CN101020579A - Process of preparing high purity light calcium carbonate fine powder with carbide residue - Google Patents

Process of preparing high purity light calcium carbonate fine powder with carbide residue Download PDF

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CN101020579A
CN101020579A CN 200610031408 CN200610031408A CN101020579A CN 101020579 A CN101020579 A CN 101020579A CN 200610031408 CN200610031408 CN 200610031408 CN 200610031408 A CN200610031408 A CN 200610031408A CN 101020579 A CN101020579 A CN 101020579A
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reaction
carbide
ammonium chloride
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calcium carbonate
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宋永才
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中国人民解放军国防科学技术大学
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Abstract

The process of preparing high purity light calcium carbonate fine powder with carbide residue includes reacting carbide residue as one kind of industrial waste directly with ammonium chloride solution to produce mixture solution of calcium chloride and ammonia water, filtering, introducing CO2 gas for carbonating reaction, filtering the produced slurry, water washing the filter cake and stoving to obtain calcite type spherical light calcium carbonate fine powder, and circulating ammonium chloride solution for reuse. The present invention has simple technological process, lowered production cost, high product purity and high product quality.

Description

一种由电石渣制备高纯轻质碳酸钙微粉的方法 A method of preparing an electrically carbide powder of high purity calcium carbonate

技术领域 FIELD

:本发明涉及一种化工原料的制造方法,具体涉及一种高纯度轻质碳酸钙微粉的制造方法。 : The present invention relates to a method for producing a chemical raw materials, particularly relates to a method for producing a light calcium carbonate powder of high purity.

背景技术 Background technique

:电石是一种重要的化工原料,主要用于生产PVC、炭黑、溶解乙炔等行业。 : Calcium carbide is an important chemical raw materials, mainly for the production of PVC, carbon black, acetylene and other industries. 用电石制取乙炔气、PVC等产品时,会产生大量的固体废弃物-电石渣。 Preparation of calcium carbide acetylene gas, while PVC and other products, a large amount of solid waste - Calcium Carbide. 据统计,全国每年生产的电石约2000万吨,其中国内使用约1500万吨,按每消耗一吨电石产生废渣1.2吨计算,每年产生的电石渣就达到1800万吨以上。 According to statistics, every year about 20 million tons of calcium carbide production, of which about 15 million tons for domestic use, consumption per one ton of calcium carbide slag produced 1.2 tons computing, carbide slag produced annually more than 18 million tons. 电石渣主要成分是氢氧化钙(含量达到90%以上),还含有其它一些杂质如SiO2、Fe2O3、MgO、Al2O3和碳渣等。 Carbide slag of calcium hydroxide is the main component (more than 90% content), also contains other impurities such as SiO2, Fe2O3, MgO, Al2O3 and the like, and carbon residue.

轻质碳酸钙是以石灰石为原料,经消化为氢氧化钙浆液后用二氧化碳碳酸化反应制得的。 PCC is composed of limestone as raw material, after digestion of the slurry of calcium hydroxide with carbon dioxide in the carbonation reaction prepared. 轻质碳酸钙用途很广,主要用于橡胶、塑料、造纸和涂料、油墨等工业中作填充剂,并可用于牙粉、牙膏、化妆品等日用化工制品中,还可用于有机合成、冶金、玻璃和石棉生产中。 Calcium carbonate is widely used, mainly used for rubber, plastics, paper and paints, inks and other industries as a filler can be used for tooth powder, toothpaste, cosmetics, household chemicals and other products, it is also used in organic synthesis, metallurgy, glass and asbestos production. 目前全国轻质碳酸钙生产企业有300余家。 PCC is currently the country has more than 300 manufacturing enterprises. 全国轻质碳酸钙的生产和消费量达到数百万吨,并且还在以每年10%以上的增长速度逐年提高。 National PCC production and consumption reached millions of tons, and is still more than 10% annual growth rate increased every year.

由于电石渣中氢氧化钙含量很高,因此它是非常有价值的二次资源,并且具有成本低,来源广的特点。 Since carbide slag in a high content of calcium hydroxide, so it is very valuable secondary resources, and has a low cost, wide source characteristics. 用于生产有广泛用途的轻质碳酸钙微粉,既有利于减少污染,保护环境,又能变废为宝,创造巨大的经济效益。 There are widely used for the production of precipitated calcium carbonate powder, not only help reduce pollution, protect the environment, but also turning waste into wealth, create huge economic benefits.

关于以电石渣为原料制备轻质碳酸钙微粉,已有较多的专利技术的报告。 Report on the electrically carbide raw material to prepare a light calcium carbonate powder, more existing patented technology. 如中国专利CN1377830(2002-11-06)报告了利用工业电石在过量水条件下分解生成乙炔后产生的氢氧化钙废渣浆(即电石渣)和生石灰生产过程中排放的二氧化碳废气体,通过碳化反应生产轻质碳酸钙。 Chinese Patent CN1377830 (2002-11-06) reported on the calcium hydroxide slurry residue (i.e., carbide slag) during the production of lime and carbon dioxide emissions from industrial waste gas produced after decomposition of acetylene carbide excess of water under conditions of use, by carbonization reaction to produce precipitated calcium carbonate. 中国专利CN1061391(1992-05-27)报告的一种由电石泥生产微细轻质碳酸钙的方法是:将电石泥经沉降除渣增浓,再进行多级旋液分离,将砂子及大量微细碳末除去,分离后的浆料调整浓度后送入碳化塔碳化,碳化后再经沉降分层、分离脱水、干燥、过筛分级得到轻质碳酸钙产品。 A method of Chinese Patent CN1061391 (1992-05-27) reported a fine calcium carbonate is produced by the calcium carbide sludge: the calcium carbide sludge slag enriched by settling, then the multi-stage hydrocyclone, and a large number of fine sand carbon was removed at the end, after adjusting the concentration of the slurry fed to the separation column carbide, carbide, carbide, and then layered over settling, dewatering separated, dried, sieved to obtain precipitated calcium carbonate products.

但是,实验研究表明,由于电石渣中杂质的存在,直接将其用于生产轻质碳酸钙存在产品质量差(杂质含量高、粒度大、白度低)的问题。 However, experimental studies have shown that, due to the presence of impurities in the electric gravel, used directly in the presence of poor product quality (high impurity content, large particle size, low whiteness) PCC production problems. 而采用复杂的分离提纯方法,则显著增加制造成本与降低收率,并且由于杂质与氢氧化钙呈细粉混杂难以彻底除去,制得产品的质量(尤其是纯度与白度)难以达标。 The use of complicated separation and purification methods, significantly increase manufacturing costs and reduce the yield, since the impurities and the calcium hydroxide was difficult to completely remove the mixed powder, the quality of the product obtained (purity, especially the whiteness) difficult to compliance.

