CN114540957A - A kind of method that utilizes titanium dioxide waste acid and titanium gypsum to prepare calcium sulfate hemihydrate whiskers - Google Patents
A kind of method that utilizes titanium dioxide waste acid and titanium gypsum to prepare calcium sulfate hemihydrate whiskers Download PDFInfo
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- CN114540957A CN114540957A CN202210166438.1A CN202210166438A CN114540957A CN 114540957 A CN114540957 A CN 114540957A CN 202210166438 A CN202210166438 A CN 202210166438A CN 114540957 A CN114540957 A CN 114540957A
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- 229910052602 gypsum Inorganic materials 0.000 title claims abstract description 76
- 239000010440 gypsum Substances 0.000 title claims abstract description 76
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 59
- 239000010936 titanium Substances 0.000 title claims abstract description 59
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 59
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 46
- ZOMBKNNSYQHRCA-UHFFFAOYSA-J calcium sulfate hemihydrate Chemical compound O.[Ca+2].[Ca+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZOMBKNNSYQHRCA-UHFFFAOYSA-J 0.000 title claims abstract description 32
- 238000000034 method Methods 0.000 title claims abstract description 28
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 22
- 239000002253 acid Substances 0.000 title claims abstract description 21
- 239000002699 waste material Substances 0.000 title claims abstract description 21
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims abstract description 42
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000002002 slurry Substances 0.000 claims abstract description 19
- 239000013078 crystal Substances 0.000 claims abstract description 17
- 229910052742 iron Inorganic materials 0.000 claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- 238000009835 boiling Methods 0.000 claims abstract description 12
- 238000005054 agglomeration Methods 0.000 claims abstract description 8
- 230000002776 aggregation Effects 0.000 claims abstract description 8
- 238000003756 stirring Methods 0.000 claims abstract description 8
- 230000003287 optical effect Effects 0.000 claims abstract description 3
- 235000011187 glycerol Nutrition 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 6
- 239000006210 lotion Substances 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- 238000001914 filtration Methods 0.000 abstract description 2
- IXQWNVPHFNLUGD-UHFFFAOYSA-N iron titanium Chemical compound [Ti].[Fe] IXQWNVPHFNLUGD-UHFFFAOYSA-N 0.000 abstract description 2
- 238000005406 washing Methods 0.000 abstract description 2
- 235000010215 titanium dioxide Nutrition 0.000 description 17
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 15
- 239000000843 powder Substances 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- 238000001035 drying Methods 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 5
- 238000012876 topography Methods 0.000 description 5
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 4
- 238000003828 vacuum filtration Methods 0.000 description 4
- 238000010586 diagram Methods 0.000 description 3
- 238000010298 pulverizing process Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 238000007873 sieving Methods 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 229910001629 magnesium chloride Inorganic materials 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical group [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- GZHZKHYXEODHJF-UHFFFAOYSA-N acetic acid;azane Chemical compound N.N.N.CC(O)=O.CC(O)=O.CC(O)=O GZHZKHYXEODHJF-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 235000011116 calcium hydroxide Nutrition 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000007952 growth promoter Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
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- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/10—Inorganic compounds or compositions
- C30B29/46—Sulfur-, selenium- or tellurium-containing compounds
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/60—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape characterised by shape
- C30B29/62—Whiskers or needles
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- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B7/00—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions
- C30B7/14—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions the crystallising materials being formed by chemical reactions in the solution
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Abstract
本发明中公开了一种利用钛白废酸和钛石膏制备半水硫酸钙晶须的方法，包括以下步骤：利用钛白废酸去除钛石膏中的铁，制得除铁钛石膏；向除铁钛石膏中加入丙三醇溶液，转移至三颈烧瓶中升温至103℃～105℃保温30min，转速400r/min，直至出现料浆结块；向料浆结块中加入75ml沸水搅拌至结块完全分散，保温60mim，取样于光学显微镜下观察，待板状石膏晶体全部消失时，停止反应，过滤洗涤得到半水硫酸钙晶须。本发明制备出超长长径比的半水硫酸钙晶须，其长径比可达90～180，显著提高了半水硫酸钙晶须的长径比，具有更广泛的应用范围；而且有效提高了生产效率和生产安全性。
The invention discloses a method for preparing calcium sulfate hemihydrate whiskers by using titanium dioxide waste acid and titanium gypsum, comprising the following steps: removing iron in titanium gypsum by using titanium dioxide waste acid to prepare iron-removing titanium gypsum; Add glycerol solution to the iron-titanium gypsum, transfer it to a three-necked flask and heat up to 103 ℃ ~ 105 ℃ for 30 minutes, rotating speed 400r/min, until the slurry agglomerates; add 75ml of boiling water to the slurry agglomeration and stir until it forms The pieces were completely dispersed, kept at a temperature of 60 mm, and sampled for observation under an optical microscope. When all the plate-like gypsum crystals disappeared, the reaction was stopped, and the calcium sulfate hemihydrate whiskers were obtained by filtration and washing. The invention prepares calcium sulfate hemihydrate whiskers with an ultra-long aspect ratio, and the aspect ratio can reach 90-180, which significantly improves the aspect ratio of the calcium sulfate hemihydrate whiskers, and has a wider application range; and effectively Improve production efficiency and production safety.
