• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    1485261 Conductive carbon black HOECHST AG 31 March 1976 [10 April 1975] 13083/76 Heading C1A Conductive carbon black is prepared by intimately mixing an aqueous suspension of carbon black with an AS-number greater than 15 with 0À5 to 10 g. of vaporizable, saturated, aliphatic or cycloaliphatic hydrocarbon(s) per gram of the carbon; the reaction being carried out at from 5‹ to 120‹ C., under 1 to 20 atmospheres pressure for 1 to 20 minutes, the resulting carbon black containing 20-30 wt. per cent of carbon is separated from the liquid phase and heated to drive off water and hydrocarbon(s) and then heated for 2 to 30 minutes at from 1100‹ to 2200‹ C.; the carbon black suspension used being prepared by heating liquid hydrocarbons to 1200‹ to 2000‹ C. at pressures of 1 to 80 atmospheres in the presence of oxygen, and, if desired steam, and water scrubbing the reaction gas. The final heating of the water- and hydrocarbon-free carbon black may be in the presence of nitrogen, hydrogen, carbon monoxide, chlorine, hydrogen chloride or halogen yielding compounds, e.g., dichlorodifluoromethane. The carbon black product is suitable for use in dry batteries, and is characterized in containing at least 97% by wt. of carbon, an AS number (which is a measure of its absorption properties) of from 15 to 35, a specific electric resistance of 10-1 to 10-3 ohm. cm. under a contact pressure of 1500 atmospheres, an apparent density of 100 to 180 g./l., a BET surface area of 100 to 1000 m.<SP>2</SP>/g. and a free moisture content equal to 35 to 55% of the free moisture of compressed acetylene-based carbon black having an identical AS number determined in a standard defined depolarizer test mixture.
    公开号:SU839441A3
    申请号:SU762343009
    申请日:1976-04-09
    公开日:1981-06-15
    发明作者:Шаллус Эрих；Митенс Герхард；Фукер Грегор；Петрель Юрген；Вильгельм Дорн Фридрих
    申请人:Хехст Аг (Фирма)；
    IPC主号:
    专利说明:

    (54) METHOD OF OBTAINING ELECTRICAL WIRING SOOT
    This invention relates to a method for producing conductive carbon black as a depolarized mass for dry batteries. Suitable soot types for this purpose must have certain properties that affect the processing of soot for electric batteries and the discharge process of the latter.
    It is known that soot species which are obtained by the decomposition of acetylene at temperatures above 2300 ° C 1 should be used for depolarization masses.
    However, a method for producing carbon black of this type, associated with the energy-intensive manufacture of acetylene, is very expensive. These species of Shiki are characterized by absorption coefficients of 15-35; moreover, the soot tigal with a higher absorption coefficient has a comparatively lower bulk density, approximately 60 g / l, which, when sent for quite a long distance, leads to significant transport costs.
    A method of producing electrically conductive carbon black is known, which includes thermal decomposition of liquid hydrocarbons in the presence of oxygen-containing gas and water vapor at 12601647С and above atmospheric pressure (for example, 6.1 atm) to form carbon black products, supplying water to carbon black gas products 2.
    However, the soot obtained by this method has a reduced discharge time for dry batteries.
    The purpose of the invention is to increase the discharge time of dry batteries.
    This goal is achieved by the fact that the proposed method includes thermal decomposition of liquid hydrocarbons in the presence of oxygen or oxygen-containing gas and water (steam at 1200–2000 ° C, a pressure of 1–80 atm with the formation of carbon black products, the supply of water into carbon black gas products). soot suspensions with an absorption coefficient of 15–35 and a soot content of 5–40 g / l of water, sweeping (at 5–120 ° C and a pressure of 1–20 atm for 1–20 min) suspensions with aliphatic and cycloaliphatic hydrocarbons with boiling point 25-100 ° С in t he 0.5-10 g / g of carbon black (preferably pH 7-10), the carbon black separation
    from the liquid medium, drying it (preferably by heating to and then nagpiv for 2-30 minutes to 1100-2200s in the medium,
    The carbon black released from hydrocarbons and water can be heated in the presence of nitrogen, hydrogen or carbon monoxide to 1400ISOO C for 5-15 minutes. On the other hand, the soot released from hydrocarbons and water can also be heated in the presence of chlorine, hydrogen chloride or splitting halogen compounds to temperatures above 12001 0. As halogen splitting compounds that can be used for corrosion prevention reasons instead of chlorine or hydrogen chloride should be especially noted; for example, carbon tetrachloride, vinyl chloride and dichlorodifluoromethane.