中国专利CN1058005(1992-01-22)(文献一)报告了一种用电石渣制取高纯度工业碳酸钙的方法。 Chinese Patent CN1058005 (1992-01-22) (a document) reported a method of preparing high purity carbide electric industrial calcium carbonate. 其技术特征为:首先对电石渣进行高温煅烧预处理(在150-200℃预热后再在1200-1350℃热处理),这种预处理相当于传统技术的石灰生产工序,将预处理后的电石渣和氯化铵及水按一定比例配成悬浮液,经充分搅拌后过滤澄清。 Its technical characteristics as follows: First, the high temperature carbide slag pretreated calcined (heat treated at 1200-1350 deg.] C after preheating 150-200 ℃), corresponding to the conventional art Such pretreatment lime production step after the pretreated carbide slag and water and ammonium chloride were suspended by a certain percentage, was clarified by filtration after stirring sufficiently. 通入二氧化碳气体进行碳酸化,反应产物经后续处理得到高纯工业碳酸钙。 Carbon dioxide gas into the carbonation, the reaction product obtained by subsequent treatment of industrial calcium carbonate of high purity. 在文献(化工环保,2004,V24,P283-285)(文献二)中报告了由电石渣循环制备超细碳酸钙的方法:将电石渣经过约100℃干燥后,溶解于质量分数为5%,过量30%的氯化铵溶液中,过滤后在一定的温度下向制备的CaCl2溶液中加入一定量的氨水调节pH值后通入CO2气体,控制制备工艺参数和条件(如温度、浓度、气流速度等),适时加入适量添加剂,搅拌、反应一定时间后过滤、干燥制得了粒径为0.5~1μm、长径比为10~20的针状文石型碳酸钙微粉。 In the literature (environmental chemical, 2004, V24, P283-285) (Document B) reports a method for the cyclic preparation of superfine calcium carbonate Calcium Carbide: the carbide slag after drying about 100 ℃, dissolved in a mass fraction of 5% , 30% excess of ammonium chloride solution, filtered and added to a quantity of the CaCl2 solution was prepared at a certain temperature after adjusting the pH value of the aqueous ammonia into CO2 gas, the control process parameters and conditions (e.g., temperature, concentration, gas flow rate, etc.), timely and proper additive, stirring, after a certain time the reaction was filtered, drying had a particle size of 0.5 ~ 1μm, an aspect ratio of needle-shaped aragonite calcium carbonate powder 10 to 20. 在该文献中所提到的循环工艺是对反应后的滤液分别进行冷凝分离或浓缩后冷却结晶以回收其中的氨水和氯化铵,并重复使用。 Circulating process in this document is mentioned in the filtrate after the reaction were condensed in a separation or concentration cooling crystallization and recovery of ammonia wherein ammonium chloride and reused. 中国专利CN1172073(1998-02-04)(文献三)公开了一种超微细轻质碳酸钙生产工艺:将电石渣或消化石灰在含氯化物中浸取,经排NH3、再过滤去渣后加入碳酸氢铵,沉淀后经过滤即可得到超微细轻质碳酸钙,滤液可返回到浸取工序循环使用。 Chinese Patent CN1172073 (1998-02-04) (Document C) discloses an ultra-fine light calcium carbonate production process: the carbide slag or lime digestion leached in a chloride-containing, through a discharge NH3, and then to the residue after filtration after addition of ammonium bicarbonate, the precipitate was filtered to obtain ultrafine precipitated calcium carbonate and the filtrate is returned to the leaching step may be recycled.

在以上三篇文献中均采用了将电石渣与氯化铵溶液反应的方法,在电石渣中加入氯化铵溶液后,废渣中的Ca(OH)2很容易反应转变为CaCl2,其反应式如下:Ca(OH)2+2NH4Cl→CaCl2+2NH3·H2O (1)这样电石渣中的Ca(OH)2以CaCl2溶液的形式被提取出来,而废渣中的SiO2、Fe2O3、MgO、Al2O3和碳渣等均不溶于氯化铵溶液中,通过过滤很容易被除去。 In the above three documents are used in the method of the reaction of carbide slag with ammonium chloride solution, and after addition of ammonium chloride solution in the carbide slag, slag of Ca (OH) 2 reacts readily converted of CaCl2, the reaction of formula as follows: Ca (OH) 2 + 2NH4Cl → CaCl2 + 2NH3 · H2O (1) so carbide slag of Ca (OH) 2 is extracted in the form of CaCl2 solution out, and waste of SiO2, Fe2O3, MgO, Al2O3 and carbon residue dissolved in ammonium chloride solution and the like are not, easily removed by filtration. 而呈碱性的CaCl2溶液在通入CO2气体后容易发生碳酸化反应生成CaCO3沉淀,经分离、洗涤、干燥即得到碳酸钙粉体产品,其反应式如下:CaCl2+2NH3·H2O+CO2→CaCO3+2NH4Cl+H2O (2)由于电石渣中的Ca(OH)2通过反应(1)转变为可溶物,而杂质作为不溶物被过滤除去,采用这种方法便可制得高纯的碳酸钙产品。 And basicity CaCl2 solution after the CO2 gas into the carbonation reaction occurs readily CaCO3 precipitate was isolated, washed, and dried to obtain calcium carbonate powder products, the following reaction formula: CaCl2 + 2NH3 · H2O + CO2 → CaCO3 + 2NH4Cl + H2O (2) carbide slag because of Ca (OH) 2 by reaction (1) into a soluble, while the impurities as insoluble matters were removed by filtration, this method can be obtained high purity calcium carbonate product.

但是采用上述这些方法在一般情况下难以得到微细轻质碳酸钙。 However, using these methods is difficult to obtain a fine calcium carbonate in general. 在文献一中没有制得粒度在5μm以下的轻质碳酸钙微粉。 No light calcium carbonate powder a particle size of less than 5μm in the literature in a. 在文献二中,需要加入较为昂贵的添加剂,才能制得粒径约为1μm的针状文石型碳酸钙微粉,而主要为方解石型的轻质碳酸钙微粉仍然未能得到,并且由于反应温度偏高,在反应中需要补加较多量的氨水,进一步提高了制备难度与成本。 In the literature two, the need to add expensive additives, particle diameter of about 1μm to acicular aragonite calcium carbonate powder, and mainly calcite light calcium carbonate powder is still not obtained, since the reaction temperature and high, the reaction required additional large amount of ammonia further increases the difficulty and cost of preparation. 在文献三中则需采用碳酸氢铵进行碳酸化,仍然存在使制备成本提高的问题。 In the literature III ammonium bicarbonate was needed to carbonation, there is still a problem that the production costs increase.

工业上制备轻质碳酸钙微粉主要采用精制的石灰浆液,控制二氧化碳碳酸化反应条件制得。 Preparation of light calcium carbonate powder mainly industrially purified lime slurry, the control of the reaction conditions of carbonated prepared. 通过碱性CaCl2溶液用二氧化碳碳酸化方法制备碳酸钙微粉,其反应原理、碳酸钙成核与生长机制与石灰浆液的碳酸化有显著的不同。 By basic CaCl2 solution with carbon dioxide carbonation method of preparing calcium carbonate, micronized, the principle of the reaction, the calcium carbonate nucleation and growth mechanism and carbonation lime slurry is significantly different. 如何通过控制制备条件,在不需加入较为昂贵的添加剂的条件下生成方解石型的轻质碳酸钙微粉,是由电石渣制备轻质碳酸钙所必须解决的一个重要的技术问题。 How controlling production conditions generated calcite light calcium carbonate powder without adding more expensive in terms of the additive, is prepared from an electrically carbide precipitated calcium carbonate must solve an important technical problem.

