WO2019051987A1 - 一种棒状沉淀碳酸钙的制备方法 - Google Patents

一种棒状沉淀碳酸钙的制备方法 Download PDF

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WO2019051987A1
WO2019051987A1 PCT/CN2017/110829 CN2017110829W WO2019051987A1 WO 2019051987 A1 WO2019051987 A1 WO 2019051987A1 CN 2017110829 W CN2017110829 W CN 2017110829W WO 2019051987 A1 WO2019051987 A1 WO 2019051987A1
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calcium carbonate
precipitated calcium
rod
reaction
shaped precipitated
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PCT/CN2017/110829
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English (en)
French (fr)
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莫英桂
朱勇
韦健毅
满治成
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广西华纳新材料科技有限公司
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Publication of WO2019051987A1 publication Critical patent/WO2019051987A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F11/00—Compounds of calcium, strontium, or barium
    • C01F11/18—Carbonates
    • C01F11/181—Preparation of calcium carbonate by carbonation of aqueous solutions and characterised by control of the carbonation conditions
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/12—Surface area

Definitions

  • the invention belongs to the technical field of inorganic materials, relates to precipitated calcium carbonate, and more particularly to a method for preparing a rod-shaped precipitated calcium carbonate using limestone as a raw material.
  • Calcium carbonate is an important inorganic filler widely used in plastics, rubber, paper and coatings. Calcium carbonate can be classified into heavy calcium carbonate and precipitated calcium carbonate depending on the method of calcium carbonate production. Heavy calcium carbonate is produced by mechanically pulverizing natural marble or limestone. Precipitated calcium carbonate is prepared by chemical precipitation crystallization. Depending on the reaction conditions, various forms of precipitated calcium carbonate can be obtained, such as rice grains, spindles, cubics, chains, flakes, spheres, and rods. There are three crystal phases of calcium carbonate: calcite, aragonite and vaterite. The rod-shaped precipitated calcium carbonate is generally an aragonite crystal phase.
  • the rod-shaped precipitated carbon calcium has some special application properties. Compared to the most widely used spindle-shaped precipitated calcium carbonate, the rod-like precipitated calcium carbonate has a high retention rate when used as a paper filler, improving paper bulk and printing suitability. Since the rod-shaped precipitated calcium carbonate is easy to bridge the papermaking fiber, the strength of the filling paper is reduced.
  • the rod-shaped precipitated calcium carbonate (aragonite structure) has a higher refractive index than other calcite calcium carbonate, and can be used as a paper coating to impart a higher hiding ratio and a printing color density.
  • Rod-shaped calcium carbonate can also be applied to plastic filling. Compared with other calcium carbonates with similar specific surface area, the rod-shaped precipitated calcium carbonate can give the product better processing fluidity, thermal stability, surface gloss, tensile/bending elastic modulus and Impact strength.
  • Patent CN105484099A discloses an aragonite-type light calcium composition for paper coating and a method for applying the same, preferably an aragonite-type light calcium having a particle size distribution of 0.5 to 2.3 um and a length to diameter ratio of 8 to 13, which may be substituted or reduced.
  • Patent WO 2009/009553 A1 discloses an aragonite-type precipitated calcium carbonate for a paper coating material, having an aragonite content of not less than 30%, and a calcium carbonate content of 2 um or more and a calcium carbonate content of less than or equal to 2 5% and less than or equal to 0.25 um.
  • the calcium content is less than 10%, which is used for paper coating to effectively improve the transparency, gloss, print gloss and brightness of the paper.
  • the carbonation method is the most important and mature industrial production method of precipitated calcium carbonate, that is, a carbon dioxide gas is introduced into a lime slurry (calcium hydroxide slurry) for precipitation crystallization.
  • the preparation of rod-shaped precipitated calcium carbonate by carbonation usually requires the addition of a crystal form controlling agent and/or seed crystal to the crystallization reaction mixture.
  • the crystal form controlling agent is mainly composed of inorganic compounds, and many applications include magnesium, antimony compounds and phosphoric acid/salts.
  • the carbonated (aragonite) precipitated calcium carbonate is prepared by a carbonation method, and magnesium chloride is an effective crystal form controlling agent, and the magnesium salt is relatively low in price.
  • magnesium chloride is used as a crystal form controlling agent, the problem of excessive use of magnesium chloride is ubiquitous, and it is difficult to remove impurities in the product. If the needle-shaped magnesium hydroxide and magnesium carbonate are used as the crystal form controlling agent, the crystal form controlling agent itself is not easily obtained.
  • the cerium-containing compound is also a commonly used crystal form controlling agent for preparing a rod-shaped (aragonite type) precipitated calcium carbonate by a carbonation method, and a high aragonite content product is often obtained.
