CN1331744C - 一种用硫酸钠法生产白炭黑和亚硫酸钠的工艺 - Google Patents

一种用硫酸钠法生产白炭黑和亚硫酸钠的工艺 Download PDF

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CN1331744C
CN1331744C CNB2005102003151A CN200510200315A CN1331744C CN 1331744 C CN1331744 C CN 1331744C CN B2005102003151 A CNB2005102003151 A CN B2005102003151A CN 200510200315 A CN200510200315 A CN 200510200315A CN 1331744 C CN1331744 C CN 1331744C
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sodium
carbon black
white carbon
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wat
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CN1699164A (zh
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卢元健
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Fujian Nanping Sanyuan Circulation Technology Co ltd
Win Jiaxen White Carbon Black Nanping Co ltd
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Degussa Wellink Silica Nanping Co Ltd
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Priority to CNB2005102003151A priority Critical patent/CN1331744C/zh
Publication of CN1699164A publication Critical patent/CN1699164A/zh
Priority to JP2008515033A priority patent/JP2008542187A/ja
Priority to US11/916,867 priority patent/US20080199385A1/en
Priority to RU2007148741/15A priority patent/RU2007148741A/ru
Priority to PCT/CN2006/001228 priority patent/WO2006131066A1/en
Priority to CNA2006800191498A priority patent/CN101184694A/zh
Priority to BRPI0611666-3A priority patent/BRPI0611666B1/pt
Priority to KR1020077028664A priority patent/KR20080016837A/ko
Priority to EP06742114A priority patent/EP1888462A1/en
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    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00Silicon; Compounds thereof
    • C01B33/113Silicon oxides; Hydrates thereof
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00Silicon; Compounds thereof
    • C01B33/113Silicon oxides; Hydrates thereof
    • C01B33/12Silica; Hydrates thereof, e.g. lepidoic silicic acid
    • C01B33/18Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof
    • C01B33/187Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof by acidic treatment of silicates
    • C01B33/193Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof by acidic treatment of silicates of aqueous solutions of silicates
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00Silicon; Compounds thereof
    • C01B33/113Silicon oxides; Hydrates thereof
    • C01B33/12Silica; Hydrates thereof, e.g. lepidoic silicic acid
    • C01B33/18Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00Silicon; Compounds thereof
    • C01B33/20Silicates
    • C01B33/32Alkali metal silicates
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01DCOMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
    • C01D5/00Sulfates or sulfites of sodium, potassium or alkali metals in general
    • C01D5/14Preparation of sulfites
    • 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
    • C09C1/28Compounds of silicon

Abstract

一种用硫酸钠法生产白炭黑和亚硫酸钠的工艺,其特征在于将石英沙、硫酸钠和炭混合后加入窑炉内反应,生成的固体和二氧化硫经下列步骤处理后生成白炭黑和亚硫酸钠:(1)将生成的硅酸钠固体溶解,过滤后得到硅酸钠液体,在硅酸钠液体中加入亚硫酸氢钠进行合成反应后过滤;(2)将生成的二氧化硫与步骤(1)产生的滤液的一部分进行反应,生成的亚硫酸氢钠循环参与如步骤(1)所述的合成反应;(3)生成白炭黑:将步骤(1)过滤后的物质进行酸化、过滤、洗涤、干燥制出白炭黑;(4)生成亚硫酸钠:将步骤(1)产生的滤液的一部分浓缩干燥制出亚硫酸钠。本发明的工艺流程简单、联产亚硫酸钠、生产成本低,具有较大的应用推广价值。