    Soot suitable for use in depolarized masses must have certain properties. Such properties are, for example, electrical conductivity and hygroscopicity, which are empirically characterized by an absorption coefficient (AS), the absorption coefficient indicates the proportion of water mixture with acetone (9: 1) in cm, which is necessary for a round bottom flask From 5 g of soot get one single ball. Carbon blacks with an absorption coefficient lower than 15 and higher than 35 do not meet the requirements imposed on them in the manufacture of batteries. Carbon black with an absorption coefficient of 15-35 is obtained by washing with water gases containing soot, and the aqueous suspension falls out with a carbon black content of from 5 to 40 g / l of water.
    The soot species thus obtained are naturally cheaper than acetylene soot, especially if the resulting CO / HQ mixture is used, but these soot do not fully meet the requirements imposed by the International Electrochemical Commission for testing batteries. .
    According to the proposed method, carbon black suspensions are therefore primarily treated with a vaporized, saturated aliphatic or cycloaliphatic hydrocarbon in an amount of 0.5-10 g / g of carbon black, and pH 7-10 should be observed, as in an acidic medium, for example, at pH 3, only a non-free flow of soot is achieved. The treatment with hydrocarbons occurs at 5-120 ° C, and if the processing temperature is above the boiling point of water or hydrocarbon, and the treatment is carried out under pressure, then the soot state is provided in the yield phase. With
    this separates soot and carbon from the main body of water. AroTyatic hydrocarbons are unsuitable for the release of soot, for example, when benzene is used, very difficult paste-like mass is obtained. In addition, the release of soot is not completely. It takes 1–20 min to process a powerful agitator. Carbon black is discharged as a dry product and contains about 2030 wt.% Of carbon, the remainder of the hydrocarbon and water. More appropriate is the use of hydrocarbons boiling at 2510 ° C, since its regeneration is envisaged, and the reactions of the hydrocarbon on the surface of the soot should be excluded.
    The PS of the proposed method releases soot in the second stage undergoes heat treatment, the hydrocarbon and water are first evaporated and regenerated, and in conclusion the temperature rises to 11002200 ° C.
    Using the AS number, empirically filling the empty volume with a liquid without mechanical load is determined. However, for the processing of carbon black into depolarizer masses, the stability of the structure is important, i.e. twisting resistance against mechanical load, especially pressing pressure.
    The possibility of close to the practice of measuring the behavior of soot in the mass of the depolarizer at the pressing pressure gives a known definition of free moisture, 4 g of the mass of the depolarizer consisting of 70 weight parts of electrolyte pyrolusite, 17 weight parts HN4C, 1 weight parts. ZnO, 12 weight.h. soot and 24 weight.h. A 20% solution of ZnCEj is pressed with a constant weight of 8 kg to a 5.4 cm filter paper, which lies on a zinc plate. The weight and zinc plate form a cathode or anode. Due to the pressing pressure, the structure of the moisture-containing soot is more or less altered and the moisture is released. The stronger the structure of the soot, the less the amount of moisture or free moisture released by pressing. Depending on the free moisture content, the filter paper is soaked through and when the voltage is applied, an appropriate current is generated. The maximum voltage drop in millivolts through a constant resistance of 10 ohms is a measure of free moisture.
