TWI606977B - 用於得到沉澱的碳酸鈣的方法 - Google Patents
用於得到沉澱的碳酸鈣的方法 Download PDFInfo
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- TWI606977B TWI606977B TW103113190A TW103113190A TWI606977B TW I606977 B TWI606977 B TW I606977B TW 103113190 A TW103113190 A TW 103113190A TW 103113190 A TW103113190 A TW 103113190A TW I606977 B TWI606977 B TW I606977B
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- Prior art keywords
- calcium carbonate
- precipitated calcium
- aragonite
- pcc
- seed
- Prior art date
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- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 title claims description 159
- 229940088417 precipitated calcium carbonate Drugs 0.000 title claims description 49
- 238000000034 method Methods 0.000 title claims description 33
- 239000013078 crystal Substances 0.000 claims description 50
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 28
- 239000011575 calcium Substances 0.000 claims description 22
- 239000002002 slurry Substances 0.000 claims description 20
- 238000004519 manufacturing process Methods 0.000 claims description 13
- 239000007900 aqueous suspension Substances 0.000 claims description 9
- 239000000725 suspension Substances 0.000 claims description 8
- 238000000227 grinding Methods 0.000 claims description 7
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 7
- 239000011707 mineral Substances 0.000 claims description 7
- 238000001354 calcination Methods 0.000 claims description 5
- 238000001556 precipitation Methods 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 235000013305 food Nutrition 0.000 claims description 3
- 238000011065 in-situ storage Methods 0.000 claims description 3
- 229910052746 lanthanum Inorganic materials 0.000 claims description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 2
- 229910052703 rhodium Inorganic materials 0.000 claims 1
- 239000010948 rhodium Substances 0.000 claims 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims 1
- 239000000047 product Substances 0.000 description 44
- 229910003514 Sr(OH) Inorganic materials 0.000 description 23
- 239000000920 calcium hydroxide Substances 0.000 description 21
- 235000011116 calcium hydroxide Nutrition 0.000 description 21
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 15
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 14
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 9
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 8
- 239000007789 gas Substances 0.000 description 8