发明内容 SUMMARY

本发明所要解决的技术问题是:针对上述现有技术制备方法中存在的问题,而提供一种以电石渣为原料、无需高温煅烧预处理、也无需加入昂贵的添加剂、氯化铵溶液能循环利用、显著降低工艺难度和制造成本、产品纯度高、粒度小、减轻环境污染、适于工业化批量生产的高纯度轻质碳酸钙微粉的制备方法。 The present invention solves the technical problem: for preparing the above-described prior art methods present problems, and to provide a carbide slag as raw material, without high-temperature calcination pretreatment, but also without the addition of expensive additives, ammonium chloride solution can be recycled use, significant reduction in the manufacturing cost and process difficulty, high purity, small particle size, reduce environmental pollution, industrial mass production method of high purity calcium carbonate powder suitable.

本发明采用的技术方案如下:以工业废弃物电石渣为原料,不经过高温预处理或分离杂质等过程直接与氯化铵溶液反应将其转化为氯化钙与氨水的混合溶液,经过滤除去不溶物杂质后,在该氯化钙溶液中通入二氧化碳气体进行碳酸化反应,反应中不需加入添加剂,并基本在室温下通过控制适宜的制备条件以提高碳酸钙的成核速度并抑制晶粒生长,产物浆液过滤后,滤饼经水洗、烘干得到晶型为方解石的球型轻质碳酸钙微粉(粒度<5um),而滤液则通过测定氯化铵浓度并适量补充氯化铵后用于下一次反应,实现氯化铵溶液的循环使用。 The present invention adopts the following technical solution: an industrial waste carbide slag as the raw material, the high temperature process without pretreatment or separation of impurities is reacted with ammonium chloride solution and the like is directly converted to a mixed solution of calcium chloride with ammonia, removed by filtration after insolubles impurities in the calcium chloride solution with carbon dioxide gas in the carbonation reaction, the reaction without addition of an additive, and substantially at room temperature by controlling the preparation conditions appropriate to increase the rate of nucleation of calcium carbonate crystals and inhibits after the grain growth, the product slurry was filtered, the filter cake was washed with water, and drying to give spherical precipitated calcium carbonate powder (particle size <5um) to calcite crystal form, and the filtrate is determined by the concentration and amount of added ammonium chloride the reaction time for the next, the ammonium chloride solution used for recycling.

具体制备工艺过程和条件如下: Specific preparation processes and conditions were as follows:

(1)在首次制备时,将工业废弃物电石渣直接加入3~10倍的水混匀,按电石渣(干基)与氯化铵重量比为1∶1.0~1.6的比例在电石渣浆液中加入工业级氯化铵,在室温浸取或一定温度如20~50℃条件下搅拌反应2~10小时。 (1) preparing the first time, the industrial waste carbide slag added directly to the water 3 to 10 times mix, press carbide slag (dry basis) weight ratio of ammonium chloride to 1.6 in the ratio 1:1.0 carbide slag slurry technical grade ammonium chloride was added, extraction, or as a temperature condition of the reaction mixture was stirred at 20 ~ 50 ℃ 2 ~ 10 hours at room temperature. 反应混合物溶液过滤除去不溶物渣滓后得到澄清碱性氯化钙溶液。 The reaction mixture solution was filtered to give a clear basic insolubles dross removing calcium chloride solution.

(2)将碱性氯化钙溶液置于反应装置中,控制反应温度在室温或5~35℃之间,边搅拌边通入CO2与空气的混合气进行碳酸化反应,保持CO2气流量为0.1~4.0L min-1、空气流量为0.3~12.0L min-1、搅拌速率100~3000rpm(转/分),用pH计或pH试纸监测反应体系的pH值变化。 (2) the alkaline calcium chloride solution was placed in the reactor, controlling the reaction temperature between room temperature or 5 ~ 35 ℃, stirring the mixture gas into CO2 and air carbonation reaction, CO2 gas flow rate was maintained 0.1 ~ 4.0L min-1, air flow rate of 0.3 ~ 12.0L min-1, a stirring rate of 100 ~ 3000rpm (revolutions / min), change in pH value with a pH meter or pH paper to monitor the reaction system.

(3)当反应体系pH值从强碱性降低至低于7.0时,即可结束反应。 (3) When the pH of the reaction system was decreased from 7.0 to less than strongly basic, to end the reaction. 根据反应条件的不同,碳酸化反应速度不同,总碳酸化时间在5min~120min。 Depending on the reaction conditions, different carbonation reaction rate, the total carbonation time of 5min ~ 120min.

(4)将反应产物过滤(普通滤纸过滤或离心甩干),滤出固体产物用水洗涤2-3遍,再在60-100℃烘干便可得到轻质CaCO3粉状产品。 (4) The reaction product was filtered (filter paper, ordinary drying or centrifugation), the solid product was filtered off and washed 2-3 times with water, and then dried at 60-100 deg.] C can be obtained a light CaCO3 powder product. 根据需要,可在反应结束后采用硬脂酸、硬脂酸盐、钛酸酯偶联剂等进行活化处理得到活性轻质碳酸钙产品。 According to need, may be employed stearic acid, stearic acid, a titanate coupling agent or the like after the reaction to an activation treatment to obtain an active light calcium carbonate.

(5)将滤液回收,测定其中的氮含量,并由此确定浓缩后的滤液中氯化铵的浓度。 (5) The filtrate recovered, wherein the determination of nitrogen content, thereby determining the concentration of the filtrate and the concentrated ammonium chloride. 根据需要补充少量水与氯化铵,调节滤液(氯化铵溶液)达到与首次制备时相同的体积和浓度。 The need to add a small amount of water and ammonium chloride, the filtrate was adjusted (ammonium chloride solution) to achieve the same volume and concentration was prepared for the first time.

(6)在第二次及以后各次制备中,按(1)中相同的加入量将电石渣直接加入到调制后的滤液中,在与首次制备相同的条件下反应。 (6) In each of the second and later times in the preparation, by (1) the same amount of carbide slag added to the filtrate was added directly after the modulation, the first reaction in the preparation of the same. 反应混合物溶液过滤除去不溶物渣滓后继续进行上述(2)(3)(4)(5)过程,便可实现轻质碳酸钙微粉的生产与滤液的循环使用。 The reaction mixture solution was filtered to remove insolubles dross continued (2) (3) (4) (5) the above-described process, can be realized and the filtrate was recycled PCC produced fine powder.