    Table 1 shows the dependence of free moisture on the time of wet mixing of some of the carbon blacks and commercial acetylene blacks produced according to the proposed method of the compared AS number. The difference between the carbon blacks produced by the proposed method is clearly expressed.
    The compressing capacity of the depolarizer mass for dry batteries depends on the moisture absorption capacity of the soot (AS-number) and on the wet-mix time. In this case, wet mixing time should be understood to mean the time required for mixing a dry mixture consisting, for example, of pyrolusite, ammonium chloride, zinc oxide and soot, with an internal electrolyte of, for example, an aqueous solution of zinc chloride. However, when soot obtained using the proposed method, it is usually not possible to draw a conclusion from AS-number about a certain behavior in the depolarizer mass, that is, soot according to the invention and commercial acetylene soot of the comparable AS number show different behavior in the depolarizer mass.
    To get an idea of the differences between individual carbon blacks, commercial acetylene black carbon with an AS number of 32 was ground for 15 minutes in a ball mill, after which the AS number was determined 16. In contrast, according to the proposed method, carbon black did not change its original size. AS number 23.
    To clarify this, the following should be indicated.
    Used in dry batteries, soot have an average particle size of 25-60 nm. As the examination shows, under an electron | 1st microscope, these primary particles are collected in chains that are more or less twisted. Depending on the degree of twisting, soot with a high or low structure is distinguished, but so far it has not been possible to at least approximate quantitatively the structure or degree of twisting.
    The result is an electrically conductive carbon black with a content of: carbon not less than 97 wt.%, Absorption coefficient 15-35, electrical resistivity -10 Ohm.m at a pressing pressure of 1500 atm, bulk density 100-180 g / l, BET-surface area 100 -1000, carbon black has free moisture measured in millivolts in a standard depolarizer solution, which is 35-55% free moisture produced with the same absorption coefficient of compacted acetylene black (370-570 mV).
    The following examples characterize the method of making electrically conductive soot as depolarized masses for dry batteries. In these examples, carbon black, which is obtained by the thermal decomposition of heavy fuel oil, with oxygen and water vapor at 1400 s and
    at a pressure of 50 atm and with subsequent washing with water of gases that took part in the reaction and containing soot in the form of an aqueous suspension containing a content of 15 g / l.
    Example 1. (control example is similarly known). The aqueous suspension of carbon black is evaporated at the following rates: Coefficient
    absorption 28
    Electrical resistivity, .2 ОИ "m 2.5-10 Bulk density, g / l 102 Vt-surface area, 600
    5 Carbon content, wt.% 97.5 Example 2. (control example). From 200 l of soot suspension in a mixer with the addition of 6 kg of gasoline
    0 | (so kip. 30-90 ° C) at pH 9, at 25 C, at a pressure of 1.2 atm and a stirring time of 10 minutes, carbon black is obtained. Bulk material consists of 20 wt.%, Soot, 40 wt.% Gasoline and 40 wt.% Water, and gasoline generation is pro-. occurs at 200 ° C. 3 kg of carbon black free from water and gasoline are obtained. This product is heated for about 0 min in the presence of nitrogen to.
    0 Indicators of soot Absorption coefficient 26 Specific electro-propane, inactivity, OMM 2.4-10 Bulk density, g / l 102 BET-surface area, 630 Carbon content, wt.% 98 Example 3. Work is done as in Example 2, however the heating
    0 dry soot free of water and gasoline is produced for 20 minutes in the presence of nitrogen at 1500 ° C. Soot indicators
    Absorption coefficient 21.5 Specific electro-proppo-2, OmM 2.510 Bulk weight, g / l 120 VBT-surface area,, 250
    0 Carbon content, wt.%: 93.6: moisture content (mixing time in the wet state is 8 minK
    5 mV. 425
    Example 4. The work is done as in Example 2, however, the treatment of dry soot free of water and gasoline is carried out for 20 minutes in
    0 in the presence of hydrogen chloride at 18000 ° C.