- 239000000123 paper Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 7
- 101100496858 Mus musculus Colec12 gene Proteins 0.000 description 7
- 235000011941 Tilia x europaea Nutrition 0.000 description 7
- 239000000945 filler Substances 0.000 description 7
- 239000004571 lime Substances 0.000 description 7
- 239000008267 milk Substances 0.000 description 7
- 210000004080 milk Anatomy 0.000 description 7
- 235000013336 milk Nutrition 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 229910021532 Calcite Inorganic materials 0.000 description 6
- 239000000654 additive Substances 0.000 description 6
- 230000000996 additive effect Effects 0.000 description 6
- 230000032683 aging Effects 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 239000000292 calcium oxide Substances 0.000 description 4
- 235000012255 calcium oxide Nutrition 0.000 description 4
- 239000001569 carbon dioxide Substances 0.000 description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 230000035800 maturation Effects 0.000 description 4
- 235000010755 mineral Nutrition 0.000 description 4
- 239000003973 paint Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 238000013459 approach Methods 0.000 description 3
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 description 3
- 229910001863 barium hydroxide Inorganic materials 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 238000001238 wet grinding Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- -1 coatings Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- BDAGIHXWWSANSR-NJFSPNSNSA-N hydroxyformaldehyde Chemical compound O[14CH]=O BDAGIHXWWSANSR-NJFSPNSNSA-N 0.000 description 2
- 239000000976 ink Substances 0.000 description 2
- 238000010899 nucleation Methods 0.000 description 2
- 239000000825 pharmaceutical preparation Substances 0.000 description 2
- 229940127557 pharmaceutical product Drugs 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 229910000018 strontium carbonate Inorganic materials 0.000 description 2
- RXSHXLOMRZJCLB-UHFFFAOYSA-L strontium;diacetate Chemical compound [Sr+2].CC([O-])=O.CC([O-])=O RXSHXLOMRZJCLB-UHFFFAOYSA-L 0.000 description 2
- MFGOFGRYDNHJTA-UHFFFAOYSA-N 2-amino-1-(2-fluorophenyl)ethanol Chemical compound NCC(O)C1=CC=CC=C1F MFGOFGRYDNHJTA-UHFFFAOYSA-N 0.000 description 1
- 150000000703 Cerium Chemical class 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 241000245165 Rhododendron ponticum Species 0.000 description 1