所述原料为工业废弃物电石渣,电石渣可以直接使用,不需要进行复杂的预处理。 The starting material is a carbide slag of industrial waste, carbide slag can be used directly, no complicated pretreatment. 在第一步反应(即反应(1))中,溶液中的氯化铵的含量以相对于电石渣中氢氧化钙含量过量为宜,若氯化铵不足量,则反应后电石渣中的氢氧化钙的转化不完全,而过量太多,则溶液中未反应氯化铵过多造成不必要的浪费。 In the first step of the reaction (i.e., reaction (1)), the amount of ammonium chloride in the solution with respect to calcium hydroxide of carbide slag content appropriate excess, if the insufficient amount of ammonium chloride, the reaction of carbide slag conversion of calcium hydroxide is not complete, but too excessive, the solution of ammonium chloride unreacted excessive unnecessary waste. 而反应条件也对这一步反应的完成程度有显著的影响,室温下延长时间或提高反应温度对提高氢氧化钙转化率有利。 And the reaction conditions have a significant influence on this degree of completion of the reaction step, the reaction temperature or increasing the extension time to improve the conversion of the calcium hydroxide is advantageously at room temperature.

所述CO2可以为工业瓶装气,但更为适宜的是采用工业上排放的含CO2的废气,例如氮肥厂脱碳CO2气体、制酒厂副产CO2气等,这类排放气纯度高,不含灰尘、硫等杂质,一般可以直接利用;也可采用热电厂烟道气、锅炉烟道气等回收的CO2,但这些混合气必须经严格除尘、降温、脱硫、增浓等方可使用;还可以采用石灰石、菱镁矿、白云石等碳酸盐非金属矿煅烧窑气,但这些含CO2的混合气必须严格除尘、降温、脱硫后才可使用。 The CO2 may be a bottled gas industry, but more suitable is the use of CO2-containing exhaust emission in the industry, for example, nitrogen fertilizer plant decarburization CO2 gas, CO2 gas byproduct wineries and the like, this type of exhaust gas of high purity, without containing dust, sulfur and other impurities, generally directly; power plant flue gas may also be employed, boiler flue gas, etc. the recovered CO2, but air-fuel mixture must be strictly dust, cooling, desulfurization, and other enriched before use; further limestone may be employed, magnesite, dolomite and other non-metallic mineral carbonates calcining kiln gas, but CO2-containing mixed gas must be strictly dust, cooling, desulfurization before use. 碳化用CO2混合气应达到CO2≥25%、温度≤35℃、含尘量基本为零、含硫≤1mg/m3等要求,否则必须采取相应净化方案,以保证其纯度。 Carbonation with CO2 gas mixture should reach CO2≥25%, a temperature of ≦ 35 deg.] C, dust content is substantially zero, sulfur ≤1mg / m3, etc., must be taken or purification scheme to ensure purity.

在第二步碳酸化反应中,适宜的制备条件对于获得微细碳酸钙产品是很重要的。 In the second step of the carbonation reaction, the suitable preparation conditions for obtaining a fine calcium carbonate products is very important.

所述碳酸化反应中由电石渣转化得到的碱性氯化钙溶液的浓度以2~15%为宜,浓度过小,生产量小,降低了生产效率,而浓度过大,则由于生成的碳酸钙微粒易于相互接触生长而得不到微细碳酸钙产物。 The alkali concentration of carbonated calcium chloride solution obtained by the reaction of conversion to carbide slag preferably 2 to 15%, the concentration is too small, a small amount of production, reducing production efficiency, and the concentration is too large, the resulting calcium carbonate particles tend to contact with each other but not the growth of fine calcium carbonate product. 更适宜的氯化钙溶液浓度为4~12%。 More suitably calcium chloride solution concentration of 4 to 12%.

所述碳酸化的反应温度以室温或5~35℃为宜,由于碳酸化反应为放热反应,而在较高的温度下碳酸钙微粒的生长速度加快,因此需要控制反应温度。 The carbonation reaction temperature is preferably room temperature or at 5 ~ 35 ℃, because the carbonation reaction is an exothermic reaction, while at higher temperatures to accelerate the growth rate of the calcium carbonate particles, it is necessary to control the reaction temperature. 但反应温度过低,将使反应时间延长,增加了微粒相互接触生长的机会,也对生成微细颗粒不利,并且需要对体系进行冷却,也增加了工艺与设备的复杂性,提高了制造成本。 However, the reaction temperature is too low, the reaction time will increase the opportunities for the growth of particles in contact with each other, generating fine particles also unfavorable, and the system needs to be cooled, but also increases the complexity of the process and equipment, increases the manufacturing cost. 更方便的方法为室温反应并通过对反应速度的控制或加水冷却使体系的反应升温低于30℃。 More convenient method is by reaction at room temperature and the reaction rate of the reaction control system or adding filling the warmed water cooled below 30 ℃.

所述碳酸化中使用的二氧化碳气体可以是二氧化碳与空气的混合气体,也可以是工业生产中排出的二氧化碳废气。 The carbon dioxide gas used in the carbonation may be a mixed gas of carbon dioxide and air, may be carbon dioxide gas discharged industrial production. 在混合气体或工业二氧化碳废气中,二氧化碳气体的浓度以20~80%为宜,二氧化碳的浓度低,造成反应时间延长,颗粒易于生长,而二氧化碳浓度过高,则颗粒的成核速度与生长速度均提高,颗粒易于团聚,对于制得微细碳酸钙产品不利。 Mixed gas or industrial waste carbon dioxide, the concentration of carbon dioxide gas is preferably from 20 to 80%, a low concentration of carbon dioxide, resulting in a longer reaction time easy to grow the particles, and the carbon dioxide concentration is too high, the particle nucleation rate and growth rate were increased, the particles tend to agglomerate, to obtain fine calcium carbonate products adversely.

所述二氧化碳气体的通入速度可以根据反应液体积或第一步反应转化后的氯化钙的浓度来确定,按纯CO2计算,通入速度以0.5~6L min-1L-1为宜,混合气体可以在保证上述二氧化碳流量的基础上确定混合气体的流量。 Into the carbon dioxide gas velocity may be determined, calculated as pure CO2, into speed 0.5 ~ 6L min-1L-1 is appropriate, depending on the concentration of calcium chloride mixed after the conversion or the first reaction volume of the reaction solution gas flow rate of the mixed gas may be determined on the basis of the flow rate to ensure that the above-described carbon dioxide. 二氧化碳流量小,造成碳酸化反应速度降低,生产效率低,通入速度过大,碳酸化反应速度加快,反应时间缩短,但两种情况下均难以得到微细碳酸钙产品。 A small flow of carbon dioxide, resulting in carbonation reaction rate decreases, low productivity, which leads to excessive speed, excessive carbonation reaction speed, the reaction time is shortened, but in both cases it is difficult to obtain a fine calcium carbonate products.

所述碳酸化反应中的搅拌速度也对反应过程有显著影响。 Stirring speed of the carbonation reaction also has a significant influence on the course of the reaction. 适宜的搅拌速度宜根据反应浆液的体积和容量进行适当调节。 Suitable agitation rate should be adjusted according to the volume and capacity of the reaction slurry. 搅拌速度过低,影响碳酸化反应的均匀性,搅拌速度过高也对产物品质有不利影响。 Stirring speed is too low, affecting the uniformity of the carbonation reaction, stirring speed was too high to have an adverse effect on product quality. 在1升反应体系中,搅拌速度以500~3000rpm(转/分)为宜。 In 1 liter of the reaction system, stirring speed of 500 ~ 3000rpm (revolutions / min) is appropriate.