Description
技术领域technical field
本发明涉及石膏晶须制备技术领域，具体涉及一种利用钛白废酸和钛石膏制备半水硫酸钙晶须的方法。The invention relates to the technical field of preparation of gypsum crystal whiskers, in particular to a method for preparing calcium sulfate hemihydrate crystal whiskers by utilizing titanium dioxide waste acid and titanium gypsum.
背景技术Background technique
钛石膏和钛白废酸是钛白粉生产过程中常见的副产物，钛石膏一般做堆积处理，既占地方又污染环境，此方法能对工业副产物进行回收再利用，有利于环境治理，提高企业经济利益。针对钛石膏，最有应用潜力的是制备半水硫酸钙晶须(石膏晶须)，超高长径比的石膏晶须可以用于造纸工业、水泥、橡胶等。但是，要制备石膏晶须，杂质铁是一大障碍，研究表明，铁的存在会降低硫酸钙晶须的长径比。因此，利用钛石膏制备硫酸钙晶须之前，需要对红棕色的钛石膏进行除铁得到白色的除铁钛石膏。Titanium gypsum and titanium dioxide waste acid are common by-products in the production process of titanium dioxide. Titanium gypsum is generally piled up, which takes up space and pollutes the environment. This method can recycle industrial by-products, which is conducive to environmental governance and improves the corporate economic interests. For titanium gypsum, the most potential application is the preparation of calcium sulfate hemihydrate whiskers (gypsum whiskers). However, the impurity iron is a major obstacle to the preparation of gypsum whiskers, and studies have shown that the presence of iron reduces the aspect ratio of calcium sulfate whiskers. Therefore, before using titanium gypsum to prepare calcium sulfate whiskers, it is necessary to remove iron from reddish-brown titanium gypsum to obtain white iron-removed titanium gypsum.
甘永乐等人以钛白废酸和石灰为原料制备钛白石膏，再以钛白石膏为原料，通过水热合成法制备硫酸钙晶须，考察反应温度、反应时间、搅拌速度、料浆浓度等因素对硫酸钙晶须形貌的影响，实验结果表明，在反应温度为120℃、反应时间为60min、搅拌速度为70rpm和料浆浓度为4％条件下，制备得到的产物形貌较为良好。此方法需要在较高温度或压强下完成，能耗较高，且对反应装置密闭性等方面的要求较高。Gan Yongle et al. used titanium dioxide waste acid and lime as raw materials to prepare titanium dioxide gypsum, and then used titanium white gypsum as raw material to prepare calcium sulfate whiskers by hydrothermal synthesis method, and investigated the reaction temperature, reaction time, stirring speed, and slurry concentration. The influence of other factors on the morphology of calcium sulfate whiskers, the experimental results show that under the conditions of reaction temperature of 120 °C, reaction time of 60 min, stirring speed of 70 rpm and slurry concentration of 4%, the morphology of the prepared product is relatively good. . This method needs to be completed at higher temperature or pressure, has higher energy consumption, and has higher requirements on the airtightness of the reaction device.
Yang等在3％K2SO4(质量分数)溶液中反应60min，制备出直径为1～5μm，长径比为50～80的HH晶须。目前，常压盐溶液法虽不需要在高压设备下进行，但制备工艺较复杂，过程难控制，且盐类主要选取氯盐与硫酸盐，对反应设备会产生较大的腐蚀性。Yang et al. reacted in a 3% K 2 SO 4 (mass fraction) solution for 60 min to prepare HH whiskers with a diameter of 1-5 μm and an aspect ratio of 50-80. At present, although the normal pressure salt solution method does not need to be carried out under high pressure equipment, the preparation process is complicated, the process is difficult to control, and the salts are mainly chlorides and sulfates, which will cause greater corrosiveness to the reaction equipment.