  • the mechanism of action of the ruthenium-containing compound crystal form control agent is complicated, and the process conditions for the carbonation reaction are high, and different carbonation processes are required for applying different ruthenium-containing compounds.
  • the ruthenium-containing compound has a high price.
  • a high aragonite content precipitated calcium carbonate is usually prepared by using a ruthenium-containing compound as a crystal form controlling agent, and then the rod-shaped precipitated calcium carbonate is prepared in batches by using the seed crystal as a seed crystal.
  • Phosphoric acid/salt is also a commonly used crystal form control agent for the preparation of rod-shaped precipitated calcium carbonate by carbonation.
  • Other single crystal form control agents for the preparation of rod-shaped calcium carbonate by carbonation also include aluminum-containing compounds. Most of the additives are difficult to control the crystal form when used alone, or the effect is poor, so it is common to use two or more crystal form control agents in combination.
  • the carbonation method for preparing the rod-shaped precipitated calcium carbonate is also often added with seed crystals, that is, a certain amount of aragonite type/rod-like substance is introduced into the lime slurry as a seed crystal to prepare rod-shaped calcium carbonate before the carbonation reaction.
  • seed crystals that is, a certain amount of aragonite type/rod-like substance is introduced into the lime slurry as a seed crystal to prepare rod-shaped calcium carbonate before the carbonation reaction.
  • Preparation of rod-shaped precipitated calcium carbonate by adding seed crystals can effectively improve the rod carbon in the product
  • the calcium acid content controls the crystal form and solves the cost problem caused by using more crystal form control agents, but requires high crystal form or aragonite content of the seed crystal.
  • the aragonite phase/rod calcium carbonate content in the final product is often lower than the seed crystal.
  • the carbonation process is also the focus of research on the preparation of rod-shaped precipitated calcium carbonate by carbonation, such as lime digestion temperature, lime digestion ash/water ratio, lime slurry solid content, carbonation reaction initiation temperature, The reaction gas carbon dioxide concentration and the like.
  • Previous studies on carbonation process conditions have mostly been carried out on the basis of the addition of crystal form control agents or seed crystals.
  • no method has been used to prepare rod-shaped precipitated calcium carbonate by adjusting the preparation process without using any additives or seed crystals. Almost all relevant researchers believe that it is difficult to prepare a rod-shaped precipitated calcium carbonate without adding a crystal form controlling agent/seed.
  • rod-shaped precipitated calcium carbonate can be prepared by adding a crystal form controlling agent/seed seed.
  • the excessive use of the crystal form controlling agent or the excessive price may lead to an increase in product cost, and the preparation of the high aragonite content calcium carbonate seed crystal is also not easy.
  • the object of the present invention is to provide a method for preparing a rod-shaped precipitated calcium carbonate, thereby overcoming the disadvantages of preparing a crystal form calcium carbonate, adding a crystal form controlling agent and/or a seed crystal, and having high energy consumption and high cost.
  • the present invention provides a method for preparing a rod-shaped precipitated calcium carbonate, comprising the following steps:
  • Carbonation reaction the lime slurry of the step (1) is placed in a carbonation reaction tower, stirring is started, the temperature of the reaction system is controlled to be 40-80 ° C, and carbon dioxide is introduced into the mixed gas within 0-30 min before the reaction.
  • the concentration is 5-15 vol%
  • the flow rate is 2-4 m 3 /h
  • the concentration of carbon dioxide in the mixed gas at the end of the carbonation reaction is 25-40 vol%
  • the flow rate is 4-6 m 3 /h.
  • the limestone is calcined to obtain quicklime, and the quicklime and the water are mixed at a mass ratio of 1:4-10 and fully digested to obtain a lime slurry, and the lime slurry is sieved, and Adjust the lime slurry solids content to 10-20%.
  • the water temperature for digestion is 20-30 °C.
  • the lime slurry is sieved to pass through an 80 mesh sieve.
  • the limestone is crushed to a block size of 2-3 cm before the limestone is calcined.
  • the limestone calcination is calcined at a temperature of 1000-1450 ° C for 200-400 min to obtain quicklime.
  • the limestone calcination is calcined at a temperature of 1100-1300 ° C for 300-400 min to obtain quicklime.
  • the stirring speed in the pre-carbonation reaction in the step (2) is 100-300 r/min.
  • the stirring speed in the middle and late stages of the carbonation reaction in the step (2) is 300-600 r/min.
  • the dehydration drying in the step (3) is drying at a temperature of 100-120 ° C for 3-7 h.