    Soot indicators
    Absorption coefficient 20
    Specific electro-i
    4.1-10
    permeability, OMM Bulk weight, g / l 160 WET surface area, m / g160 Carbon content, wt.%. . 99.5 Humidity available. (mixing time in the wet state is 8 minutes), mV 500 A similar result is obtained when nitrogen is used instead of hydrogen chloride, to which 5 vol.% fluoromethane dichloride is added. Example 5. 200 l / h of soot suspension and 9 l / h (b kg / h) of gasoline (since 30-90 0, the content of aromatic hydrocarbons up to 1 wt.% Is continuously fed to the bottom of the mixer, in which the contact Intensive contact of the soot suspension and hydrocarbon is carried out. The processing time is 15 minutes at a pH value and temperature and pressure of 1.1 atm. Water and activated soot are poured into the upper part of the tank and sent to a buffer tank in which there is little turbidity. soot free water and a dry bulk product consisting of 25 wt.% soot , 50% by weight of gasoline and 25% by weight of water. Bulk material is delivered through the 1X33 intermediate tank from the metering device to a rotary tube furnace heated outside, in which, at 200 ° C, the gas and water are evaporated and condensed in a cooling system. the carbon black is extracted and heated to a nitrogen atmosphere in a furnace heated by electrical contact heating, and 3 kg / h of carbon black are removed through a tank device subjected to cooling. Soot Indicators Absorption Rate 22 Electrical Resistivity, OMM Bulk Weight, g / l WET surface area, m / g Carbon Content, Free Humidity, mV Table 2 presents the test results of the depolarized masses of dry batteries using carbon black obtained by the proposed method and by famous. Soot quality control for the purpose of using it in batteries is carried out in zinc (pyrolusite) cells of size R 20 (according to the standard of the International Electrochemical Commission). The depolarized mass (cathode mass) is a mixture consisting of 70 parts by weight. pyrolusite, 18 weight.h. ammonium chloride, 1 weight.h. zinc oxide, 12 weight.h soot, manufactured according to examples 1-5 and 27 weight.h. an internal electrolyte consisting of a 23.5 wt.% aqueous solution of zinc chloride with 0.2% HgClg. Each of the six electroplating cells after five days of exposure at or after five days of exposure and after thirty days of exposure had the following conditions of discharge: the discharge time of the battery when powered 30 min / day over 5 Ohm light sources to 0.75 B / discharge time Batteries with 4 hours / day power over 40 ohms transistors to 0.9 V; battery discharge time at 2 hours / day over 5 ohm tape recorders up to 1.1 V. Batteries that were made from carbon black in example 1 when stored at a tropical climate (showed a significant amount of sedimentation due to expansion. Table 2 shows , that only when using carbon black made according to the invention (Example 3-5), results were achieved that can be compared with results obtained using acetylene black. Table 1 Acetylene black, highly compressed 1 030 1050 and Acetylene black, compressed 22 1 005 1 020 Carbon black of Example 3 21.5
    Normal Temperature Formula Invention
    1. A method of producing electrically conductive soot, mainly for depolarized mass of dry batteries, including thermal decomposition of liquid, hydrocarbons in the presence of oxygen or oxygen-containing gas and water vapor at 1200-2000 ° C and pressure of 1-80 atm with the formation of carbon black products, supply into the carbon black products of water, characterized in that, in order to increase the battery discharge time, water is supplied into the carbon black products before forming a water suspension of carbon black with an absorption coefficient of 15-35 and a carbon black content of 5-40 g / l of water, mixing a slurry with aliphatic or cycloaliphatic hydrocarbon with
    table 2
    boiling point of 25-100 ° C in the amount of 0.5-10 g / g of carbon black, the carbon black is separated from the liquid medium, dried during heating and then heated in 2-30 minutes to 1100-2200 ° C in a gaseous environment.
    2. The method according to Claim 1, characterized in that the aqueous
    45 suspension of carbon black with hydrocarbons at pH 7-10.