Description

一种用硫酸钠法生产白炭黑和亚硫酸钠的工艺
本发明涉及一种用硫酸钠法生产白炭黑和亚硫酸钠的工艺。
技术背景
白炭黑又名轻质二氧化硅,是橡胶的良好补强剂;也用作润滑剂、绝缘材料及塑料制品、纸张、油漆、纺织品等的填充料或白色颜料。目前,国内外最常用的生产白炭黑的传统方法是沉淀法,该法需要消耗大量的纯碱和硫酸,成本较高。
发明内容
本发明的目的在于提供一种用硫酸钠法生产白炭黑和亚硫酸钠的工艺,该工艺降低了生产白炭黑的成本。
本发明的理论基础是:
2Na2SO4+2nSiO2+C→2Na2O·nSiO2+2SO2+CO2
SO2+Na2SO3+H2O→2NaHSO3
2NaHSO3+Na2O·nSiO2→nSiO2+2Na2SO3+H2O
本发明是一种用硫酸钠法生产白炭黑和亚硫酸钠的工艺,其特征在于将石英沙、硫酸钠和炭按118.3~147.9∶100∶4~12的重量比混合后加入窑炉内,于1200℃~1500℃下进行反应,生成的硅酸钠固体和二氧化硫经下列步骤处理后生成白炭黑和亚硫酸钠:(1)将生成的硅酸钠固体按100∶180~488的重量比加入水进行溶解,过滤,在硅酸钠滤液中按硅酸钠∶亚硫酸氢钠为1∶2的摩尔比加入浓度为1%~40%的亚硫酸氢钠溶液,于70~95℃下进行合成反应,反应1~4h后,再进行过滤;2)将生成的二氧化硫与步骤(1)产生的滤液的一部分于20~50℃下进行反应,生成的亚硫酸氢钠继续参与如步骤(1)所述的合成反应;(3)生成白炭黑:将步骤(1)中过滤后的物质进行酸化至3.5~6.0,经过滤、洗涤、干燥制出白炭黑;(4)生成亚硫酸钠:将步骤(1)产生的滤液的另一部分浓缩干燥制出亚硫酸钠。
较之已有的技术,本发明的优点在于:一是不使用纯碱或者烧碱,硫酸或者盐酸:二是在生产白炭黑同时,联产亚硫酸钠产品:三是无废物排放;四是利用全保温马蹄焰窑炉连续生产由硫酸钠法制得的水玻璃。
具体实施方式
本发明是这样实现的:将原料石英砂、硫酸钠和炭(已经粉碎)按照SiO2∶Na2SO4∶C=100∶81.4∶6.5的重量比例混合,投入连续投入全保温马蹄焰窑炉,反应温度1420℃~171450℃,连续出料,物料经水淬、溶解得到3.5M、29Be’硅酸钠液体。在6L的反应釜中加入底水1.875L,预加硅酸钠溶液0.043L,加温至85℃,在90分钟的时间内,同时均匀加入硅酸钠溶液0.706L和8.25%亚硫酸氢钠溶液2.273L,反应结束后进行过滤,回收亚硫酸钠溶液,过滤所得的物质进行酸化调整PH值到4.5。所得物料经过滤、洗涤、干燥制出白炭黑209.50g(BET为172m2/g),取一半亚硫酸钠溶液通入5%的二氧化硫气体,得到8.25%亚硫酸氢钠溶液,该溶液回用生产白炭黑。另取一半亚硫酸钠溶液通过浓缩干燥制出112.37g亚硫酸钠。
本发明的工艺流程简单、生产成本低,具有较大的应用推广价值。

Claims (2)

1.一种用硫酸钠法生产白炭黑和亚硫酸钠的工艺,其特征在于将石英沙、硫酸钠和炭按118.3~147.9∶100∶4~12的重量比混合后加入窑炉内,于1200℃~1500℃下进行反应,生成的硅酸钠固体和二氧化硫经下列步骤处理后生成白炭黑和亚硫酸钠:
(1)将生成的硅酸钠固体按100∶180~488的重量比加入水进行溶解,过滤,在硅酸钠滤液中按硅酸钠∶亚硫酸氢钠为1∶2的摩尔比加入浓度为1%~40%的亚硫酸氢钠溶液,于70~95℃下进行合成反应,反应1~4h后,再次过滤;
(2)将生成的二氧化硫与步骤(1)中所述再次过滤得到的滤液的一部分于20~50℃下进行反应,生成的亚硫酸氢钠继续参与如步骤(1)所述的合成反应:
(3)生成白炭黑:将步骤(1)中所述再次过滤得到的物质进行酸化至3.5~6.0,经过滤、洗涤、干燥制出白炭黑;
(4)生成亚硫酸钠:将步骤(1)中所述再次过滤得到的滤液的另一部分浓缩干燥制出亚硫酸钠。
2.根据权利要求1所述的一种用硫酸钠法生产白炭黑和亚硫酸钠的工艺,其特征在于所述的窑炉为全保温马蹄焰窑炉。
CNB2005102003151A 2005-06-08 2005-06-08 一种用硫酸钠法生产白炭黑和亚硫酸钠的工艺 Active CN1331744C (zh)