  • the invention has the following beneficial effects: the preparation method of the rod-shaped precipitated calcium carbonate of the invention does not need to add a crystal form controlling agent and/or a seed crystal in the preparation process, and the rod shape can be prepared only by the control of the process.
  • Precipitated calcium carbonate can solve the problems of high cost and poor product quality caused by the use of the crystal form controlling agent in the prior art, and the problems of difficult seed crystal preparation and long process flow in the seed crystal method.
  • a is an X-ray diffraction pattern of the product of Example 1;
  • b is an X-ray diffraction pattern of the product of Example 2;
  • d is the X-ray diffraction pattern of the product of Example 4;
  • e is the X-ray diffraction pattern of the product of Example 5;
  • f is the X-ray diffraction pattern of the product of Comparative Example 1;
  • Figure 2 is a SEM photograph of the product obtained in Example 1 of the method for producing a rod-shaped precipitated calcium carbonate according to the present invention.
  • Figure 3 is a SEM photograph of a product prepared in Example 2 of the method for producing a rod-shaped precipitated calcium carbonate according to the present invention.
  • Figure 4 is a SEM photograph of the product obtained in Example 3 of the preparation method of the rod-shaped precipitated calcium carbonate according to the present invention.
  • Figure 5 is a SEM photograph of the product obtained in Example 4 of the preparation method of the rod-shaped precipitated calcium carbonate according to the present invention.
  • Figure 6 is a SEM photograph of a product prepared in Example 5 of the method for producing a rod-shaped precipitated calcium carbonate according to the present invention.
  • Figure 7 is a SEM photograph of the preparation of the rod-like precipitated calcium carbonate according to the present invention, prepared in Comparative Example 1.
  • the preparation method of the rod-shaped precipitated calcium carbonate is as follows: the limestone is crushed to a 2-3 cm block by a jaw crusher, and calcined at 1100 ° C for 400 minutes to obtain quicklime, and 2 kg of quicklime is discharged at a mass ratio of gray water of 1:4. After adding 25 ° C digested water and stirring for 20 min, the obtained lime milk was filtered through an 80 mesh vibrating sieve to remove the slag, and the lime emulsion solid content was adjusted to be 13.0%.
  • the obtained product had a specific surface area of 7.11 m 2 /g and an aragonite content of 74.88%.
  • the XRD pattern is shown in Fig. 1 (a), and the electron micrograph is shown in Fig. 2.
  • the preparation method of the rod-shaped precipitated calcium carbonate is as follows: the limestone is crushed to a block size of 2 to 3 cm by a jaw crusher, calcined at 1150 ° C for 350 minutes to obtain quicklime, and 2 kg of quicklime is discharged at a mass ratio of gray water of 1:6. After adding 25 ° C digested water and stirring for 15 min, the obtained lime milk was filtered through an 80 mesh vibrating sieve to remove the slag, and the lime emulsion solid content was adjusted to 15.3%.
  • the obtained product had a specific surface area of 7.56 m 2 /g and an aragonite content of 83.35%.
  • the XRD pattern is shown in Fig. 1 (b), and the electron micrograph is shown in Fig. 3.
  • the preparation method of the rod-shaped precipitated calcium carbonate is as follows: the limestone is crushed to a block size of 2 to 3 cm by a jaw crusher, and calcined at 1350 ° C for 300 minutes to obtain quicklime, and 2 kg of quicklime is discharged at a mass ratio of gray water of 1:7. After adding 25 ° C digested water and stirring for 20 min, the obtained lime milk was filtered through a 80 mesh vibrating sieve to remove the slag, and the lime emulsion solid content was adjusted to 19.5%.
  • control temperature is 70 ⁇ 75°C
  • control temperature is 70 ⁇ 75°C
  • start the reaction by introducing the mixed gas containing carbon dioxide, control 0
  • concentration of carbon dioxide in the mixed gas is 10%
  • the flow rate is 4m 3 /h in 30 minutes
  • the stirring rate is 600r/min when the reaction is 30 minutes
  • the carbon dioxide concentration is 20%
  • the flow rate is 4m 3 /h
  • the obtained product had a specific surface area of 6.84 m2/g and an aragonite content of 85.10%.
  • the XRD pattern is shown in Fig. 1(c), and the electron micrograph is shown in Fig. 4.
  • the preparation method of the rod-shaped precipitated calcium carbonate is as follows: the limestone is crushed to a block size of 2 to 3 cm by a jaw crusher, and calcined at 1200 ° C for 300 minutes to obtain quicklime, and 2 kg of quicklime is discharged at a mass ratio of gray water of 1:5. After adding 25 ° C digested water and stirring for 20 min, the obtained lime milk was filtered through an 80 mesh vibrating sieve to remove the slag, and the lime emulsion solid content was adjusted to 12.1%.
