CN1078727A - 炭黑生产 - Google Patents

炭黑生产 Download PDF

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CN1078727A
CN1078727A CN 93104525 CN93104525A CN1078727A CN 1078727 A CN1078727 A CN 1078727A CN 93104525 CN93104525 CN 93104525 CN 93104525 A CN93104525 A CN 93104525A CN 1078727 A CN1078727 A CN 1078727A
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carbon black
methane
natural gas
sweet natural
regulation
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CN1051786C (zh
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S·赖纳姆
J·哈格达尔
K·霍斯
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Kvaerner Technology and Research Ltd
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    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09CTREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/44Carbon
    • C09C1/48Carbon black
    • C09C1/487Separation; Recovery
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00Physical properties of inorganic compounds
    • C01P2006/12Surface area
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00Physical properties of inorganic compounds
    • C01P2006/19Oil-absorption capacity, e.g. DBP values

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Pigments, Carbon Blacks, Or Wood Stains (AREA)
  • Carbon And Carbon Compounds (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Powder Metallurgy (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
  • Polyesters Or Polycarbonates (AREA)
  • Saccharide Compounds (AREA)
  • Electrolytic Production Of Metals (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)
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Abstract

应用基于由天然气或甲烷而产生的纯炭黑作为 橡胶工业特别适用的混合物,颜料和印刷油墨,冶金 工业的还原材料,铝生产中的阳极材料和钢铁工业的 脱碳材料。

Description

本发明与用天然气或甲烷生产纯净的炭黑有关。
生产炭黑的烃分解作用是一公知的过程并为此有许多现成的方法。用甲烷生产炭黑还被同一申请人介绍在挪威专利申请第91    4904号中。在本申请所介绍的方法中,现已表明,有可能以这样的方式分解烃类以使炭黑的物理性质在很大程度能根据给定的加工参数而被预测。
这已证明是非常有价值的加工性能,它能开拓较宽应用和达到更高产品质量的已经使用炭黑作为基本原料的道路。
现已出现一种寻求新的应用天然气的需求,因为现已确定的天然气资源是非常巨大的。用天然气取代某些当今的产品能提供较重量的环境上好处。甲烷是一种大量存在的气体烃,它的价格合理,并已被证明是非常适于作为制造纯净的炭黑与氢的原料。然而,迄今对这种可能性和使用纯炭黑作为最终产品的基本原料只给予不充分的注意。
因此本发明的目的是提供应用甲烷以及特别是应用纯炭黑的方法。本发明的另一目的是提供以基本原料形式应用这些材料的机会,它们既在财务上是有利的同时还提供高的质量。
这些目的是通过将由天然气或甲烷分解为其基本元素而产生的纯碳黑和氢用作橡胶工业的生产混合物,颜料和印刷油墨,电池生产冶金工业中的还原材料,铝生产的阳极料,钢铁工业的渗碳剂,活性碳等而实现的。