专利号CN112342624，将二水硫酸钙在60～80℃下溶解，过滤，滤液冷却结晶，洗涤、干燥得到制得二水硫酸钙晶须。该方法包括向每升盐酸中加入0.12～0.21摩尔二水合硫酸钙。还包括在溶解过程中加入结晶促进剂，结晶促进剂包括氯化镁，氯化镁的加入量为每升盐酸0.01～0.02摩尔。二水硫酸钙是通过从钛石膏中除去游离水制备的。此方法制的二水硫酸钙晶须，性能不如半水。Patent No. CN112342624, calcium sulfate dihydrate crystal whiskers are obtained by dissolving calcium sulfate dihydrate at 60-80° C., filtering, cooling and crystallizing the filtrate, washing and drying. The method includes adding 0.12-0.21 moles of calcium sulfate dihydrate per liter of hydrochloric acid. It also includes adding a crystallization accelerator during the dissolving process. The crystallization accelerator includes magnesium chloride, and the amount of magnesium chloride added is 0.01-0.02 moles per liter of hydrochloric acid. Calcium sulfate dihydrate is prepared by removing free water from titanium gypsum. The calcium sulfate dihydrate whiskers prepared by this method are not as good as hemihydrate.
专利号CN109161971A，在钛石膏提纯中，用1～5mol L-1盐酸溶解，过滤，调节溶液的pH值，沉淀出纯白色钛石膏。水热反应时间为6～12小时，温度为120～130℃。得到的硫酸钙晶须长径比为40～60。优选成分：纯白钛石膏浆的质量分数为2.5～5％。外加剂为甘油，甘油的体积为浆液体积的10～30％。晶体生长促进剂为摩尔浓度为0.01～0.1mol/l的磺酸镁。此方法水热时间过长，温度过高，能耗大，制得的晶须长径比也不够长。Patent No. CN109161971A, in the purification of titanium gypsum, dissolve with 1-5mol L-1 hydrochloric acid, filter, adjust the pH value of the solution, and precipitate pure white titanium gypsum. The hydrothermal reaction time is 6 to 12 hours, and the temperature is 120 to 130°C. The obtained calcium sulfate whiskers have an aspect ratio of 40-60. Preferred components: the mass fraction of pure white titanium gypsum slurry is 2.5-5%. The admixture is glycerol, and the volume of glycerin is 10-30% of the volume of the slurry. The crystal growth promoter is magnesium sulfonate with a molar concentration of 0.01 to 0.1 mol/l. In this method, the hydrothermal time is too long, the temperature is too high, the energy consumption is large, and the aspect ratio of the obtained whisker is not long enough.
专利号CN111270312A，钛石膏经过浓盐酸净化，后通过贝壳熟石灰调PH至7，过滤得清液1，加入混合转晶剂(3g硫酸钠+4ml三乙酸铵+4ml丙三醇)，混合液置于密封于真空干燥箱(140℃，4h)，长径比40～90。此方法用到浓盐酸净化和复杂成分的转晶剂。Patent No. CN111270312A, titanium gypsum is purified by concentrated hydrochloric acid, and then adjusted to pH 7 by shell slaked lime, filtered to obtain clear liquid 1, and mixed crystallizer (3g sodium sulfate + 4ml ammonium triacetate + 4ml glycerol) was added, and the mixed solution was placed It is sealed in a vacuum drying oven (140°C, 4h), with an aspect ratio of 40 to 90. This method uses concentrated hydrochloric acid for purification and complex composition of crystallizers.
以上现有的方法操作步骤复杂、对温度、压强等反应条件要求较高，而且制备的石膏晶须的长径比较短。The above existing method has complicated operation steps, high requirements on reaction conditions such as temperature and pressure, and the length and diameter of the prepared gypsum whiskers are relatively short.
发明内容SUMMARY OF THE INVENTION
本发明的目的在于解决现有技术存在的以上问题，提供一种利用钛白废酸和钛石膏制备半水硫酸钙晶须的方法，步骤简单，仅在常压下反应1-2h就能制备得到长径比为90～180的半水硫酸钙晶须。The object of the present invention is to solve the above problems existing in the prior art, and to provide a method for preparing calcium sulfate hemihydrate whiskers by utilizing titanium dioxide waste acid and titanium gypsum. Calcium sulfate hemihydrate whiskers with an aspect ratio of 90-180 were obtained.