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CNB2005102003151A CN1331744C (zh) 2005-06-08 2005-06-08 一种用硫酸钠法生产白炭黑和亚硫酸钠的工艺
US11/916,867 US20080199385A1 (en) 2005-06-08 2006-06-06 Process for Producing Silica and Sodium Sulfite with Sodium Sulfate
JP2008515033A JP2008542187A (ja) 2005-06-08 2006-06-06 硫酸ナトリウムを用いてシリカと亜硫酸ナトリウムとを製造する方法
RU2007148741/15A RU2007148741A (ru) 2005-06-08 2006-06-06 Способ получения двуокиси кремния и сульфита натрия с использованием сульфата натрия
PCT/CN2006/001228 WO2006131066A1 (en) 2005-06-08 2006-06-06 A process for producing silica and sodium sulfite with sodium sulfate
CNA2006800191498A CN101184694A (zh) 2005-06-08 2006-06-06 一种用硫酸钠法生产轻质二氧化硅和亚硫酸钠的工艺
BRPI0611666-3A BRPI0611666B1 (pt) 2005-06-08 2006-06-06 Process for the production of sodium soil and sulfite with sodium sulfate
KR1020077028664A KR20080016837A (ko) 2005-06-08 2006-06-06 황산 나트륨을 사용한 실리카 및 아황산 나트륨의 제조방법
EP06742114A EP1888462A1 (en) 2005-06-08 2006-06-06 A process for producing silica and sodium sulfite with sodium sulfate
IL186833A IL186833A0 (en) 2005-06-08 2007-10-22 A process for producing silica and sodium sulfite with sodium sulfate

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IL (1) IL186833A0 (zh)
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US20080202387A1 (en) * 2005-06-08 2008-08-28 Yuanjian Lu Process For Producing Silica and Sodium Sulfite With Sodium Sulfate
CN100545085C (zh) * 2005-06-10 2009-09-30 德固赛嘉联白炭黑(南平)有限公司 硫酸钠法生产白炭黑、亚硫酸钠和亚硫酸氢钠的工艺
CN101280127B (zh) * 2008-06-02 2010-11-17 通化双龙化工股份有限公司 塑料薄膜开口剂用沉淀白碳黑的制备方法
FR2933392B1 (fr) * 2008-07-04 2011-04-22 Rhodia Operations Procede de preparation de silice precipitee a partir de metabisulfite ou sulfite de sodium
CN101503193B (zh) * 2008-10-17 2011-09-07 株洲兴隆化工实业有限公司 一种使用燃煤循环流化床热风炉的白炭黑干燥系统
CN101811701B (zh) * 2010-04-10 2011-08-03 湖南新恒光科技有限公司 一种采用无水硫酸钠制备白炭黑与亚硫酸钠的生产工艺
CN102633266A (zh) * 2012-04-19 2012-08-15 浙江宇达化工有限公司 一种纳米二氧化硅的制备方法
CN107215878A (zh) * 2017-05-24 2017-09-29 安徽龙泉硅材料有限公司 高品质工业硅酸钠的生产技术
CN107090250A (zh) * 2017-05-24 2017-08-25 安徽龙泉硅材料有限公司 一种制备工业硅酸钠胶黏剂的方法
CN110284004B (zh) * 2019-06-25 2021-03-23 中南大学 一种铜渣与硫酸钠废渣协同资源化的方法
CN111620348B (zh) * 2020-06-22 2022-11-22 安徽龙泉硅材料有限公司 一种纳米二氧化硅用硅酸钠的制备方法
CN112938994B (zh) * 2021-03-23 2021-11-19 广州市飞雪材料科技有限公司 一种具有沙粒感的牙膏用二氧化硅及其制备方法

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JP2008542187A (ja) 2008-11-27
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CN1699164A (zh) 2005-11-23
KR20080016837A (ko) 2008-02-22
RU2007148741A (ru) 2009-07-20
BRPI0611666A2 (pt) 2010-09-28
BRPI0611666B1 (pt) 2017-10-31
IL186833A0 (en) 2008-02-09
EP1888462A1 (en) 2008-02-20
WO2006131066A1 (en) 2006-12-14

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