CN1723173A - 超干燥碳酸钙 - Google Patents

超干燥碳酸钙 Download PDF

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CN1723173A
CN1723173A CNA2003801056220A CN200380105622A CN1723173A CN 1723173 A CN1723173 A CN 1723173A CN A2003801056220 A CNA2003801056220 A CN A2003801056220A CN 200380105622 A CN200380105622 A CN 200380105622A CN 1723173 A CN1723173 A CN 1723173A
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calcium carbonate
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dry calcium
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CN100448777C (zh
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克里斯托夫·诺弗
赫尔穆特·迪伦堡
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Solvay Chemicals GmbH
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    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02Non-macromolecular additives
    • C09J11/04Non-macromolecular additives inorganic
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    • C01INORGANIC CHEMISTRY
    • C01FCOMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F11/00Compounds of calcium, strontium, or barium
    • C01F11/18Carbonates
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    • C01FCOMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F11/00Compounds of calcium, strontium, or barium
    • C01F11/18Carbonates
    • C01F11/185After-treatment, e.g. grinding, purification, conversion of crystal morphology
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/18Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24Acids; Salts thereof
    • C08K3/26Carbonates; Bicarbonates
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    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09D5/00Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/34Filling pastes
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    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00Physical properties of inorganic compounds
    • C01P2006/80Compositional purity
    • C01P2006/82Compositional purity water content
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/18Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24Acids; Salts thereof
    • C08K3/26Carbonates; Bicarbonates
    • C08K2003/265Calcium, strontium or barium carbonate

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Abstract

本发明涉及超干燥碳酸钙颗粒、干燥碳酸钙颗粒的方法以及所述碳酸钙的应用。根据本发明,碳酸钙颗粒使用微波进行干燥。干燥可以在连续带式设备、箱式设备或旋转管式设备内进行。可以制备干燥程度为含0-0.1%H2O的碳酸钙颗粒。

Description

超干燥碳酸钙
本发明涉及超干燥碳酸钙。碳酸钙通过使氢氧化钙水悬浮液与CO2或含有二氧化碳的气体反应或者通过充分研磨天然碳酸钙而得到。使用已知方法对该碳酸钙进行脱水干燥。
碳酸钙用于例如纸张、染料、密封剂、胶粘剂、聚合物、印刷油墨、橡胶等的生产。将其用作具有颜料性质的功能填料。
碳酸钙的应用范围一直在扩大,这归功于其优越的应用性。同时,生产碳酸钙的方法技术也被改进,以致可以根据预期应用生产不同性质的碳酸钙。例如可以改变颗粒结构。通过改变干燥条件而改变最终产物中的残余水分含量也是可能的。
通常,首先通过过滤或离心进行脱水,然后借助例如带式干燥机、流化床干燥机、粉碎干燥机等进行干燥。这些方法的缺点是碳酸钙在刚干燥完时效果较好,但在冷却过程中又从周围空气中吸收水分。根据粒度不同,或者最好根据比表面积不同,水分含量可达质量百分数的3%。
本发明的目的是通过后续微波处理完全干燥使用常规方法生产的碳酸钙并备用。
根据本发明,例如借助带式干燥机干燥的沉淀碳酸钙,其残余水分含量为0.1-3%,在特殊情况下残余水分含量达到80%,可随后使用微波进行干燥。
微波是具有不同频率的电磁波。常用频率是915MHz和2.45GHz。在微波处理过程中,通过电磁能直接转变为分子动能而产生热,即在不是太干的产品本身内产生热。
由于被加热材料的电磁特性而发生电磁能向热能的转变。一种材料是否能够利用微波进行加热或干燥,或者能够利用微波加热或干燥到什么程度,取决于其分子结构。极性分子,即具有不同电荷范围的分子,如水,能够使用微波进行有效加热。极性分子受到微波高频交变场的作用而旋转,并同时将电磁能转变成热。基于材料情况,由于每个分子都能生热,并且微波能够深入穿透,因此整体得到加热。这是与传统加热或干燥方法相比的一个主要优点,在传统方法中,热仅仅通过材料表面向材料内部传导。
完全吸收时转变的微波能为:
Pverl=2·π·f·E2εoε’rtan·δ,W/m3          (1).
穿透深度计算如下:
d = λ ϵ ′ r 2 π ϵ ′ ′ r , cm - - - ( 2 ) .
f      频率,Hz
εo   绝对介电常数(DC)
        8.85×10-12As/Vm
E      电场强度
       交变场,V/m
ε       =εo *r’-jεr”),复介电常数(DC)
tanδ    =εr”/ε’r
δ         介电损耗角,度
λ0  波长,cm,λ0=C/f
微波加热的温度分布与传统加热是相反的。在微波干燥中,这种反温度分布是有利的,这是由于这样可以在材料内部形成高压,并将水推动到表面。这些水在表面蒸发,使得表面湿度保持平衡,直到内部的水被实质上完全去除。只有该过程结束,表面才开始变干。
水由于其极性而吸收大量微波能或者微波能的主要部分,因此在已经变干的区域仅发生极少量的能量转变,以致微波能够从这儿更深地穿透材料。因此,大大降低材料中的残余水分含量是可能的,从而能够得到超干燥产品。
已经发现,仍具有0.1-3%H2O的残余水分含量的碳酸钙颗粒能够利用微波进行进一步的干燥。而且,通过沉淀或湿磨得到的悬浮液,或者由此得到的残余水分含量超过80%或超过30%的滤饼也能进行干燥。该处理适用于任何初始水分含量。干燥程度达0-0.1%。
已知具有不同构造的微波干燥设备。对于大的块状的材料,使用连续带式设备或者间歇式运转的箱式设备。
粉末或细小颗粒优选在微波旋转干燥炉设备中干燥。在这种情况下,使材料在旋转管中通过加热区,并在此时利用微波对其进行加热或干燥。
设备能够在真空、保护气体或空气环境中运转。根据设备的构造不同,床高可达20cm。对碳酸钙来说,至多10cm的床高已被证明是有利的。由于只需使用该设备除去残余水分,因此不需要很高的输出功率。几kW就足够了,但25kW-100kW以上也可使用。
根据本发明干燥的碳酸钙能够用作控制例如密封剂或胶粘剂流动性的添加剂。这种超干燥碳酸钙能够用作例如单组分或双组分聚氨酯密封剂、硅氧烷密封剂或者改性硅氧烷密封剂,尤其是MS聚合物密封剂的添加剂。
微波干燥的优点在于:
1.带式设备干燥是静态干燥,即:产品不承受任何机械应力的作用。
2.温度梯度指向表面,即:内部温度比表面温度高,随之产生的较高分压将待蒸发的液体传递到表面。
3.表面层不会干枯,即保持可渗透性。
4.内部液体蒸发时,液体通过孔隙结构传递到外部,因此干燥速率更高。
5.在微波的作用下产生在芯部的分压加速扩散过程。
6.快速干燥具有低热传导性的湿产品。
7.干燥时间短。
下面的实施例旨在阐明本发明,但不是限定本发明的范围。
实施例:
经过预干燥的CaCO3在连续带式设备中进行干燥,该设备置于工作长度为2m的微波信道(最大输出:6kW/2450MHz)中。
实施例1-10:
输送带覆盖范围:15mm高
使用残余水分含量为0.37%H2O的CaCO3
表1和表2示出不同条件下的干燥结果:
表1:
  实施例1-6 参比样品   1   2   3   4   5   6
  输送带速度m/min   0.8   0.4   1   1   1.7   1.7
  输出功率(kW)   1.5   1.5   1.5   1.3   1   1.7
  产量(kg/h)   4.8   2.4   5.4   5.4   12   12
  保压时间(s)   150   300   120   120   71   71
  含水量(%)   0.37   0.00   0.00   0.02   0.04   0.05   0.06
表2:
  实施例7-11 参比样品   7   8   9   10
  输送带速度m/min   2   2   3   4
  输出功率(kW)   5   5   5   5
  产量(kg/h)   60   60   90   120
  保压时间(s)   105   105   70   53
  含水量(%)   0.37   0.01   0.0   0.11   0.26