    3. The method according to claim 1, characterized in that the carbon black is dried at
    heated to. .
    50
    Sources of information taken into account in the examination
    1.Zuev V.P. and Mikhailov V.V. Salsi production. M., 1970, pp. 190-194.
    2. US Patent 3,832,450,
    55 cl. C 01 V 31/02 (423-450),
    .1ub.2.2.08.74 (prototype).
    权利要求:
    Claims (3)
    [1]
    Claim
    1. A method of producing electrically conductive carbon black, mainly for depolarized mass. Dry batteries, comprising the thermal decomposition of liquid hydrocarbons in the presence of oxygen or an oxygen-containing gas and water vapor at 1200-2000 ° C and a pressure of 1-80 atm with the formation of carbon black products, feeding carbon black gas products, characterized in that, in order to increase the battery discharge time, they supply water to carbon black products until an aqueous suspension of carbon black with an absorption coefficient of 15-35 and a carbon black content of 5-40 g / l of water is mixed, mix a suspension with aliphatic or cycloaliphatic hydrocarbons with a boiling point of 25-100 ° C in an amount of 0.5-10 g / g of carbon black, soot is separated from the liquid medium, dried by heating and then heated for 2-30 minutes to 1100-2200 ° C in a gas environment.
    [2]
    2. The method according to claim 1, characterized in that the aqueous suspension of carbon black with hydrocarbons is mixed at a pH of 7-10.
    [3]
    3. The method of pop. 1, characterized in that the soot is dried by heating to 200 ° C. . *
    类似技术:
    公开号 | 公开日 | 专利标题
    SU839441A3|1981-06-15|Method of producing elestroconducting carbon black
    US4082694A|1978-04-04|Active carbon process and composition
    US2719779A|1955-10-04|Process of making hard carbon black pellets
    US3066099A|1962-11-27|Mineral active carbon and process for producing same
    SU791204A3|1980-12-23|Method of preparing catalyst for electrochemical hydrogen oxidation or oxygen reduction
    US4279880A|1981-07-21|Acetylene black with high electrical conductivity and high absorptive power
    CA1139921A|1983-01-25|Process and apparatus for improving the degree ofgraphitization of carbon black,and its uses
    US2682448A|1954-06-29|Process for treating high ph furnace carbon black
    EP0002275B1|1983-05-11|Granular activated carbon manufacture from brown coal treated with dilute inorganic acid
    HU222689B1|2003-09-29|Furnace black, process, use
    US5718844A|1998-02-17|Cobalt/cobalt oxide powder
    EP0002674B1|1983-05-11|Granular activated carbon manufactured from brown coal treated with concentrated inorganic acid without pitch
    CA1075219A|1980-04-08|Granular activated carbon manufacture from sub-bituminous coal mixed with concentrated inorganic acid without pitch
    US3053627A|1962-09-11|Process for the production of hydrophilic silicon dioxide
    US3216843A|1965-11-09|Treatment of carbon black
    JPH0624725A|1994-02-01|Manufacturing process of activated carbon
    IE44193B1|1981-09-09|Active carbon
    US4282117A|1981-08-04|Method for producing electrically conductive zinc oxide
    Winans et al.1995|Novel forms of carbon as potential anodes for lithium batteries
    CA1074768A|1980-04-01|Granular activated carbon manufacture from low tank bituminous coal leached with dilute inorganic acid
    JP3960397B2|2007-08-15|Electric double layer capacitor