- 239000003082 abrasive agent Substances 0.000 description 1
- 229920006243 acrylic copolymer Polymers 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 239000013466 adhesive and sealant Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 description 1
- 229910001626 barium chloride Inorganic materials 0.000 description 1
- AIYUHDOJVYHVIT-UHFFFAOYSA-M caesium chloride Chemical compound [Cl-].[Cs+] AIYUHDOJVYHVIT-UHFFFAOYSA-M 0.000 description 1
- HUCVOHYBFXVBRW-UHFFFAOYSA-M caesium hydroxide Inorganic materials [OH-].[Cs+] HUCVOHYBFXVBRW-UHFFFAOYSA-M 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 229910001748 carbonate mineral Inorganic materials 0.000 description 1
- 150000001785 cerium compounds Chemical class 0.000 description 1
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 description 1
- VGBWDOLBWVJTRZ-UHFFFAOYSA-K cerium(3+);triacetate Chemical compound [Ce+3].CC([O-])=O.CC([O-])=O.CC([O-])=O VGBWDOLBWVJTRZ-UHFFFAOYSA-K 0.000 description 1
- UNJPQTDTZAKTFK-UHFFFAOYSA-K cerium(iii) hydroxide Chemical compound [OH-].[OH-].[OH-].[Ce+3] UNJPQTDTZAKTFK-UHFFFAOYSA-K 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000009837 dry grinding Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 238000009533 lab test Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000001459 lithography Methods 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 150000004714 phosphonium salts Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 150000003304 ruthenium compounds Chemical class 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 229910001631 strontium chloride Inorganic materials 0.000 description 1
- AHBGXTDRMVNFER-UHFFFAOYSA-L strontium dichloride Chemical compound [Cl-].[Cl-].[Sr+2] AHBGXTDRMVNFER-UHFFFAOYSA-L 0.000 description 1
- 229910001427 strontium ion Inorganic materials 0.000 description 1
- 159000000008 strontium salts Chemical class 0.000 description 1
- UJPWWRPNIRRCPJ-UHFFFAOYSA-L strontium;dihydroxide;octahydrate Chemical compound O.O.O.O.O.O.O.O.[OH-].[OH-].[Sr+2] UJPWWRPNIRRCPJ-UHFFFAOYSA-L 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- ZSDSQXJSNMTJDA-UHFFFAOYSA-N trifluralin Chemical compound CCCN(CCC)C1=C([N+]([O-])=O)C=C(C(F)(F)F)C=C1[N+]([O-])=O ZSDSQXJSNMTJDA-UHFFFAOYSA-N 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J6/00—Heat treatments such as Calcining; Fusing ; Pyrolysis
-
- 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
- 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
-
- 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