Claims (10)

1.超干燥碳酸钙,具有含0-0.1%H2O的干燥程度。
2.用于生产超干燥碳酸钙颗粒的方法,其特征在于使用微波干燥碳酸钙颗粒。
3.根据权利要求2的用于生产超干燥碳酸钙颗粒的方法,其特征在于使残余水分含量为0.1-3%的碳酸钙颗粒接触微波。
4.根据权利要求2的用于生产超干燥碳酸钙颗粒的方法,其特征在于使用微波对通过沉淀或湿磨得到的碳酸钙悬浮液,或者由此得到的残余水分含量大于80%的滤饼进行干燥。
5.根据权利要求2的用于生产超干燥碳酸钙颗粒的方法,其特征在于借助连续带式设备、箱式设备或旋转干燥炉设备进行微波干燥。
6.根据权利要求2的用于生产超干燥碳酸钙颗粒的方法,其特征在于微波干燥在真空或保护气氛条件下进行。
7.根据权利要求2-6的方法生产的超干燥碳酸钙用作控制密封剂和胶粘剂流动性的添加剂的用途。
8.根据权利要求7的超干燥碳酸钙的用途,用于聚氨酯密封剂,尤其是单组分和双组分密封剂。
9.根据权利要求7的超干燥碳酸钙的用途,用于硅氧烷密封剂。
10.根据权利要求7的超干燥碳酸钙的用途,用于改性硅氧烷密封剂,尤其是MS聚合物密封剂。
CNB2003801056220A 2002-12-11 2003-12-04 超干燥碳酸钙 Expired - Fee Related CN100448777C (zh)

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DE10257696A DE10257696A1 (de) 2002-12-11 2002-12-11 Ultratrockenes Calciumcarbonat

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TWI565660B (zh) * 2011-01-17 2017-01-11 Maruo Calcium Surface treatment of heavy calcium carbonate, a method for producing the same, and a resin composition incorporating the calcium carbonate
CN104619762A (zh) * 2012-07-18 2015-05-13 丸尾钙株式会社 重质碳酸钙、其制备方法及含有该碳酸钙的树脂组合物
CN104619762B (zh) * 2012-07-18 2019-08-23 丸尾钙株式会社 重质碳酸钙、其制备方法及含有该碳酸钙的树脂组合物
CN104448938A (zh) * 2014-11-18 2015-03-25 江苏群鑫粉体材料有限公司 胶粘剂用超细活性重质碳酸钙的生产方法

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AU2003293758A1 (en) 2004-06-30
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CA2509394A1 (en) 2005-06-09
IL169086A0 (en) 2009-02-11
WO2004052784A3 (de) 2004-11-18
RU2347164C2 (ru) 2009-02-20
RU2005121534A (ru) 2006-01-20
KR20050088425A (ko) 2005-09-06
EP1572589A2 (de) 2005-09-14
WO2004052784A2 (de) 2004-06-24
ZA200504655B (en) 2006-04-26
PL377383A1 (pl) 2006-02-06
DE10257696A1 (de) 2004-06-24
CN100448777C (zh) 2009-01-07
US20050276897A1 (en) 2005-12-15
HK1081939A1 (en) 2006-05-26
AU2003293758A8 (en) 2004-06-30
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MXPA05006233A (es) 2005-12-05
BR0317136A (pt) 2005-10-25

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