    CN112408362A|2021-02-26|Carbon quantum dot and preparation method and application thereof
    JPH077667B2|1995-01-30|Preparation method of titanium disulfide for use as electrode material in storage batteries
    US2992901A|1961-07-18|Production of artificial graphite
    US1391211A|1921-09-20|Otto e
    同族专利:
    公开号 | 公开日
    SE7602712L|1976-10-11|
    JPS5415874B2|1979-06-18|
    DK144976C|1982-12-06|
    DE2515633A1|1976-10-28|
    ATA255276A|1979-01-15|
    GR60423B|1978-05-25|
    FR2307023A1|1976-11-05|
    NL7603483A|1976-10-12|
    DE2515633B2|1979-09-27|
    IE42975B1|1980-11-19|
    CA1069676A|1980-01-15|
    DK168076A|1976-10-11|
    NL182485C|1988-03-16|
    IE42975L|1976-10-10|
    NL182485B|1987-10-16|
    US4061719A|1977-12-06|
    FR2307023B1|1980-06-06|
    DK144976B|1982-07-19|
    SE412373B|1980-03-03|
    CH619259A5|1980-09-15|
    AT351626B|1979-08-10|
    DE2515633C3|1980-06-19|
    IT1057484B|1982-03-10|
    ES446601A1|1977-06-01|
    BE840589A|1976-10-11|
    JPS51124693A|1976-10-30|
    GB1485261A|1977-09-08|
    DD124256A5|1977-02-09|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    DE72088C|SÄCHSISCHE OFEN- UND CHAMOTTE-Vv'AAREN-FABRIK, VORM. ERNST TEICHERT in Cölln a. Elbe|Method of making mosaic tiles|
    GB741135A|1952-09-12|1955-11-30|Jones Gas Process Company Ltd|Improvements in or relating to the dewatering of aqueous pastes or slurries of fine-particle hydrophobic solids|
    US3401020A|1964-11-25|1968-09-10|Phillips Petroleum Co|Process and apparatus for the production of carbon black|
    US3832450A|1972-12-18|1974-08-27|Cities Service Co|Carbon black process|JPS5546268A|1978-09-27|1980-03-31|Hitachi Maxell Ltd|Dry cell|
    DE2846352A1|1978-10-25|1980-05-08|Hoechst Ag|METHOD AND DEVICE FOR INCREASING THE GRADE GRADE OF RUSSIANS AND THE USE OF THESE RUSSIANS|
    DE2944916A1|1979-11-07|1981-05-21|Hoechst Ag, 6000 Frankfurt|METHOD FOR SEPARATING METALS FROM CARBON|
    JPS5682572A|1979-12-06|1981-07-06|Hitachi Maxell Ltd|Dry cell|
    DE2949286A1|1979-12-07|1981-06-11|Hoechst Ag, 6000 Frankfurt|METHOD FOR REMOVING SOOT FROM AQUEOUS SUSPENSIONS|
    DE2950705A1|1979-12-17|1981-06-25|Union Rheinische Braunkohlen Kraftstoff AG, 5000 Köln|METHOD FOR OBTAINING SOOT FROM AQUEOUS SUSPENSIONS|
    DE3202659A1|1982-01-28|1983-08-04|Hoechst Ag, 6230 Frankfurt|METHOD FOR PURIFYING WET METHOD PHOSPHORIC ACID|
    US4836998A|1984-12-21|1989-06-06|Aluminum Company Of America|Production of partially calcined carbonaceous reductant using steam|
    US4957722A|1984-12-21|1990-09-18|Aluminum Company Of America|Production of partially calcined carbonaceous reductant using steam|
    JP2674602B2|1988-11-25|1997-11-12|三菱化学株式会社|Easy dispersible carbon black|
    US5626986A|1995-10-12|1997-05-06|Zbb Technologies, Inc.|Carbon coating for an electrode|
    JP5471591B2|2010-02-26|2014-04-16|東洋インキＳｃホールディングス株式会社|Conductive composition for electrode|
    HUE034878T2|2011-12-22|2018-03-28|Cabot Corp|Carbon blacks and use in electrodes for lead acid batteries|
    DE112017000597T5|2016-02-01|2018-12-13|Cabot Corporation|Compounded rubber with improved heat transfer|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    DE2515633A|DE2515633C3|1975-04-10|1975-04-10|Process for the production of a conductive carbon black for depolarizer masses of dry batteries|
    [返回顶部]