- C01F11/182—Preparation of calcium carbonate by carbonation of aqueous solutions and characterised by an additive other than CaCO3-seeds
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/30—Three-dimensional structures
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/10—Particle morphology extending in one dimension, e.g. needle-like
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Description
本發明係關於一種用於產生沉澱的碳酸鈣且尤其具有較高重量百分比之文石晶體多形物之沉澱的碳酸鈣產物的方法。
近年來，碳酸鈣已在許多領域中得到廣泛使用。舉例而言，碳酸鈣為紙張、塑膠、油漆及塗料行業中最廣泛使用的礦物質之一，其用作填料且因其色彩為白色而用作塗佈顏料。在造紙業中，碳酸鈣因其高亮度、不透明度及光澤而有價值，且通常用作填料以製造光亮的不透明紙張。此外，碳酸鈣在油漆中常用作增效劑，且亦在黏著劑及密封劑中用作填料。高等級碳酸鈣亦已在醫藥調配中得到使用。
已知碳酸鈣以三種類型之晶體多形物的形式存在：方解石、文石及六方方解石。方解石為最常見的晶體多形物，其被視為碳酸鈣之最穩定晶體形式。文石較為少見，其具有離散或叢集之針狀斜方晶晶體結構。六方方解石為最罕見的碳酸鈣多形物，且一般不穩定。
在此三種形式中，文石因其提供增強之紙張鬆厚度(paper bulk)及不透明度的針形晶體結構而尤其適用於許多應用，諸如無機填料或紙面塗料。因此，對具有顯著文石晶體含量之碳酸鈣的需要已有實質性增加。
一般而言，一種商業上產生碳酸鈣之方式為藉由鍛燒過粗碳酸鈣而得到生石灰。接著添加水以產生氫氧化鈣之水性懸浮液(「石灰乳」)，且向此漿液中再引入二氧化碳以使碳酸鈣沉澱。此方法之產物稱為沉澱的碳酸鈣(「PCC」)。所得碳酸鈣水性懸浮液或漿液可按原樣使用或經進一步處理(亦即脫水、研磨等)以形成乾產物。視所使用之確切反應條件而定，沉澱反應能夠產生三種多形物(方解石、文石及六方方解石)中之每一者。
用於產生具有較高文石晶體含量之PCC產物的先前技術方法一般採取許多途徑。在第一種途徑中，已開發出在碳酸化期間使用諸如鍶鹽之添加劑來促進文石晶體產生，從而形成PCC的方法。舉例而言，GB 2145074A揭示一種藉由在碳酸化期間添加氯化鍶(SrCl2)以充當形成文石晶體之試劑來產生沉澱的文石碳酸鈣的方法。
使用鍶化合物作為碳酸化過程之添加劑以供製備PCC亦揭示於以下日本專利公開案之PCC生產方法中：JP63260815、JP59223225、JP5116936及JP1018911。
在第二種途徑中，方法已利用文石種晶(seed crystal)來增加文石晶體形成。舉例而言，GB 941900A教示一種藉由在碳酸化期間引入碳酸鈉溶液來產生文石碳酸鈣的方法。該參考文獻表明，向所揭示之方法中添加文石種晶可加速文石晶體的產生。
上文所論述之生產方法已顯示或多或少地增加PCC產物之總文石晶體含量。然而，此等方法一般不能產生總文石含量大於60%之PCC。
因此，需要一種用於產生含有較高量之文石多形物之沉澱的
PCC的低成本方法。
本發明提供一種產生低成本的包含PCC之物質的方法，其
中在包含PCC之物質中，相對於PCC大於60%且較佳大於70%為文石多形物。在其一般形式中，本發明藉由利用兩階段製造方法來實現此等需求。
在第一階段中，可藉由在碳酸化之前每莫耳Ca(OH)2 0.005至0.030莫耳或更佳0.01至0.02莫耳呈Sr(OH)2形式之鍶存在下使Ca(OH)2懸浮液碳酸化來形成沉澱的碳酸鈣晶種之水性懸浮液。在第二階段中，藉由在以乾重計0.5%至5%沉澱的碳酸鈣晶種存在下使Ca(OH)2漿液碳酸化來形成沉澱的碳酸鈣產物之水性懸浮液。沉澱的碳酸鈣晶種之D50可小於沉澱的碳酸鈣產物之D50，且沉澱的碳酸鈣晶種之文石多形物含量可大於或等於沉澱的碳酸鈣產物之文石多形物含量。如以下實施例中將論述，此兩階段方法之產物解決了先前PCC生產方法的不足且最終產物中文石多形物之總重量百分比得到所要增加。
本發明亦提供一種由本發明方法製備的沉澱的碳酸鈣產物。
此外，本發明提供一種包含本發明之沉澱的碳酸鈣產物的物
質。該物質可包括例如需要包括碳酸鈣作為填料之產品，諸如紙張、紙製品、油墨、油漆、塗料、塑膠、黏著劑、建築產品、食品及醫藥產品。
最後，本發明之沉澱的碳酸鈣產物係針對使用該產物來製造
需要使用文石PCC作為填料之物質。
本發明之其他目的將自以下描述顯而易見。
如上文所論述，PCC典型地藉由熟石灰碳酸化來製造。在此
方法中，首先鍛燒(加熱)粉碎的碳酸鈣以形成石灰(CaO)及二氧化碳氣體(CO2)。此反應展示於反應(1)中：(1)CaCO3→CaO+CO2
接著用水使石灰熟化(slake)以形成氫氧化鈣(Ca(OH)2)或石灰乳，其展示於反應(2)中：(2)CaO+H2O→Ca(OH)2
最後，將氫氧化鈣與二氧化碳(通常在鍛燒步驟期間捕獲)組合以使碳酸鈣沉澱。此碳酸化步驟展示於反應(3)中：(3)Ca(OH)2+CO2→CaCO3+H2O
根據本發明，以兩階段方法製備沉澱的碳酸鈣產物。在第一階段中，藉由在碳酸化之前以Ca(OH)2之莫耳數計，0.005至0.030莫耳或更佳0.01至0.02莫耳呈Sr(OH)2形式之鍶存在下使Ca(OH)2懸浮液碳酸化來製備沉澱的碳酸鈣晶種之水性懸浮液(或漿液)。可經由Ca(OH)2懸浮液之石灰引入Sr(OH)2，或更佳可藉由在熟化及/或碳酸化期間添加包含SrO之礦物質而就地形成Sr(OH)2。若藉由添加包含SrO之礦物質而就地形成Sr(OH)2，則較佳可藉由鍛燒包含SrCO3之礦物質或粗菱鍶礦原料石而得到包含SrO之礦物質。