为解决上述技术问题，本发明采用的技术方案如下：一种利用钛白废酸和钛石膏制备半水硫酸钙晶须的方法，包括以下步骤：In order to solve the above-mentioned technical problems, the technical scheme adopted in the present invention is as follows: a method for preparing calcium sulfate hemihydrate crystal whiskers by utilizing titanium dioxide waste acid and titanium gypsum, comprising the following steps:
S1、利用钛白废酸去除钛石膏中的铁，制得除铁钛石膏；S1, utilize titanium dioxide waste acid to remove iron in titanium gypsum to obtain iron-removing titanium gypsum;
S2、向除铁钛石膏中加入丙三醇溶液，转移至三颈烧瓶中升温至103℃～105℃保温30min，转速400r/min，直至出现料浆结块；S2, add glycerol solution to the iron-removing titanium gypsum, transfer to a three-necked flask and heat up to 103 ℃ ~ 105 ℃ for 30min, rotating speed 400r/min, until slurry agglomeration occurs;
S3、向料浆结块中加入75ml沸水搅拌至结块完全分散，保温60mim，取样于光学显微镜下观察，待板状石膏晶体全部消失时，停止反应，过滤洗涤得到半水硫酸钙晶须。S3, add 75ml boiling water to the slurry agglomeration and stir until the agglomeration is completely dispersed, keep the temperature for 60mim, take a sample and observe it under an optical microscope, when the plate-shaped gypsum crystals all disappear, stop the reaction, filter and wash to obtain calcium sulfate hemihydrate crystal whiskers.
优选地，所述S1中将钛白废酸加入三颈烧瓶中于水浴锅中预热到70℃，再加入粒径为75～150μm的钛石膏混合均匀，反应1-2h，真空抽滤，用沸水洗至洗液无色，再用无水乙醇固定，干燥12h后得到除铁钛石膏。Preferably, in said S1, titanium dioxide waste acid is added to a three-necked flask, preheated to 70° C. in a water bath, and then titanium gypsum with a particle size of 75-150 μm is added to mix evenly, react for 1-2 hours, and vacuum filtration. Wash with boiling water until the lotion is colorless, then fix with absolute ethanol, and dry for 12 hours to obtain iron-removing titanium gypsum.
优选地，所述S1中，钛石膏与钛白废酸的质量比为1:5。Preferably, in the S1, the mass ratio of titanium gypsum to titanium dioxide waste acid is 1:5.
优选地，所述S1中制得的除铁钛石膏为白色，所述除铁钛石膏中铁含量小于4％。Preferably, the iron-removing titanium gypsum prepared in the S1 is white, and the iron content in the iron-removing titanium gypsum is less than 4%.
优选地，所述S2中丙三醇溶液与除铁钛石膏的液固比为9:1。Preferably, the liquid-solid ratio of the glycerol solution and the iron-removing titanium gypsum in the S2 is 9:1.
进一步优选，所述S2中丙三醇溶液的浓度为40wt％～50wt％。Further preferably, the concentration of the glycerin solution in the S2 is 40wt% to 50wt%.
进一步优选，所述S2中升温速率为6℃/min。Further preferably, the heating rate in the S2 is 6°C/min.
更进一步优选，所述S3中制备的半水硫酸钙晶须的长径比为90～180。More preferably, the aspect ratio of the calcium sulfate hemihydrate whiskers prepared in the S3 is 90-180.