  • the obtained product has a specific surface area of 6.95 m 2 /g, an aragonite content of 79.42%, and an XRD pattern as shown in Fig. 1 (d). Electron micrographs are shown in Figure 4.
  • the preparation method of the rod-shaped precipitated calcium carbonate is as follows: the limestone is crushed to a block size of 2 to 3 cm by a jaw crusher, and calcined at 1400 ° C for 200 minutes to obtain quicklime, and 2 kg of quicklime is discharged at a mass ratio of gray water of 1:10. After adding 25 ° C digested water and stirring for 20 min, the obtained lime milk was filtered through a 80 mesh vibrating sieve to remove the slag, and the lime emulsion solid content was adjusted to be 11.0%.
  • the obtained product had a specific surface area of 7.12 m 2 /g and an aragonite content of 80.33%.
  • the XRD pattern is shown in Fig. 1 (e), and the electron micrograph is shown in Fig. 6.
  • the products of different examples and comparative examples were analyzed and compared.
  • the aragonite content of the rod-shaped precipitated calcium carbonate was analyzed by X-ray diffractometry (XRD), and the morphology was characterized by scanning electron microscopy (SEM).
  • the specific surface area was determined by BET specific surface area. Analyzer characterization.
  • the basic characterization information of the products of Examples 1-5 and Comparative Example 1 of the present invention is shown in Table 1.
  • the rod-like precipitated calcium carbonate can be prepared by using the preparation method of the present invention, and the aragonite content is 74.88-85.35%, and the specific surface area is 6.84 - 7.12 m 2 /g.
  • the calcium carbonate prepared in the comparative example was spindle-shaped, and there was no aragonite, and the specific surface area was 7.79 m 2 /g.