本发明与现有方法相比有如下积极效果:本发明采用氯化铵溶液与电石渣反应将其转化为氯化钙溶液,不溶物杂质通过过滤除去从而保证了产品的高纯度。 The present invention has as compared with the conventional method of positive effects: the present invention uses carbide is reacted with ammonium chloride solution to convert it into an electrical calcium chloride solution, insoluble matter was removed by filtration and the impurities thus ensuring a high product purity. 与现有方法相比,不需要对电石渣进行预处理,显著降低了制造工艺难度与制造成本;本发明主要采用工业上排出的含CO2的废气作为气源,既可减轻CO2对环境的污染,也显著地降低了制造成本;本发明通过对制备工艺条件的综合控制,对由电石渣转化的碱性氯化钙溶液通过二氧化碳碳酸化反应制得了微细轻质碳酸钙。 Compared with the prior methods, does not require pretreatment of the carbide slag, significantly reduces the difficulty of manufacturing process and manufacturing costs; the present invention is mainly CO2-containing exhaust gas discharged from the industrial gas source, can reduce environmental pollution caused by CO2 , also significantly reduces the manufacturing cost; the present invention is prepared by integrated control of the process conditions, a solution of an alkaline calcium carbide slag had transformed the fine precipitated calcium carbonate by the carbonation reaction of carbon dioxide. 与现有方法相比,采用二氧化碳进行碳酸化,且反应中不需加入任何添加剂,且产物为方解石型的球型碳酸钙微粉;由于不需加入较为昂贵的添加剂,显著降低了制造成本;本发明将产物浆液过滤后的滤液(氯化铵溶液)反复循环使用。 Compared with the conventional methods, carbon dioxide carbonation, and the reaction without adding any additives, and the product is a calcite type spherical calcium carbonate powder; since without the addition of more expensive additives, significantly reduces the manufacturing cost; the present invention the filtrate (ammonium chloride solution) the product slurry was filtered after repeated recycling. 与现有方法相比,不需将滤液中的氯化铵分离提取,而是直接循环使用,只需少量补充损耗的氯化铵,因此显著简化了工艺过程,降低了氯化铵的损耗;采用本方法,可以化害为利,减少电石渣对环境的污染,而且由于制备方法简便,生产效率高,原料成本低,而且制得的轻质碳酸钙微粉纯度高,粒度小,因此本方法是一种低成本、适于工业化批量制造高品质轻质碳酸钙微粉的方法。 Compared with the conventional method, without separation of ammonium chloride and the filtrate was extracted, but direct recycling, only a small amount of ammonium chloride was added losses, thus significantly simplifying the process, reducing the loss of ammonium chloride; according to the present method, can harm into carbide slag reduce pollution of the environment, and because of easy preparation, high efficiency, low cost of raw materials, and the obtained high purity calcium carbonate powder, small particle size, so this method It is a low cost, and suitable for industrial mass production of high-quality light calcium carbonate powder method.

附图说明 BRIEF DESCRIPTION

:图1为由电石渣制备轻质碳酸钙工艺流程图图2为实施例1所制得轻质碳酸钙微粉的扫描电镜照片图3为对照例1所制得碳酸钙微粉的扫描电镜照片图4为对照例2所制得碳酸钙微粉的扫描电镜照片图5为实施例2所得产物的组成表具体实施方式:实施例1取电石渣(干基)40g,加入质量分数为20%、过量30%的氯化铵溶液中,室温搅拌反应4小时后用普通滤纸过滤(或抽滤),除去不溶物渣滓后得到澄清透明碱性CaCl2溶液。 : FIG. 1 carbide slag prepared by the PCC process flow diagram of FIG. 2 as an example a light calcium carbonate powder obtained SEM photograph of Example 3 is a scanning electron micrograph of Comparative Example FIG prepared calcium carbonate powder 1 4 is a scanning electron micrograph of Comparative Example prepared calcium carbonate powder 2 5 2 resulting product Example compositions table specific embodiments: EXAMPLE 1 carbide slag (dry basis) 4Og, mass fraction of 20% excess 30% ammonium chloride solution, stirred at room temperature filtered with ordinary filter paper for 4 hours (or filtration), the insoluble matter was removed to give a clear and transparent dross CaCl2 solution alkaline. 将所得CaCl2溶液置于1L三口烧瓶中加水稀释至溶液浓度为4%,在室温下边搅拌(搅拌速度为500rpm),边按800mL/min的空气流速、600mL/min的CO2气流速通入空气与CO2的混合气体开始碳酸化反应,约5min后溶液变浑浊,溶液温度逐步升高,反应25min后体系温度升高到约30℃。 The resultant CaCl2 solution was placed in 1L three-neck flask diluted with water to the solution concentration of 4%, was stirred (stirring speed 500 rpm for) at room temperature under, side-by 800mL / air flow min., CO2 flow rate 600mL / min through the air a mixed gas of CO2 carbonation reaction began, the solution became cloudy after ~ 5min, the solution temperature gradually increased, after 25min the reaction system temperature was increased to about 30 ℃. 测定溶液pH值,反应初期pH值为10.6,反应中缓慢降低至8.6,反应后期迅速降低至6.8,停止反应。 Determination of pH, initial 10.6 pH of the reaction, the reaction was slowly lowered to 8.6, the latter reaction was rapidly reduced to 6.8, the reaction was stopped. 产物抽滤并加水洗涤1~2遍,在60℃温度下干燥。 Product was filtered off with suction and washed with water, add 1 to 2 times, and dried at a temperature of 60 ℃. 用X-射线衍射仪测定产物为方解石,用扫描电镜观察(如附图2)均为球形颗粒,且粒径较为均匀,大颗粒为4~5μm,主要颗粒尺寸为2~3μm。 Measured by X- ray diffractometer calcite product with a scanning electron microscope (e.g., FIG. 2) are spherical particles, and more uniform particle size, large particles of 4 ~ 5μm, the main particle size of 2 ~ 3μm. 产物称重后可计算出反应产率为95%。 After the reaction product was weighed to calculate the yield was 95%. 测定该产物的沉降体积为2.5ml/g,白度为96%。 Determination of sedimentation volume of the product was 2.5ml / g, a whiteness of 96%.

实施例2同实施例1由电石渣制得CaCl2溶液后置于1L三口烧瓶中加水稀释至溶液浓度为10%,在室温下边搅拌(搅拌速度为700rpm),边以1500mL/min的空气流速、1000mL/minCO2气速度通入混合气体开始碳酸化反应,反应21min后溶液pH值降至7.0,停止反应。 Example 2 in Example 1 after obtained CaCl2 solution from the calcium carbide is placed diluted 1L three-neck flask was added aqueous solution to a concentration of 10%, stirring (stirring speed 700 rpm) at room temperature under, side air 1500mL / min flow rate, 1000mL / minCO2 gas velocity gas mixture starts carbonation reaction, the reaction solution pH to 7.0 21min, the reaction was stopped. 产物抽滤并加水洗涤1~2遍并在60℃温度下干燥后。 Product was filtered off with suction and washed with water, add 1 to 2 times and dried at a temperature of 60 ℃. 用扫描电镜观察为均匀球型颗粒,直径为2~4μm,沉降体积为2.6ml/g,白度为97%。 By scanning electron microscope of a uniform spherical particles, having a diameter of 2 ~ 4μm, the sedimentation volume of 2.6ml / g, a whiteness of 97%. 采用ICP-AES方法分析其组成,结果示于表1,可以看出产物中重金属元素含量极低,达到国家食品级碳酸钙国家标准。 ICP-AES analysis method using the composition, the results shown in Table 1, it can be seen very low levels of heavy metal elements in the product, up to the national standard national food grade calcium carbonate.