本发明所具有的有益效果：The beneficial effects that the present invention has:
一)本发明采用钛白废酸除去钛石膏中的铁，再利用醇水法制备半水硫酸钙晶须，并用沸水洗去多余的醇，阻止半水硫酸钙晶须水化，从而制备出超长长径比的半水硫酸钙晶须，其长径比可达90～180，显著提高了半水硫酸钙晶须的长径比，具有更广泛的应用范围；1) The present invention adopts titanium dioxide waste acid to remove iron in the titanium gypsum, and then utilizes the alcohol-water method to prepare calcium sulfate hemihydrate whiskers, and washes off excess alcohol with boiling water to prevent the hydration of calcium sulfate hemihydrate whiskers, thereby preparing Calcium sulfate hemihydrate whiskers with ultra-long aspect ratio can reach 90 to 180, which significantly improves the aspect ratio of calcium sulfate hemihydrate whiskers and has a wider range of applications;
二)本发明中制备工艺步骤简单，且反应条件温和，无需高压条件，仅在常压下反应1-2h就能制得长径比为90～180的半水硫酸钙晶须，有效提高了生产效率和生产安全性，并且节约能源。2) in the present invention, the preparation process steps are simple, and the reaction conditions are mild, no high pressure conditions are required, and the calcium sulfate hemihydrate whiskers with an aspect ratio of 90 to 180 can be obtained only by reacting under normal pressure for 1-2 h, which effectively improves the Production efficiency and production safety, and energy savings.
附图说明Description of drawings
图1为本发明中制备半水硫酸钙晶须的步骤流程图；Fig. 1 is the step flow chart of preparing calcium sulfate hemihydrate crystal whisker in the present invention;
图2为本发明中实施例1制备的半水硫酸钙晶须的形貌图；Fig. 2 is the topography of the calcium sulfate hemihydrate crystal whisker prepared in Example 1 of the present invention;
图3为本发明中实施例2制备的半水硫酸钙晶须的形貌图；Fig. 3 is the topography of the calcium sulfate hemihydrate crystal whisker prepared in Example 2 of the present invention;
图4为本发明中实施例3制备的半水硫酸钙晶须的形貌图；Fig. 4 is the topography of the calcium sulfate hemihydrate crystal whisker prepared in Example 3 of the present invention;
图5为本发明中对比例1制备的石膏形貌图；Fig. 5 is the gypsum topography figure prepared by comparative example 1 in the present invention;
图6为本发明中对比例2制备的石膏形貌图；Fig. 6 is the gypsum topography figure prepared by comparative example 2 in the present invention;
图7为本发明中对比例2的料浆和实施例1的料浆对比图(图7-A为对比例2的料浆图；图7-B为实施例1的料浆图)。Fig. 7 is a comparison diagram of the slurry of Comparative Example 2 and the slurry of Example 1 in the present invention (Fig. 7-A is the slurry diagram of Comparative Example 2; Fig. 7-B is the slurry diagram of Example 1).
具体实施方式Detailed ways
下面结合附图和具体实施例对本发明作进一步的说明。The present invention will be further described below with reference to the accompanying drawings and specific embodiments.
实施例1Example 1
如附图1所示，将红棕色的钛石膏进行烘干、粉碎和过筛的预处理，得到粒径为75μm的钛石膏粉，将400g钛白废酸加入三颈烧瓶中于水浴锅中预热到70℃，再加入80g钛石膏粉末混合均匀，反应2h，真空抽滤，用沸水洗至洗液无色，再用无水乙醇固定，干燥12h后研磨过筛得到铁含量为3.83％的除铁钛石膏粉。As shown in accompanying drawing 1, carry out the pretreatment of drying, pulverizing and sieving the reddish-brown titanium gypsum to obtain titanium gypsum powder with a particle size of 75 μm, adding 400g of titanium white waste acid to a three-necked flask and placing it in a water bath. Preheat to 70°C, then add 80g of titanium gypsum powder to mix evenly, react for 2 hours, vacuum filter, wash with boiling water until the lotion is colorless, then fix with absolute ethanol, dry for 12 hours, grind and sieve to obtain an iron content of 3.83% of iron-removing titanium gypsum powder.
取上述除铁钛石膏粉11g与100g40wt％丙三醇溶液放入三颈烧瓶充分混合，除铁钛石膏粒度为100目；20分钟加热至103度，保温30分钟，转速400r/min，出现料浆结块；向三颈烧瓶中加入75ml沸水搅拌至结块完全分散成质地均匀的料浆(图7-B所示)，继续保温60分钟；用电子显微镜取样观察，待板状石膏完全转换为晶须时(如图2所示)，停止反应；真空抽滤，用无水乙醇冲洗后放置恒温干燥箱12小时制得半水硫酸钙晶须。Take 11g of the above-mentioned iron-removing titanium gypsum powder and 100g of 40wt% glycerol solution and put it into a three-necked flask to fully mix, and the particle size of iron-removing titanium gypsum is 100 mesh; heat to 103 degrees in 20 minutes, keep warm for 30 minutes, and rotate at 400r/min, and the material appears Slurry agglomerates; add 75ml of boiling water to the three-necked flask and stir until the agglomerates are completely dispersed into a slurry with a uniform texture (as shown in Figure 7-B), and continue to keep warm for 60 minutes; take samples and observe with an electron microscope, and wait until the plate gypsum is completely converted When it is a whisker (as shown in Figure 2), stop the reaction; vacuum filtration, rinse with absolute ethanol, place it in a constant temperature drying oven for 12 hours to obtain calcium sulfate hemihydrate crystal whisker.