  • the preparation method using the rod-shaped precipitated calcium carbonate of the present invention is described, and it is not necessary to add a crystal form controlling agent and/or a seed crystal in the preparation process, and the rod-shaped precipitated calcium carbonate can be prepared only by the control of the process.

Abstract

一种棒状沉淀碳酸钙的制备方法，包括以下步骤：(1)制备石灰浆；(2)碳酸化反应：将石灰浆置入碳酸化反应塔中，开启搅拌，控制反应体系温度为40-80℃，反应前期0-30min内通入混合气体中二氧化碳的浓度为5-15vol％，流量为2-4m3/h，碳酸化反应后期通入混合气体中二氧化碳的浓度为25-40vol％，流量为4-6m3/h，当反应体系pH值达到7.5时停止通气，终止碳酸化反应，得到沉淀碳酸钙悬浮液；(3)脱水干燥：将沉淀碳酸钙悬浮液经脱水，干燥得到棒状沉淀碳酸钙。

Description

一种棒状沉淀碳酸钙的制备方法 技术领域
本发明属于无机材料技术领域，涉及沉淀碳酸钙，更准确地说，涉及以石灰石为原料的棒状沉淀碳酸钙的制备方法。
背景技术
碳酸钙是一种重要的无机填料，广泛应用于塑料、橡胶、造纸和涂料等领域。根据碳酸钙生产方法的不同，可以将碳酸钙分为重质碳酸钙和沉淀碳酸钙。重质碳酸钙经机械的方法直接粉碎天然的大理石或石灰石制得。沉淀碳酸钙经化学沉淀结晶制备。根据不同的反应条件，可获得多种形貌的沉淀碳酸钙，如米粒状、纺锤状、类立方状、链状、片状、球状和棒状等。碳酸钙的晶相有三种：方解石、文石和球霰石。棒状沉淀碳酸钙一般为文石晶相。
因为晶粒长径比较大，棒状沉淀碳钙具有一些特殊的应用性能。相对于应用最为广泛的纺锤形沉淀碳酸钙，棒状沉淀碳酸钙用作纸张填料时，具有较高的留着率，改善纸张松厚度和印刷适应性。因棒状沉淀碳酸钙易于和造纸纤维产生搭桥作用，填充纸张强度降低率较小。棒状沉淀碳酸钙(文石结构)比其他方解石碳酸钙具有更高的折光率，用作造纸涂料时可赋予纸张更高的遮盖率和印刷显色光密度。棒状碳酸钙还可应用于塑料填充，与比表面积相近的其他碳酸钙相比，棒状沉淀碳酸钙可赋予制品更好的加工流动性、热稳定性、表面光泽、拉伸/弯曲弹性模量和抗冲击强度。
用作纸张涂料时，棒状沉淀碳酸钙可在涂料中形成均匀的空隙，加快纸张的油墨吸收速度，有利于高速印刷，也可提高纸张厚度和光泽度，有望取代价格较高的高岭土。专利CN105484099A公开了一种用于纸张涂料的文石型轻钙组合物及其应用方法，优选粒子大小分布为0.5～2.3um，长径比8～13的文石型轻钙，可替代或减少纸张中的高岭土，提高铜版纸和白卡纸表面强度 和光泽度，在不影响涂布纸质量的情况下降低纸张涂料成本。专利WO2009/009553A1公开了一种用于纸张涂布材料的文石型沉淀碳酸钙，文石含量不小于30％，且粒径大于等于2um的碳酸钙含量小于4％，小于等于0.25um的碳酸钙含量小于10％，用于纸张涂布有效改善纸张的透明度，光泽，打印光泽和亮度。
碳酸化法是最重要和最成熟的沉淀碳酸钙工业生产方法，即在石灰浆(氢氧化钙料浆)中通入含二氧化碳气体进行沉淀结晶反应。采用碳酸化法制备棒状沉淀碳酸钙，通常需要在结晶反应混合物中加入晶型控制剂和/或晶种。晶型控制剂主要以无机化合物为主，应用较多的包括镁、锶化合物及磷酸/盐等。
碳酸化法制备棒状(文石型)沉淀碳酸钙，氯化镁是有效的晶型控制剂，且镁盐价格较低。但以氯化镁作晶型控制剂时普遍存在氯化镁用量过大的问题，在产物中难以除去成为杂质。若以针状氢氧化镁和碳酸镁作晶型控制剂，晶型控制剂本身不易得到。
含锶化合物也是碳酸化法制备棒状(文石型)沉淀碳酸钙常用的晶型控制剂，往往可得到高文石含量产物。但含锶化合物晶型控制剂作用机理复杂，对碳酸化反应工艺条件要求高，应用不同的含锶化合物需要不同的碳酸化工艺。含锶化合物价格较高，出于成本考虑，通常以含锶化合物作晶型控制剂制备高文石含量沉淀碳酸钙，再以此作晶种批量制备棒状沉淀碳酸钙。
磷酸/盐也是碳酸化法制备棒状沉淀碳酸钙常用的晶型控制剂。其它用于碳酸化法制备棒状碳酸钙的单一晶型控制剂还有含铝化合物。大多数添加剂单独使用时难以起晶型控制的作用，或效果较差，因此采用两种或两种以上晶型控制剂复合使用是常用办法。
除采用晶型控制剂外，碳酸化法制备棒状沉淀碳酸钙还常添加晶种，即碳酸化反应前在石灰浆中引入一定量的文石型/棒状物质作晶种制备棒状碳酸钙。采用添加晶种的方法制备棒状沉淀碳酸钙，可有效提高产物中棒状碳 酸钙含量，控制其结晶形态，同时可解决使用较多晶型控制剂导致的成本问题，但对晶种的结晶形态或文石含量要求高。最终产物中的文石相/棒状碳酸钙含量往往低于晶种。
