlling the high temperature purification temperature and time, and the flow of purifying agent, can determine according to the amount of the carbon black of processing and the size of high temperature purification furnace volume, ordinary carbon black is carried out to purification process, make ash content, fugitive constituent and metallic impurity be discharged from the pyroprocessing system with gaseous form, thereby obtain high-purity carbon black.
In the present invention, the ultimate principle of ordinary carbon black being carried out to purifying is: because the main component of carbon black is carbon, at high temperature have very strong stability, the moisture in carbon black, organic constituent can at high temperature be vaporized, and take body of heater out of by carrier gas.Therefore, the ash content in carbon black and metallic impurity are the keys that affect purification effect.The present inventor passes through great many of experiments, filtered out suitable purifying agent, such purifying agent has very strong reactive behavior, at high temperature the metal impurities oxidation in carbon black can be generated and has the material than low melting point, after the gasification substance of low melting point, just can leave carbon black, make carbon black obtain purifying.
Specifically, the moisture in carbon black and organic constituent are by volatilization or decomposition, and other impurity with after the purifying agent reaction that contains the chlorine element is taken out of body of heater with muriatic form.The chlorination of impurity in being conducive to carbon black more than 900 ℃, because chlorine and metal impurities at high temperature have very strong reactive behavior.Iron is the major metal impurity in carbon black, and metal chloride has lower fusing point, and metal chloride is in case formation is left proceeding of carbon black promotion purifying thereby they will be vaporized.Because the pushing effect of carrier gas is arranged, so thermodynamic condition also is conducive to the spontaneous removal of metal chloride.In like manner, other metallic impurity are also removed.
The high-purity carbon black that the present invention produces, its moisture content is very low, and the ash content of coal is below 100ppm, and 45 μ m screeningss can reach below 20 ppm; Metals content impurity is extremely low, and particularly Fe content is below 50ppm.
Adopt present method to produce high-purity carbon black, production technique is simple, and strong operability can be applied rapidly.
In sum, owing to having adopted technique scheme, the invention has the beneficial effects as follows: the high-purity carbon black of the present invention's exploitation, both can meet the needs of energy field battery, also can be used for simultaneously food, metallurgical product, improve Technological Economy content and the competitive strength of China's related products, have great economic worth and social benefit.
Embodiment
Below in conjunction with embodiment, the present invention is described in detail.
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 explain the present invention, is not intended to limit the present invention.
Embodiment 1
Get 1 kg ordinary carbon black A, put into again the high temperature purification treatment unit after in the crystal vessel of packing into, after high-temperature purification device is evacuated to 1Pa, pass into chlorine and Refrigerant 12 as vapor phase purification agent (flow is 0.02 liter/second), be warming up to 950 ℃; Under 950 ℃, be incubated after 30 hours and purifying agent switched to argon gas (flow is 0.01 liter/second), be incubated 5 hours to get rid of residual halogen species; Finally cool to room temperature with the furnace, close argon gas and namely obtain high-purity black B.
Carbon black A, B major impurity and content thereof are in Table 1.
Embodiment 2
Get 10 kg ordinary carbon black C, put into again the high temperature purification treatment unit after in the crystal vessel of packing into, after high-temperature purification device is evacuated to 10 Pa, then pass into chlorine as vapor phase purification agent (flow is 0.12 liter/second), be warming up to 2000 ℃; Under 2000 ℃, be incubated after 10 hours and purifying agent switched to argon gas (flow is 0.05 liter/second), be incubated 3 hours to get rid of residual halogen species; Finally cool to room temperature with the furnace, close argon gas and namely obtain high-purity carbon black D.
Carbon black C, D major impurity and content thereof are in Table 1.
Embodiment 3
Get 20 kg ordinary carbon black E, put into again the high temperature purification treatment unit after in the crystal vessel of packing into, after high-temperature purification device is evacuated to 20 Pa, then pass into tetracol phenixin and chlorine as vapor phase purification agent (flow is 0.16 liter/second), be warming up to 2500 ℃; Under 2500 ℃, be incubated after 5 hours and purifying agent switched to nitrogen (flow is 0.1 liter/second), be incubated 1 hour to get rid of residual halogen species; Finally cool to room temperature with the furnace, close nitrogen and namely obtain high-purity carbon black F.