实施例2Example 2
如附图1所示，将红棕色的钛石膏进行烘干、粉碎和过筛的预处理，得到粒径为150μm的钛石膏粉，将400g钛白废酸加入三颈烧瓶中于水浴锅中预热到70℃，再加入80g钛石膏粉末混合均匀，反应1h，真空抽滤，用沸水洗至洗液无色，再用无水乙醇固定，干燥12h后研磨过筛得到铁含量为3.22％的除铁钛石膏粉。As shown in accompanying drawing 1, carry out the pretreatment of drying, pulverizing and sieving the reddish-brown titanium gypsum to obtain titanium gypsum powder with a particle size of 150 μm, adding 400 g of titanium dioxide waste acid to a three-necked flask and placing it in a water bath. Preheat to 70°C, then add 80g of titanium gypsum powder and mix evenly, react for 1 hour, vacuum filter, wash with boiling water until the lotion is colorless, then fix with absolute ethanol, dry for 12 hours, grind and sieve to obtain an iron content of 3.22% of iron-removing titanium gypsum powder.
取上述除铁钛石膏粉11g与100g50wt％丙三醇溶液放入三颈烧瓶充分混合，除铁钛石膏粒度为100目；20分钟加热至105度，保温30分钟，转速400r/min，出现料浆结块；向三颈烧瓶中加入75ml沸水搅拌至结块完全分散，继续保温60分钟；用电子显微镜取样观察，待板状石膏完全转换为晶须时(如图3所示)，停止反应；真空抽滤，用无水乙醇冲洗后放置恒温干燥箱12小时制得半水硫酸钙晶须。Take 11 g of the above-mentioned iron-removing titanium gypsum powder and 100g of 50wt% glycerol solution and put it into a three-necked flask to fully mix, and the particle size of iron-removing titanium gypsum is 100 mesh; heat to 105 degrees in 20 minutes, keep warm for 30 minutes, and rotate at 400 r/min. Slurry agglomerates; add 75ml of boiling water to the three-necked flask and stir until the agglomerates are completely dispersed, and continue to keep the temperature for 60 minutes; take samples and observe with an electron microscope, when the plate gypsum is completely converted into whiskers (as shown in Figure 3), stop the reaction ; Vacuum filtration, rinse with absolute ethanol and place in a constant temperature drying oven for 12 hours to obtain calcium sulfate hemihydrate whiskers.
实施例3Example 3
如附图1所示，将红棕色的钛石膏进行烘干、粉碎和过筛的预处理，得到粒径为100μm的钛石膏粉，将400g钛白废酸加入三颈烧瓶中于水浴锅中预热到70℃，再加入80g钛石膏粉末混合均匀，反应1.5h，真空抽滤，用沸水洗至洗液无色，再用无水乙醇固定，干燥12h后研磨过筛得到铁含量为3.64％的除铁钛石膏粉。As shown in accompanying drawing 1, carry out the pretreatment of drying, pulverizing and sieving the reddish-brown titanium gypsum to obtain titanium gypsum powder with a particle size of 100 μm, adding 400 g of titanium dioxide waste acid to a three-necked flask and placing it in a water bath. Preheat to 70°C, then add 80g of titanium gypsum powder to mix evenly, react for 1.5h, vacuum filter, wash with boiling water until the lotion is colorless, then fix with absolute ethanol, dry for 12h, grind and sieve to obtain an iron content of 3.64 % of iron-removing titanium gypsum powder.