除采用晶型控制剂和晶种外，碳酸化工艺也是碳酸化法制备棒状沉淀碳酸钙研究重点，如石灰消化温度，石灰消化灰/水比，石灰浆固含量，碳酸化反应起始温度，反应气体二氧化碳浓度等。以往对碳酸化工艺条件的研究多是在添加晶型控制剂或者晶种的基础上进行的。截至目前，不采用任何添加剂或晶种，仅仅通过调整制备工艺制备棒状沉淀碳酸钙的方法尚未见报道。几乎所有的相关研究者认为不添加晶型控制剂/晶种难以制备出棒状沉淀碳酸钙。
总的来说，通过添加晶型控制剂/晶种的方法可制备棒状沉淀碳酸钙。但就工业生产来说，晶型控制剂的用量过大或者价格过高都会导致产品成本上升，而高文石含量碳酸钙晶种的制备也很不容易。
公开于该背景技术部分的信息仅仅旨在增加对本发明的总体背景的理解，而不应当被视为承认或以任何形式暗示该信息构成已为本领域一般技术人员所公知的现有技术。
发明内容
本发明的目的在于提供一种棒状沉淀碳酸钙的制备方法，从而克服制备文石晶相碳酸钙需要加入晶型控制剂和/或晶种、能耗大、成本高的缺点。
为实现上述目的，本发明提供了一种棒状沉淀碳酸钙的制备方法，包括以下步骤：
(1)石灰石煅烧及生石灰的消化：制备得到石灰浆；
(2)碳酸化反应：将所述步骤(1)的石灰浆置入碳酸化反应塔中，开启搅拌，控制反应体系温度为40-80℃，反应前期0-30min内通入混合气体中二氧化碳的浓度为5-15vol％，流量为2-4m3/h，碳酸化反应后期通入混合气体 中二氧化碳的浓度为25-40vol％，流量为4-6m3/h，当反应体系pH值达到7.5时停止通气，终止碳酸化反应，得到沉淀碳酸钙悬浮液；
(3)脱水干燥：将所述步骤(2)得到沉淀碳酸钙悬浮液经脱水，干燥得到棒状沉淀碳酸钙。
优选地，上述技术方案中，所述步骤(1)中将石灰石进行煅烧后得到生石灰，将生石灰和水按质量比为1:4-10混合并充分消化得到石灰浆，石灰浆过筛，并调节石灰浆固含量至10-20％。
优选地，上述技术方案中，所述消化用的水温度为20-30℃。
优选地，上述技术方案中，所述石灰浆过筛为过80目筛。
优选地，上述技术方案中，对石灰石进行煅烧前，将石灰石破碎至2-3cm的块度。
优选地，上述技术方案中，所述石灰石煅烧是在1000-1450℃温度下煅烧200-400min得生石灰。
优选地，上述技术方案中，所述石灰石煅烧是在1100-1300℃温度下煅烧300-400min得生石灰。
优选地，上述技术方案中，所述步骤(2)中碳酸化反应前期的搅拌速度是100-300r/min。
优选地，上述技术方案中，所述步骤(2)中碳酸化反应中后期的搅拌速度是300-600r/min。
优选地，上述技术方案中，所述步骤(3)中的脱水干燥为在温度100-120℃的条件下干燥3-7h。
与现有技术相比，本发明具有如下有益效果：本发明棒状沉淀碳酸钙的制备方法，在制备过程中不需要添加晶型控制剂和/或晶种，仅通过工艺的控制即可制备棒状沉淀碳酸钙，可解决现有技术使用晶型控制剂导致的成本高和产品质量差的问题，以及晶种法中晶种制备困难，工艺流程长等问题。
附图说明
图1是根据不同棒状沉淀碳酸钙的制备方法制备得到产物的X射线衍射图谱；其中图中a为实施例1产物的X射线衍射图谱；b为实施例2产物的X射线衍射图谱；c为实施例3产物的X射线衍射图谱；d为实施例4产物的X射线衍射图谱；e为实施例5产物的X射线衍射图谱；f为对比例1产物的X射线衍射图谱；
图2是根据本发明的棒状沉淀碳酸钙的制备方法实施例1制备得到产物的SEM照片。
图3是根据本发明的棒状沉淀碳酸钙的制备方法实施例2制备得到产物的SEM照片。
图4是根据本发明的棒状沉淀碳酸钙的制备方法实施例3制备得到产物的SEM照片。
图5是根据本发明的棒状沉淀碳酸钙的制备方法实施例4制备得到产物的SEM照片。
图6是根据本发明的棒状沉淀碳酸钙的制备方法实施例5制备得到产物的SEM照片。
图7是根据本发明的棒状沉淀碳酸钙的制备方法对比例1制备得到产物的SEM照片。
具体实施方式
下面结合附图，对本发明的具体实施方式进行详细描述，但应当理解本发明的保护范围并不受具体实施方式的限制。
除非另有其它明确表示，否则在整个说明书和权利要求书中，术语“包括”或其变换如“包含”或“包括有”等等将被理解为包括所陈述的元件或组成部分，而并未排除其它元件或其它组成部分。
实施例1