实施例3将实施例1中产物过滤后的滤液回收后,测定溶液的氮含量,补加少量水和氯化铵使溶液达到与实施例1相同体积和氯化铵浓度。 Example 3 After the filtrate recovered after filtration the product of Example 1 embodiment, the nitrogen content of the solution, supplemented with a small amount of water and ammonium chloride solution to achieve the same volume and concentration of ammonium chloride in Example 1 and the embodiment. 在该溶液中加入40g电石渣后,按实施例1相同条件进行电石渣的处理,得到的CaCl2溶液补加少量氨水后按与实施例1同样条件进行碳酸化反应,产物轻质碳酸钙微粉为球形颗粒(粒径为1~4μm),产物的沉降体积为2.6ml/g。 After addition of 40g of carbide slag to the solution, under the same conditions as in Example 1 carbide electrical treatment, the resulting solution was supplemented with CaCl2 little ammonia carbonation reaction under the same conditions as in Example 1, the product is precipitated calcium carbonate powder spherical particles (particle diameter of 1 ~ 4μm), sedimentation volume of the product was 2.6ml / g.

对照例1同实施例1由电石渣与氯化铵溶液反应制得澄清透明碱性CaCl2溶液后。 Comparative Example 1 Example 1 by reaction with the carbide slag and ammonium chloride solution to obtain a clear transparent rear CaCl2 solution alkaline. 将所得CaCl2溶液置于1L三口烧瓶中加水稀释至溶液浓度为12%,在室温下边搅拌(搅拌速度为600rpm),边按600mL/min的空气流速、400mL/min的CO2气流速通入空气与CO2的混合气体开始碳酸化反应,约5min后溶液变浑浊,反应25min后溶液pH值降至7.0以下结束反应。 The resultant CaCl2 solution was placed in 1L three-neck flask was added water to dilute the concentration of the solution 12% was stirred (stirring speed 600rpm) at room temperature under, side-by 600mL / air flow min., CO2 flow rate 400mL / min through the air a mixed gas of CO2 carbonation reaction began, the solution became cloudy after ~ 5min, the solution pH to below 7.0 after the completion of the reaction the reaction 25min. 产物抽滤并加水洗涤1~2遍,在60℃温度下干燥。 Product was filtered off with suction and washed with water, add 1 to 2 times, and dried at a temperature of 60 ℃. 产物用扫描电镜观察颗粒为立方体,边长为10~30μm,并夹杂有少量球形颗粒,长度为2~5μm(见附图3)。 The product particles with a scanning electron microscope cube side length of 10 ~ 30μm, and mixed with a small amount of spherical particles, a length of 2 ~ 5μm (see FIG. 3). 产物的沉降体积为1.4ml/g。 The product was settled volume 1.4ml / g.

对照例2同实施例1由电石渣与氯化铵溶液反应制得澄清透明碱性CaCl2溶液后。 Comparative Example 2 Example 1 by reaction with the carbide slag and ammonium chloride solution to obtain a clear transparent rear CaCl2 solution alkaline. 将所得CaCl2溶液置于1L三口烧瓶中加水稀释至溶液浓度为7%,在室温下边搅拌(搅拌速度为560rpm),边按1500mL/min的空气流速、1000mL/min的CO2气流速通入空气与CO2的混合气体开始碳酸化反应,反应19min后溶液pH值降至7.0以下结束反应。 The resultant CaCl2 solution was placed in 1L three-neck flask diluted with water to the solution a concentration of 7%, stirring (stirring speed 560 rpm) at room temperature under, side-by-1500mL / air flow min., CO2 flow rate 1000mL / min through the air CO2 mixed gas starts the carbonation reaction, the solution pH to below 7.0 after the completion of the reaction the reaction 19min. 产物抽滤、洗涤、烘干后用扫描电镜观察颗粒为立方体,边长为6~16μm,大小极不均匀,基本没有并夹杂球形颗粒。 The product is suction filtered, washed, and dried by scanning electron particle is cubic edge length of 6 ~ 16μm, the size is very uneven, and substantially no inclusions spherical particles. (见附图4)。 (See FIG. 4). 产物的沉降体积为1.7ml/g。 The product was settled volume 1.7ml / g.

以上实施例1、实施例2说明,控制适宜的制备条件,可以在不需加入控制晶核生长的添加剂的条件下制得粒径≤5μm球形碳酸钙微粉,从实施例1与实施例3的对比说明,产物浆液过滤后的滤液(氯化铵溶液)回收使用可以同样制得轻质碳酸钙微粉,因此滤液可以反复循环使用,进一步有效地降低制造成本。 The above Example 1, Example 2 described embodiment, the appropriate control preparation conditions, the particle size can be obtained at ≤5μm spherical calcium carbonate powder without addition of crystal nuclei growth control additives conditions from Example 1 and Example 3 comparative illustration, the filtrate (ammonium chloride solution) the product slurry was recovered by filtration using precipitated calcium carbonate powder can be prepared similarly, so the filtrate can be recycled repeatedly, the manufacturing cost is further effectively reduced. 而由实施例与对照例的比较说明,不适当的制备条件,或者得到立方形粗大颗粒,或者得到立方形颗粒与球形颗粒的混合物,但都难以得到粒径<5μm的球形碳酸钙微粉。 And the description of the Examples and Comparative Comparative Example embodiment, inappropriate manufacturing conditions, or coarse particles to obtain a cubic, or cuboidal particle to give a mixture of spherical particles but are difficult to obtain a particle size <5μm spherical fine powder of calcium carbonate. 而实施例1~3产物的组成、白度测定结果说明本方法制得了高纯度、高白度的碳酸钙微粉。 Which consists of the product of Examples 1 to 3, whiteness measurement result of the method described calcium carbonate powder was prepared in high purity and high whiteness. 以上结果表明,采用本方法-即由氯化铵溶液反应过滤纯化、无须使用添加剂、通过控制制备条件,可以由工业废弃物电石渣,高效率、低成本地制得高纯度、高白度的轻质碳酸钙微粉。 These results show that the method - i.e. the reaction of ammonium chloride was filtered from solution purification without the use of additives, by controlling the preparation conditions, carbide slag by industrial waste, high efficiency, low cost high purity, high whiteness, Ltd. light calcium carbonate powder.