取上述除铁钛石膏粉11g与100g45wt％丙三醇溶液放入三颈烧瓶充分混合，除铁钛石膏粒度为100目；20分钟加热至104度，保温30分钟，转速400r/min，出现料浆结块；向三颈烧瓶中加入75ml沸水搅拌至结块完全分散，继续保温60分钟；用电子显微镜取样观察，待板状石膏完全转换为晶须时(如图4所示)，停止反应；真空抽滤，用无水乙醇冲洗后放置恒温干燥箱12小时制得半水硫酸钙晶须。Take 11g of the above-mentioned iron-removing titanium gypsum powder and 100g of 45wt% glycerol solution and put it into a three-necked flask to fully mix, and the particle size of iron-removing titanium gypsum is 100 mesh; heat to 104 degrees in 20 minutes, keep warm for 30 minutes, and rotate at 400r/min. Slurry agglomerates; add 75ml of boiling water to the three-necked flask and stir until the agglomerates are completely dispersed, and continue to be incubated for 60 minutes; take samples and observe with an electron microscope, when the plate gypsum is completely converted into whiskers (as shown in Figure 4), stop the reaction ; Vacuum filtration, rinse with absolute ethanol and place in a constant temperature drying oven for 12 hours to obtain calcium sulfate hemihydrate whiskers.
对比例1Comparative Example 1
以未除铁钛石膏为原料，加入丙三醇溶液，液固比为9，于105℃下反应2h，取样于电子显微镜下观察，未出现半水硫酸钙晶须(如图5所示)。Using unremoved iron-titanium gypsum as raw material, adding glycerol solution, the liquid-solid ratio is 9, and reacting at 105 ° C for 2 hours, taking samples and observing under an electron microscope, no calcium sulfate hemihydrate whiskers appear (as shown in Figure 5) .
对比例2Comparative Example 2
以除铁钛石膏为例，加入丙三醇溶液，液固比为9，于105℃下反应30min，料浆结块严重(如图7-A所示)，类似水分蒸干，取样于电子显微镜下观察，块状石膏未完全转化为晶须(如图6所示)，但已无法继续反应。Taking iron-removing titanium gypsum as an example, add glycerol solution, the liquid-solid ratio is 9, and react at 105 ° C for 30 minutes, the slurry agglomerates seriously (as shown in Figure 7-A), similar to the water evaporated to dryness, and the sample is taken in the electronic Observed under the microscope, the massive gypsum was not completely transformed into whiskers (as shown in Figure 6), but the reaction could no longer be continued.
表1-本发明与对比例制备的半水硫酸钙晶须的长径比数据对比表Table 1-the aspect ratio data comparison table of the calcium sulfate hemihydrate whiskers prepared by the present invention and comparative example
表2-本发明中钛白废酸除铁的除铁率数据表Table 2-the iron removal rate data table of titanium dioxide waste acid iron removal in the present invention
表2数据表明，本发明采用钛白废酸可以高效除去钛石膏中的铁，获得含铁率低于4％的钛石膏；在此基础上，以除铁钛石膏为原料，再利用醇水法制备长径比为90～180的半水硫酸钙晶须(如表1、图2、图3和图4所示)。而对比例1和对比例2同样采用醇水法，却无法有效获得长径比为90～180的半水硫酸钙晶须，因此本发明能有效制备超长长径比的半水硫酸钙晶须，并且整个反应条件温和，无需高压条件，仅在常压下反应1-2h就能制得，显著提高了生产效率和生产安全性，非常适于工业大规模生产。The data in Table 2 shows that the present invention can efficiently remove iron in titanium gypsum by using titanium dioxide waste acid, and obtain titanium gypsum with iron content lower than 4%; Calcium sulfate hemihydrate whiskers with an aspect ratio of 90 to 180 were prepared by the method (as shown in Table 1, Figure 2, Figure 3 and Figure 4). And Comparative Example 1 and Comparative Example 2 also use alcohol-water method, but can not effectively obtain calcium sulfate hemihydrate crystal whiskers with an aspect ratio of 90 to 180, so the present invention can effectively prepare calcium sulfate hemihydrate crystals with an ultra-long aspect ratio. The whole reaction conditions are mild, no high pressure conditions are required, and it can be prepared by only reacting under normal pressure for 1-2 hours, which significantly improves the production efficiency and production safety, and is very suitable for industrial large-scale production.
本发明的说明书和附图被认为是说明性的而非限制性的，在本发明基础上，本领域技术人员根据所公开的技术内容，不需要创造性的劳动就可以对其中一些技术特征做出一些替换和变形，均在本发明的保护范围内。The description and drawings of the present invention are considered to be illustrative rather than restrictive. On the basis of the present invention, those skilled in the art can make some technical features without creative work according to the disclosed technical content. Some replacements and modifications are within the protection scope of the present invention.
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