棒状沉淀碳酸钙的制备方法，具体方法如下：将石灰石经颚式破碎机破 碎至2-3cm块度，在1100℃下煅烧400min得到生石灰，按1:4的灰水质量比将2kg生石灰一次性加入25℃消化水中，搅拌20min后，得到的石灰乳经80目振动筛过滤除渣，调节石灰乳固含量为13.0％。取20kg石灰乳，控制温度为55-60℃，并送入碳化塔内，开启搅拌，待体系温度达到50℃，调节搅拌速率为200r/min，通入含二氧化碳的混合气体开始反应，控制碳化反应0-20分钟内混合气体中二氧化碳的浓度为10％，流量为2m3/h，反应至20分钟时调整搅拌速率为500r/min，二氧化碳浓度为30％，流量为4m3/h，碳酸化至反应混合物pH为7.5即停止通入气体，终止碳酸化反应，得到沉淀碳酸钙悬浮液，经脱水、110℃条件下干燥5h后即得产物。
所得产物比表面积为7.11m2/g，文石含量为74.88％，XRD图谱见图1(a)，电镜照片见图2。
实施例2
棒状沉淀碳酸钙的制备方法，具体方法如下：将石灰石经颚式破碎机破碎至2～3cm块度，在1150℃下煅烧350min得到生石灰，按1:6的灰水质量比将2kg生石灰一次性加入25℃消化水中，搅拌15min后，得到的石灰乳经80目振动筛过滤除渣，调节石灰乳固含量为15.3％。取20kg石灰乳，控制温度为60-65℃，并送入碳化塔内，开启搅拌，待体系温度达到55℃，调节搅拌速率为100r/min，通入含二氧化碳的混合气体开始反应，控制0-20分钟内混合气体中二氧化碳的浓度为15％，流量为3m3/h，反应至20分钟时调整搅拌速率为300r/min，二氧化碳浓度为33％，流量为4m3/h，碳酸化至反应混合物pH为7.5即停止通入气体，终止碳酸化反应，得到沉淀碳酸钙悬浮液，经脱水、110℃条件下干燥5h后即得产物。
所得产物比表面积为7.56m2/g，文石含量为83.35％，XRD图谱见图1(b)，电镜照片见图3。
实施例3
棒状沉淀碳酸钙的制备方法，具体方法如下：将石灰石经颚式破碎机破碎至2～3cm块度，在1350℃下煅烧300min得到生石灰，按1:7的灰水质量比将2kg生石灰一次性加入25℃消化水中，搅拌20min后，得到的石灰乳经80目振动筛过滤除渣，调节石灰乳固含量为19.5％。取20kg石灰乳，控制温度为70～75℃，并送入碳化塔内，开启搅拌，待体系温度达到65℃，调节搅拌速率为300r/min，通入含二氧化碳的混合气体开始反应，控制0～30分钟内混合气体中二氧化碳的浓度为10％，流量为4m3/h，反应至30分钟时调整搅拌速率为600r/min，二氧化碳浓度为20％，流量为4m3/h，碳酸化至反应混合物pH为7.5即停止通入气体，终止碳酸化反应，得到沉淀碳酸钙悬浮液，经脱水、110℃条件下干燥5h后即得产物。
所得产物比表面积为6.84m2/g，文石含量为85.10％，XRD图谱见图1(c)，电镜照片见图4。
实施例4
棒状沉淀碳酸钙的制备方法，具体方法如下：将石灰石经颚式破碎机破碎至2～3cm块度，在1200℃下煅烧300min得到生石灰，按1:5的灰水质量比将2kg生石灰一次性加入25℃消化水中，搅拌20min后，得到的石灰乳经80目振动筛过滤除渣，调节石灰乳固含量为12.1％。取20kg石灰乳，控制温度为50～55℃，并送入碳化塔内，开启搅拌，待体系温度达到45℃，调节搅拌速率为200r/min，通入含二氧化碳的混合气体开始反应，控制0～30分钟内混合气体中二氧化碳的浓度为10％，流量为3m3/h，反应至20分钟时调整搅拌速率为300r/min，二氧化碳浓度为25％，流量为4m3/h，碳酸化至反应混合物pH为7.5即停止通入气体，终止碳酸化反应，得到沉淀碳酸钙悬浮液，经脱水、110℃条件下干燥5h后即得产物。
所得产物比表面积为6.95m2/g，文石含量为79.42％，XRD图谱见图1(d)， 电镜照片见图4。
实施例5
棒状沉淀碳酸钙的制备方法，具体方法如下：将石灰石经颚式破碎机破碎至2～3cm块度，在1400℃下煅烧200min得到生石灰，按1:10的灰水质量比将2kg生石灰一次性加入25℃消化水中，搅拌20min后，得到的石灰乳经80目振动筛过滤除渣，调节石灰乳固含量为11.0％。取20kg石灰乳，控制温度为75～80℃，并送入碳化塔内，开启搅拌，待体系温度达到70℃，调节搅拌速率为200r/min，通入含二氧化碳的混合气体开始反应，控制0～20分钟内混合气体中二氧化碳的浓度为8％，流量为3m3/h，反应至20分钟时调整搅拌速率为600r/min，二氧化碳浓度为28％，流量为5m3/h，碳酸化至反应混合物pH为7.5即停止通入气体，终止碳酸化反应，得到沉淀碳酸钙悬浮液，经脱水、110℃条件下干燥5h后即得产物。