令人惊奇的事实表明,基于被分解成为其基本元素即碳黑和氢的天然气或甲烷,特别能得到含碳材料,其碳性质,即其比重、粒径、表面特性、孔隙率和结构能在以所得的最终产物尤其适用于上述特定目的。用天然气作为原料提供特殊用途的具有特殊性质的价格合理的炭黑,并且现已表明,通过根据本发明的特殊应用,能得到具有有利性质的,例如铝业或其他冶金工业中用的电极、混合物等和更无污染的生产方法。在活性炭生产中表明,通过本发明能得到一种比迄今所用的基于传统原料诸如木材、沥青炭、褐煤、泥炭、椰壳等的活性炭具有高得多的吸附性能的材料,在本发明方法中还有可能通过改变表面孔径来控制活性炭的吸附性。作为本发明的结果所显示出的应用可能性业已被证明是非常惊人的。借助使用表明的原始产物,天然气或甲烷,并利用由这特定原料提供的可能性,在已经出现的调整所生成碳的物理性质的可能性方面,现已获得令人惊奇的结果,在用于所说场合时对最终产品提供明显的改进和赋于最终产品以更多的获得特殊产品性质的机会。在橡胶工业中,例如,应用本发明的炭黑使有可能生产出具有意想不到的弹性和回弹性的优质橡胶。就活性炭来说,能提供其吸附能力完全适于此目的的质量。作为电极材料来说,本发明使有可能以合理的成本生产出意想不到的纯的电极,因此基本上避免了由不纯材料所引起的污染。
在本发明的另一个有利的实施方案中,在使用混合物的专门应用时,它在具体情况下也可能是有利的。于是本发明为指出的领域提供许多新产品的可能性,在这些中污染碳可被具有相当的或更好性质的完全纯净的碳所取代。
现通过某些应用例对本发明作进一步的介绍。
实施例1
在应用通过甲烷分解而产生的碳黑时,在生产汽车轮胎橡胶和工业橡胶的生产过程中对碳的质量进行选择和调整。各被选值示于下表。
橡胶 BETm2/g DBPml/100g ASTM分类
汽车轮胎工业橡胶 20~2005~80 65~20040~150 N110-N660N550-N990
BET:“Brunauer,Emmet    &    Telfer”法
DBP:ASTM    D-2414“炭黑的邻苯二甲酸二丁酯吸收”
分类:ASTM    D-1765“用于橡胶制品中的炭黑”
此炭黑适用于全部等级的橡胶。
实施例2
所提供的具有以下物理性质的由甲烷制得的炭黑被用作颜料/印刷油墨。
颜料/印刷油墨
B E Tm2/g D B Pml/100g 色调强度% PH
20-N500 30~150 20~130 3~9
色调强度:ASTM    D-3265“炭黑的色调强度测定法”
此炭黑适用于所有等级。
实施例3
根据本发明的具有以下质量规格的炭黑被用于干电池制造。
干电池
B E Tm2/g A Sml/5g 规定的电阻率,欧姆·厘米(Spec.el.resistance,ohm·cm)
40~80 20~50 <0.1(200巴)
AS:“吸附刚性”(adsorption    rigidity),即,为能摇晃粉末使之成球体而所需的丙酮溶液混合物,单位为ml/5g粉末,“Knapsack”法。
适用“乙炔黑”级。
实施例4
使用具有以下质量特性的本发明的炭黑。用于冶金工业的还原金属。
B  E  Tm2/g D  B  P(ml/100g) 规定的电阻率欧姆·厘米 反应性(ml Sio)
5~30 30~200 <0.1 250~1000
反应性:根据J.Kr.Tuset和Q.Raaness的“Reactivity    of    Reduction    Materials    in    the    Production    of    Silicon,Silicon-rich    Ferro    Alloys    and    Silicon-Carbide”,AIME    El.Furnace    Conf.,St.Louis,Miss.7~10    December    1976。
对颗粒结构必须进行改进。使用具有晶体形式和良好导电性的碳颗粒。
炭黑必须通过糖蜜型的、沥青和其他树脂型的粘合剂混合物进行精加工处理,以便在高温下达到高的强度,使它被制造所要求的产品形式(具有“开式结构”的炭砖/附聚物)。
产品的必要性质:
反应性:高反应性,即,开式结构。小于1000ml/Sio(Sintef法)。
机械强度:“很高”,应能经受高温时的炉中装载负荷而不结渣。
实施例5
用作铝生产中的阳极材料。
铝生产中的阳极材料
B E Tm2/g D B Pml/100g 压缩的比重g/cm3 规定的电阻率Ohm·cm
<5 <30 1.5~1.7 <01
对炭黑的要求:
-“无”结构,即“重于”N-990级。
-高度石墨化而形成具有结晶形状/良好导电性的碳颗粒。
-较小的反应性(小的开孔率)。
对炭黑与粘合剂一起进行精加工处理,得到合适的产品形式(具有“紧密”结构的“焦炭”、炭砖、附聚体)。
对所制成的阳极材料的要求:
密度:1.5~1.6g/cm3
规定的导电率:30~60    Ohm·m
抗压强度:接近45MPa
总的孔隙度:接近30%
实施例6
钢铁工业用的炭化料
B E T D B P 规定的电阻率 H
m2/g ml/100g Ohm·cm ppm
5~30 30~200 <0.1 <200
对炭黑的要求:
-炭黑必须是“活性的”,即,就此而论,它作为碳原子应快速地溶于材料中。
-氢的比例应该是低的,否则会形成氢“泡”。
实施例7
活性炭
BET    DBP
m2/g ml/100g
5~50    30~200
对炭黑与粘合剂一起进行精加工处理而产生所需的产品形式(附聚体/挤出物形式),随后进行活化。
对活性炭的要求:
BET    孔径
m2/g A
500~1500 10~100*
*取决于用途(即,取决于被吸附分子的类型)。
实施例8
在改性的反应器气氛,即,例如氧化介质诸如O2、空气、H2O、CO2或其它介质的混合物中,对碳的物理性质诸如BET、DBP、PH和颗粒形状既可各别地加以控制,也可多重地加以控制以达到所要求的值。