Claims (8)

  1. 1.一种由电石渣制备高纯轻质碳酸钙微粉的方法,其特征在于以工业废弃物电石渣为原料,不经过高温预处理或分离杂质过程直接与氯化铵溶液反应将其转化为氯化钙与氨水的混合溶液,经过滤除去不溶物杂质后,在该氯化钙溶液中通入二氧化碳气体进行碳酸化反应,反应中不需加入添加剂,并基本在室温下通过控制适宜的制备条件以抑制晶粒生长,产物浆液过滤后,滤饼经水洗、烘干得到晶型为方解石的球型轻质碳酸钙微粉,粒度<5μm,而滤液则通过测定氯化铵浓度并适量补充氯化铵后用于下一次反应,实现氯化铵溶液的循环使用。 1. A process for preparing high-purity calcium carbonate powder carbide electrical, wherein the industrial waste carbide slag as raw material, a high temperature without pretreatment or separation of impurities during the reaction with ammonium chloride solution, which was converted directly to a mixed solution of calcium chloride with ammonia, the insoluble matter was filtered to remove impurities, the calcium chloride solution with carbon dioxide gas in the carbonation reaction, the reaction without addition of an additive, and substantially at room temperature is prepared by a suitable control conditions to inhibit grain growth, the product slurry was filtered, the filter cake was washed with water, dried to give crystal form of calcite type spherical calcium carbonate powder, particle size <5μm, and the filtrate is determined by the concentration and amount of added ammonium chloride a reaction for the ammonium, the ammonium chloride solution used for recycling.
  2. 2.根据权利要求1所述的一种由电石渣制备高纯轻质碳酸钙微粉的方法,其特征在于具体制备工艺过程和条件如下:(1)在首次制备时,将工业废弃物电石渣直接加入3~10倍的水混匀,按电石渣与氯化铵重量比为1∶1.0~1.6的比例在电石渣浆液中加入工业级氯化铵,在室温浸取或20~50℃条件下搅拌反应2~10小时,反应混合物溶液过滤除去不溶物渣滓后得到澄清碱性氯化钙溶液;(2)将碱性氯化钙溶液置于反应装置中,控制反应温度在室温或5~35℃之间,边搅拌边通入CO2与空气的混合气进行碳酸化反应,保持CO2气流量为0.1~4.0Lmin-1、空气流量为0.3~12.0Lmin-1、搅拌速率100~3000rpm,用pH计或pH试纸监测反应体系的pH值变化;(3)当反应体系pH值从强碱性降低至低于7.0时,即可结束反应,根据反应条件的不同,碳酸化反应速度不同,总碳酸化时间在5min~120min;(4)将反 According to one of the claim 1 prepared by the process of the carbide powder of high purity PCC electrically, characterized in that the preparation process and the specific conditions are as follows: (1) preparing the first time, the industrial waste carbide slag direct addition of water 3 to 10 times mix according carbide slag weight ratio of ammonium chloride to 1.6 1:1.0 industrial grade ammonium chloride was added carbide slag slurry, or leach conditions of 20 ~ 50 ℃ at room temperature reaction was stirred for 2 to 10 hours, the reaction mixture solution was filtered to remove insoluble matter to give a clear basic calcium scum solution; (2) the alkaline calcium chloride solution was placed in a reactor, at room temperature or controlling the reaction temperature ~ 5 between 35 ℃, stirring into CO2 and air mixture gas carbonation reaction, CO2 gas flow rate was maintained 0.1 ~ 4.0Lmin-1, air flow rate of 0.3 ~ 12.0Lmin-1, stirring rate 100 ~ 3000rpm, using pH values ​​pH paper or pH meter to monitor the reaction system; (3) when the pH of the reaction system was decreased from 7.0 to less than strongly basic, the reaction can, depending on the carbonation reaction speed different conditions, total carbonation time in 5min ~ 120min; (4) trans 应产物过滤,滤出固体产物用水洗涤2-3遍,再在60-100℃烘干便可得到轻质CaCO3粉状产品,还可在反应结束后采用硬脂酸、硬脂酸盐、钛酸酯偶联剂进行活化处理得到活性轻质碳酸钙产品;(5)将滤液回收,测定其中的氮含量,并由此确定浓缩后的滤液中氯化铵的浓度,根据需要补充少量水与氯化铵,调节滤液氯化铵溶液达到与首次制备时相同的体积和浓度;(6)在第二次及以后各次制备中,按(1)中相同的加入量将电石渣直接加入到调制后的滤液中,在与首次制备相同的条件下反应,反应混合物溶液过滤除去不溶物渣滓后继续进行上述(2)(3)(4)(5)过程,便可实现轻质碳酸钙微粉的生产与滤液的循环使用。 The product should be filtered, the solid product was filtered off and washed 2-3 times with water, and then dried at 60-100 deg.] C can be obtained a light powder product CaCO3, may be employed after the reaction of stearic acid, stearate, titanium coupling agent activation treatment to obtain an active light calcium carbonate; (5) the filtrate recovered, wherein the nitrogen content of the filtrate was determined, and thereby the concentrated ammonium chloride concentration, and add a small amount of water as needed ammonium chloride, ammonium chloride solution and the filtrate was adjusted to achieve the same when the volume and concentration of the first preparation; (6) in the second and each time after the preparation, the same amount of (1) was added directly to the carbide slag filtrate after modulation, prepared under the same conditions as the first reaction, the reaction proceeds (2) (3) (4) (5) during the above-described mixture solution and insoluble matter was filtered to remove the dross, can realize light calcium carbonate powder production and the filtrate recycled.
  3. 3.根据权利要求1所述的一种由电石渣制备高纯轻质碳酸钙微粉的方法,其特征在于直接与电石渣反应的氯化铵溶液中氯化铵的含量相对于电石渣中氢氧化钙含量以过量为宜。 According to one of the claim 1 prepared by the process of the carbide powder of high purity PCC electrically, characterized in that the solution is directly reacted with ammonium chloride in ammonium chloride carbide slag content of the electrically hydrogen carbide preferably calcium oxide content in excess.
  4. 4.根据权利要求1所述的一种由电石渣制备高纯轻质碳酸钙微粉的方法,其特征在于所述的碳酸化反应中由电石渣转化得到的碱性氯化钙溶液的浓度以2-15%为宜,最佳值的氯化钙溶液浓度为4-12%。 4. According to one of claim 1 prepared by the process as claimed in claim carbide powder of high purity PCC electrical, wherein the concentration of the alkaline carbonate calcium chloride solution obtained by the reaction of conversion to carbide slag preferably 2-15%, calcium chloride solution concentration of 4-12% of the optimal value.
  5. 5.根据权利要求1所述的一种由电石渣制备高纯轻质碳酸钙微粉的方法,其特征在于所述的碳酸化的反应温度以室温或5-35℃为宜,体系的反应升温低于30℃。 According to one of the claim 1 prepared by the process of the carbide powder of high purity PCC electrically, characterized in that the temperature of the carbonation reaction is preferably room temperature or at 5-35 deg.] C, the reaction system was raised below 30 ℃.
  6. 6.根据权利要求1所述的一种由电石渣制备高纯轻质碳酸钙微粉的方法,其特征在于所述的碳酸化中使用的二氧化碳气体为二氧化碳与空气的混合气体或工业生产中排出的二氧化碳废气,在混合气体或工业二氧化碳废气中,二氧化碳气体的浓度以20-80%为宜。 According to one of the claim 1 prepared by the process of the carbide powder of high purity PCC electrically, characterized in that the carbon dioxide gas used in the carbonation of industrial exhaust gas or carbon dioxide in the air carbon dioxide gas, mixed gas or industrial waste carbon dioxide, the concentration of carbon dioxide gas is preferably 20 to 80%.
  7. 7.根据权利要求1所述的一种由电石渣制备高纯轻质碳酸钙微粉的方法,其特征在于所述的碳酸化反应中二氧化碳气体的通入速度按纯CO2计算,通入速度以0.5-6Lmin-1L-1为宜。 According to one of the claim 1 prepared by the process of the carbide powder of high purity PCC electrically, characterized in that the speed of carbonation introduced into the reaction, calculated as pure carbon dioxide gas CO2, into speed 0.5-6Lmin-1L-1 is appropriate.
  8. 8.根据权利要求1所述的一种由电石渣制备高纯轻质碳酸钙微粉的方法,其特征在于所述碳酸化反应中搅拌速度在1升反应体系中,搅拌速度以500-3000转/分为宜。 According to one of the claim 1 prepared by the process of the carbide powder of high purity PCC electrically, characterized in that the carbonation reaction rate was stirred in 1 liter of the reaction system, stirring speed of 500-3000 rpm / into appropriate.
CN 200610031408 2006-03-27 2006-03-27 Process of preparing high purity light calcium carbonate fine powder with carbide residue CN101020579A (en)