所得产物比表面积为7.12m2/g，文石含量为80.33％，XRD图谱见图1(e)，电镜照片见图6。
对比例1
将石灰石破碎后，在950℃下煅烧200min得到生石灰，按1:5的灰水质量比将2kg生石灰一次性加入25℃消化水中消化得到的石灰乳经80目振动筛过滤除渣，调节石灰乳固含量为12.5％。取20kg石灰乳，控制温度为55～60℃，并送入碳化塔内，开启搅拌，待体系温度达到50℃，调节搅拌速率为500r/min，通入含二氧化碳的混合气体开始反应，混合气体中二氧化碳的浓度为30％，流量为5m3/h，碳酸化至反应混合物pH为7.5即停止通入气体，终止碳酸化反应，得到沉淀碳酸钙悬浮液，经脱水、干燥后即得产品。所得产物比表面积为7.79m2/g，无文石，XRD图谱见图1(f)，电镜照片见图6。
产物形状对比
对不同实施例和对比例的产物进行分析对比，棒状沉淀碳酸钙的文石含量由X射线衍射仪(XRD)测试后分析，形貌由扫描电子显微镜(SEM)表征，比表面积由BET比表面积分析仪表征。本发明实施例1-5与对比例1产物的基本表征信息见表1。
表1 不同实施例和对比例产物形状对比表
组别 文石含量 形貌 比表面积
实施例1 74.88％ 棒状 7.11
实施例2 83.35％ 棒状 7.56
实施例3 85.10％ 棒状 6.84
实施例4 79.42％ 棒状 6.95
实施例5 80.33％ 棒状 7.12
对比例1 0 纺锤状 7.79
如表1所示，使用本发明的制备方法能制备得到棒状的沉淀碳酸钙，文石含量达到74.88-85.35％，比表面积为6.84-7.12m2/g。而对比例制备得到的碳酸钙则成纺锤状，也就没有文石，比表面积为7.79m2/g。说明使用本发明棒状沉淀碳酸钙的制备方法，在制备过程中不需要添加晶型控制剂和/或晶种，仅通过工艺的控制即可制备棒状沉淀碳酸钙。
前述对本发明的具体示例性实施方案的描述是为了说明和例证的目的。这些描述并非想将本发明限定为所公开的精确形式，并且很显然，根据上述教导，可以进行很多改变和变化。对示例性实施例进行选择和描述的目的在于解释本发明的特定原理及其实际应用，从而使得本领域的技术人员能够实现并利用本发明的各种不同的示例性实施方案以及各种不同的选择和改变。本发明的范围意在由权利要求书及其等同形式所限定。

Claims (10)

  1. 一种棒状沉淀碳酸钙的制备方法，其特征在于，包括以下步骤：
    (1)石灰石煅烧及生石灰的消化：制备得到石灰浆；
    (2)碳酸化反应：将所述步骤(1)的石灰浆置入碳酸化反应塔中，开启搅拌，控制反应体系温度为40-80℃，反应前期0-30min内通入混合气体中二氧化碳的浓度为5-15vol％，流量为2-4m3/h，碳酸化反应后期通入混合气体中二氧化碳的浓度为25-40vol％，流量为4-6m3/h，当反应体系pH值达到7.5时停止通气，终止碳酸化反应，得到沉淀碳酸钙悬浮液；
    (3)脱水干燥：将所述步骤(2)得到沉淀碳酸钙悬浮液经脱水，干燥得到棒状沉淀碳酸钙。
  2. 根据权利要求1所述的棒状沉淀碳酸钙的制备方法，其特征在于，所述步骤(1)中将石灰石进行煅烧后得到生石灰，将生石灰和水按质量比为1:4-10混合并充分消化得到石灰浆，石灰浆过筛，并调节石灰浆固含量至10-20％。
  3. 根据权利要求2所述的棒状沉淀碳酸钙的制备方法，其特征在于，所述消化用的水温度为20-30℃。
  4. 根据权利要求2所述的棒状沉淀碳酸钙的制备方法，其特征在于，所述石灰浆过筛为过80目筛。
  5. 根据权利要求1所述的棒状沉淀碳酸钙的制备方法，其特征在于，对石灰石进行煅烧前，将石灰石破碎至2-3cm的块度。
  6. 根据权利要求1所述的棒状沉淀碳酸钙的制备方法，其特征在于，所述石灰石煅烧是在1000-1450℃温度下煅烧200-400min得生石灰。
  7. 根据权利要求1所述的棒状沉淀碳酸钙的制备方法，其特征在于，所述石灰石煅烧是在1100-1300℃温度下煅烧300-400min得生石灰。
  8. 根据权利要求1所述的棒状沉淀碳酸钙的制备方法，其特征在于，所述步骤(2)中碳酸化反应前期的搅拌速度是100-300r/min。
  9. 根据权利要求1所述的棒状沉淀碳酸钙的制备方法，其特征在于，所述步骤(2)中碳酸化反应中后期的搅拌速度是300-600r/min。
  10. 根据权利要求1所述的棒状沉淀碳酸钙的制备方法，其特征在于，所述步骤(3)中的脱水干燥为在温度100-120℃的条件下干燥3-7h。
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