Claims (9)

1、碳粒形式的纯炭黑,它是基于天然气和/或甲烷的热分解而产生的,热分解时天然气和甲烷被分解成为炭黑和氢,而氢可再循环并被用作过程中的等离子形成气体,其特征在于此炭黑是一种在粒径、结构、表面、比重、酸度、导电率、反应性等方面有专门规定的材料,它供制备特殊性质的产品和/或创造特殊产品之用,特别是被用于冶金工业。
2、如权利要求1中所说的炭黑,其特征在于它是基于天然气和/或甲烷而生产的,特别适于作活性炭。
3、如前述权利要求1中的任一权利要求中所说的炭黑,其特征在于它特别适用作冶金工业中的还原材料、阳极材料、碳化材料或衬里材料。
4、如前述权利要求中的任一权利要求中所说的炭黑,其特征在于它的表面积(BET)为5~30m2/g,邻苯二甲酸二丁酯吸附(DBP)为30~200ml/100g和具有小于0.1Ohm·cm的规定的电阻率。
5、应用碳粒形式的纯炭黑,所说的炭黑是基于天然气和/或甲烷于等离子反应器中的热分解而产生的,热分解时天然气和/或甲烷被分解成为炭黑和氢,而氢可再循环并被用作过程中的等离子形成气体,它以一种在粒径、结构、表面、比重、酸度、导电率、反应性等方面具有专门规定的材料而供制备特殊性质的产品和/或创造特殊产品之用,特别被用于冶金工业。
6、如权利要求5中所说的基于天然气和/或甲烷而生产的纯炭黑的应用,特别适用作活性炭。
7、如权利要求5~6的任一项权利要求中所说的应用,其中炭黑被用作冶金工业的还原材料、阳极材料、脱碳材料或衬里材料。
8、如权利要求5~7的任一项权利要求中所说的应用,其中添加剂与炭黑一起使用。
9、如权利要求5~8的任一项权利要求中所说的应用,其中炭黑的表面积(BET)为5~30m2/g、邻苯二甲酸二丁酯吸附(DBP)为30~200ml/100g和具有小于0.1Ohm·cm的规定的电阻率。
CN93104525A 1992-04-07 1993-04-06 从天然气和/或甲烷的热分解生产纯炭黑颗粒的方法和用途 Expired - Fee Related CN1051786C (zh)

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CA2133768C (en) 1998-01-06
HU9402781D0 (en) 1994-12-28
JPH07504707A (ja) 1995-05-25
CA2133768A1 (en) 1993-10-14
NO921358D0 (no) 1992-04-07
CN1051786C (zh) 2000-04-26
MA22861A1 (fr) 1993-12-31
EG20092A (en) 1997-05-31
AU3962793A (en) 1993-11-08
NO176885C (no) 1995-06-14
DE69301568T2 (de) 1996-08-01
ATE134211T1 (de) 1996-02-15
EP0635045A1 (en) 1995-01-25
NO921358L (no) 1993-10-08
MY109087A (en) 1996-11-30
MX186050B (es) 1997-09-22
DZ1678A1 (fr) 2002-02-17
MX9301975A (es) 1994-03-31
HU215905B (hu) 1999-03-29
CZ287532B6 (en) 2000-12-13
US5527518A (en) 1996-06-18
EP0635045B1 (en) 1996-02-14
NO176885B (no) 1995-03-06
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DE69301568D1 (de) 1996-03-28
ES2083859T3 (es) 1996-04-16

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