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Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101823695A (en) * 2010-04-30 2010-09-08 汪晋强 Method for co-production of light calcium carbonate and ammonium chloride in preparation of potassium chlorate by carbide slag
CN101823745A (en) * 2010-04-30 2010-09-08 汪晋强 Method for producing super-fine light-weighted calcium carbonate, ammonium chloride and carbon powder with waste associated alkali solution and acetylene sludge
CN101823729A (en) * 2009-04-08 2010-09-08 王嘉兴 Method for preparing common-activity calcium carbonate series product and co-producing ammonia chloride
CN101920983A (en) * 2010-08-06 2010-12-22 东北大学 Method for recovering carbon dioxide and preparing calcium carbonate micropowder by utilizing converter slag
CN101362048B (en) 2008-09-02 2011-01-26 李发修;李发升;李翠萍 Method for absorbing carbon dioxide using carbide mud residue and special carbon dioxide absorber
CN102114383A (en) * 2011-01-18 2011-07-06 上海交通大学 Ammonia-chemical-chain-cycle-based carbon dioxide capture and conversion method
CN102303884A (en) * 2011-08-17 2012-01-04 山东益丰生化环保股份有限公司 Method for producing calcium carbonate by adopting thiourea waste residues and resolution gas from petroleum coking hydrogenation and hydrogen preparation apparatus as raw materials
CN102935329A (en) * 2012-11-29 2013-02-20 广东大众农业科技股份有限公司 Method and device for preparing light calcium carbonate by recycling exhaust gas of coal burning boiler
CN102992372A (en) * 2011-09-14 2013-03-27 现代自动车株式会社 Method for fixing carbon dioxide
CN103011209A (en) * 2011-09-23 2013-04-03 但建明 Ammonium chloride circulation method for producing magnesium hydroxide and calcium chloride from carbide slag and salt lake magnesium chloride
CN103170226A (en) * 2011-12-23 2013-06-26 杨晓林 New process for fixing carbon dioxide
CN103446868A (en) * 2013-08-28 2013-12-18 东北大学 Device for preparing calcium carbonate and recycling CO by collecting and mineralizing CO2 in aluminum electrolysis flue gas
CN103738997A (en) * 2013-12-17 2014-04-23 柳州东风化工股份有限公司 Method for preparing nano calcium carbonate by taking carbide slag as raw material
CN104310452A (en) * 2014-09-30 2015-01-28 武汉科技大学 Method for preparing light calcium carbonate by using LF refined waste residues
US20150307400A1 (en) * 2014-04-23 2015-10-29 Calera Corporation Methods and systems for utilizing carbide lime or slag

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101362048B (en) 2008-09-02 2011-01-26 李发修;李发升;李翠萍 Method for absorbing carbon dioxide using carbide mud residue and special carbon dioxide absorber
CN101823729A (en) * 2009-04-08 2010-09-08 王嘉兴 Method for preparing common-activity calcium carbonate series product and co-producing ammonia chloride
CN101823745A (en) * 2010-04-30 2010-09-08 汪晋强 Method for producing super-fine light-weighted calcium carbonate, ammonium chloride and carbon powder with waste associated alkali solution and acetylene sludge
CN101823695A (en) * 2010-04-30 2010-09-08 汪晋强 Method for co-production of light calcium carbonate and ammonium chloride in preparation of potassium chlorate by carbide slag
CN101920983B (en) 2010-08-06 2012-11-14 东北大学 Method for recovering carbon dioxide and preparing calcium carbonate micropowder by utilizing converter slag
CN101920983A (en) * 2010-08-06 2010-12-22 东北大学 Method for recovering carbon dioxide and preparing calcium carbonate micropowder by utilizing converter slag
CN102114383A (en) * 2011-01-18 2011-07-06 上海交通大学 Ammonia-chemical-chain-cycle-based carbon dioxide capture and conversion method
CN102114383B (en) 2011-01-18 2013-01-09 上海交通大学 Ammonia-chemical-chain-cycle-based carbon dioxide capture and conversion method
CN102303884A (en) * 2011-08-17 2012-01-04 山东益丰生化环保股份有限公司 Method for producing calcium carbonate by adopting thiourea waste residues and resolution gas from petroleum coking hydrogenation and hydrogen preparation apparatus as raw materials
CN102992372A (en) * 2011-09-14 2013-03-27 现代自动车株式会社 Method for fixing carbon dioxide
CN103011209A (en) * 2011-09-23 2013-04-03 但建明 Ammonium chloride circulation method for producing magnesium hydroxide and calcium chloride from carbide slag and salt lake magnesium chloride
CN103170226A (en) * 2011-12-23 2013-06-26 杨晓林 New process for fixing carbon dioxide
CN102935329A (en) * 2012-11-29 2013-02-20 广东大众农业科技股份有限公司 Method and device for preparing light calcium carbonate by recycling exhaust gas of coal burning boiler
CN103446868A (en) * 2013-08-28 2013-12-18 东北大学 Device for preparing calcium carbonate and recycling CO by collecting and mineralizing CO2 in aluminum electrolysis flue gas
CN103446868B (en) * 2013-08-28 2015-02-25 东北大学 Device for preparing calcium carbonate and recycling CO by collecting and mineralizing CO2 in aluminum electrolysis flue gas
CN103738997A (en) * 2013-12-17 2014-04-23 柳州东风化工股份有限公司 Method for preparing nano calcium carbonate by taking carbide slag as raw material
US20150307400A1 (en) * 2014-04-23 2015-10-29 Calera Corporation Methods and systems for utilizing carbide lime or slag
US9902652B2 (en) * 2014-04-23 2018-02-27 Calera Corporation Methods and systems for utilizing carbide lime or slag
CN104310452A (en) * 2014-09-30 2015-01-28 武汉科技大学 Method for preparing light calcium carbonate by using LF refined waste residues

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