Carbon black E, F major impurity and content thereof are in Table 1.
Embodiment 4
Get 30kg ordinary carbon black G, put into again the high temperature purification treatment unit after in the crystal vessel of packing into, after high-temperature purification device is evacuated to 50 Pa, then pass into vinylchlorid as vapor phase purification agent (flow is 0.4 liter/second), be warming up to 3000 ℃; Under 3000 ℃, be incubated after 5 hours and purifying agent switched to helium (flow is 0.1 liter/second), be incubated 1 hour to get rid of residual halogen species; Finally cool to room temperature with the furnace, close nitrogen and namely obtain high-purity carbon black H.
Carbon black G, H major impurity and content thereof are in Table 1.
Embodiment 5
Get 50 kg ordinary carbon black I, after packing in crystal vessel, put into again the high temperature purification treatment unit, after high-temperature purification device is evacuated to 100 Pa, then pass into tetracol phenixin and Refrigerant 12 as vapor phase purification agent (flow is 0.8 liter/second), be warming up to 3500 ℃; Under 3500 ℃, be incubated after 0.5 hour and purifying agent switched to nitrogen (flow is 0.2 liter/second), be incubated 0.5 hour to get rid of residual halogen species; Finally cool to room temperature with the furnace, close nitrogen and namely obtain high-purity carbon black J.
Carbon black I, J major impurity and content thereof are in Table 1.
Table 1 carbon black high temperature purification is processed the front and back foreign matter content
Claims (4)
1. the production method of a high-purity carbon black is characterized in that: comprises the following steps successively,
(1) ordinary carbon black is put into to airtight heating unit;
(2) after heating unit is vacuumized, then pass into purifying agent, be warming up to 900～3500 ℃, purifying agent is at least a in chlorine, Refrigerant 12, tetracol phenixin;
(3), under 900～3500 ℃, be incubated at least 5 minutes;
(4) in heating unit, pass into rare gas element again;
(5) heating unit is cooled to room temperature, closes aforesaid purifying agent and rare gas element, obtains.
2. the production method of a kind of high-purity carbon black according to claim 1 is characterized in that: in (2) step, be evacuated to 100Pa or below 100Pa.
3. the production method of a kind of high-purity carbon black according to claim 1, it is characterized in that: the rare gas element described in (4) step is argon gas or nitrogen.
4. the prepared high-purity carbon black of the described production method of claims 1 to 3 any one.
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| CN103360799B (en) * | 2013-07-23 | 2014-08-13 | 上海一品颜料有限公司 | Refined carbon black and preparation method thereof |
| US20160190594A1 (en) * | 2013-08-08 | 2016-06-30 | Lion Specialty Chemicals Co., Ltd. | Carbon black and production method therefor, and electricity storage device and conductive resin composition |
| US11939477B2 (en) | 2014-01-30 | 2024-03-26 | Monolith Materials, Inc. | High temperature heat integration method of making carbon black |
| US10370539B2 (en) | 2014-01-30 | 2019-08-06 | Monolith Materials, Inc. | System for high temperature chemical processing |
| CN111278928A (en) * | 2017-08-28 | 2020-06-12 | 巨石材料公司 | Particle system and method |
| CN110116999A (en) * | 2019-06-05 | 2019-08-13 | 张家港宝诚电子有限公司 | A kind of apparatus and method using paraffin preparation high-purity carbon |
| CN112391068B (en) * | 2019-08-16 | 2024-01-30 | 烁元新材料(东营)股份有限公司 | Device for carrying out high-temperature treatment on carbon black in anaerobic state |
| CN116457428A (en) * | 2020-12-04 | 2023-07-18 | 电化株式会社 | Carbon black, slurry and lithium ion secondary battery |
| CN113652103A (en) * | 2021-07-09 | 2021-11-16 | 中国化学工业桂林工程有限公司 | Regeneration method of pyrolysis 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 |