本發明之沉澱的碳酸鈣晶種的特徵為文石多形物含量大於或等於第二階段中所產生之沉澱的碳酸鈣產物的文石多形物含量。特定言
之，在本發明方法中，沉澱的碳酸鈣晶種之水溶液可具有以乾重計大於85%、較佳為90%或最佳為95%的文石多形物含量。如本文所述之乾重百分比係藉由X射線繞射分析(XRD)來測定。
在製造方法之第一階段期間所產生之沉澱的碳酸鈣晶種的
另一特徵為D50小於沉澱的碳酸鈣產物的D50。D50尺寸定義為如下尺寸：在該尺寸下以累積體積分數計50%之產物小於該尺寸。使用Micrometrics SedigraphTM 5100量測粒徑。
在本發明之範圍內，晶種產生過程可進行其他處理步驟，諸
如進行脫水、分散及/或研磨。在較佳具體實例中，可進一步處理沉澱的碳酸鈣晶種之水性懸浮液以得到小於或等於0.1至0.3μm之D50及10至30m2/g之BET SSA。使用TriStar 3000，藉由根據BET程序量測乾燥樣品上之氮吸收來量測BET或表面積。
關於研磨，可對方法第一階段中所得之PCC晶種進行乾式
研磨及/或濕式研磨。濕式研磨係指在液體介質(例如漿液)中研磨PCC。
濕式研磨可在不存在助磨劑或存在助磨劑的情況下進行。可包括一或多種研磨劑，諸如聚丙烯酸鈉、聚丙烯酸鹽及/或丙烯酸共聚物之鹽。乾燥可使用任何適合之乾燥設備進行，且可包括例如熱乾燥及/或在減壓下使用諸如蒸發器、急驟乾燥器、烘箱、噴霧乾燥器(諸如由Niro及/或Nara出售之噴霧乾燥器)之設備乾燥及/或在真空腔室中乾燥。
在本發明方法之第二階段中，藉由在以乾重計0.5%至5%自
生產方法第一階段得到之沉澱的碳酸鈣晶種存在下使Ca(OH)2漿液碳酸化來形成沉澱的碳酸鈣產物之水性懸浮液。就此而言，可在沉澱的碳酸鈣產
物碳酸化之前將沉澱的碳酸鈣晶種添加至Ca(OH)2漿液中。或者，可在前四分之一的總碳酸化時間內將沉澱的碳酸鈣晶種添加至Ca(OH)2漿液中，其中總碳酸化時間包括自碳酸化開始直至電導率最小之時間所量測的總時間跨度。
本文所述之方法能夠產生沉澱的碳酸鈣產物，其含有以乾重
計大於60%且較佳以乾重計大於70%之文石多形物含量，如藉由XRD分析所測定。此外，第二階段中所產生之沉澱的碳酸鈣產物較佳具有1至5莫耳/乾公噸之總鍶量。
可對第二階段中得到之沉澱的碳酸鈣產物進行進一步處
理，包括例如脫水、分散及/或研磨步驟，以得到具有所要特徵之沉澱的碳酸鈣產物，其亦處於本發明之範圍內。較佳可對第二階段中得到之沉澱的碳酸鈣產物進行額外處理以得到0.35至0.45微米之D50及8至20m2/g之BET SSA。
最後，根據本發明產生之沉澱的文石碳酸鈣產物可用於需要
使用碳酸鈣作為填料的各種物質中。舉例而言，沉澱的文石碳酸鈣產物可用於醫藥領域產品(諸如醫藥)、人類或動物食品、造紙領域(諸如填料或紙面塗料)、水基或非水基油漆、塑膠或印刷油墨(例如平板印刷、輪轉凹版印刷)中。
初步試驗
作為起點，考慮八水合氫氧化鍶(Sr(OH)2．8H2O)，其目前用
作文石-PCC(「A-PCC」)晶種碳酸化之文石促進劑。進行實驗室試驗以評估替代性的且比Sr(OH)2．8H2O更經濟之Sr2+來源。
在第一個試驗中，經由在25% w/w乙酸中溶解SrCO3來製備
乙酸鍶(Sr(CH3COO)2)之26% w/w溶液。隨後評估乙酸鍶在A-PCC晶種製造中作為Sr(OH)2．8H2O之替代物用作碳酸化添加劑。此碳酸化試驗之結果指示，在以石灰乳計相同的Sr2+莫耳添加率下，乙酸鍶與Sr(OH)2．8H2O相比效果較差。詳言之，XRD分析揭示，當與Sr(OH)2．8H2O添加劑相比時，晶種碳酸化之後文石含量已自97%降至38%。
基於第一個試驗之結果，在第二個試驗中，在1300℃下將
化學純之沉澱的SrCO3鍛燒2小時以得到SrO。在添加2% SrO(乾/乾CaO)作為熟化添加劑下進行A-PCC晶種碳酸化，得到與使用7.5% Sr(OH)2．8H2O(乾/乾Ca(OH)2)相同的結果(97%文石)。此等初步試驗之結果展示於表1中。使用該等經後處理之A-PCC晶種的A-PCC製造試驗亦取得成功且在以下實施例中加以論述。
此外，藉由處於技術現狀下之X射線繞射對第二個試驗中
得到之PCC晶種進行礦物學分析。顯然，未偵測到結晶碳酸鍶，此指示所有鍶離子皆以外來離子形式併入文石晶格中。此證實在初始晶核生成期期間最終沉澱之碳酸鍶似乎不會干預晶種形成，而鍶離子則會如此。基於此
等發現，熟習此項技術者將預期用高度可溶性鍶鹽(諸如SrCl2)會得到最佳結果。然而，如下文進一步論述之結果所指示，SrCl2並不如Sr(OH)2(或向水中添加SrO所得之Sr(OH)2)一般有助於A-PCC晶種形成，儘管氯化鍶在水中之溶解度為53.8g/100mL(20℃)，而氫氧化鍶之溶解度為1.77g/100ml(20℃)。
可藉由比較使用單階段碳酸化方法之先前技術方法與利用兩階段方法之本發明實施例來說明此等結果。此等實施例僅欲作為說明，且不應視為以任何方式限制以下申請專利範圍所界定之本發明範疇。
表2展示由本發明得到之文石百分比相比使用先前技術方法得到之文石百分比的比較。
實施例
實施例1
階段1：A-PCC晶種
藉由將160kg生石灰CaO(例如Mississippi Lime公司，Ste.Geneviève，Mo供應之生石灰)添加至攪拌反應器中之1,300公升50℃自來水中而使該化合物熟化。熟化前，向CaO中添加藉由在1300℃下將化學純
之沉澱的SrCO3鍛燒2小時而得到之3.2kg SrO。在連續攪拌下使生石灰熟化30分鐘，且經由用60℃水稀釋將所得氫氧化鈣漿液(「石灰乳」)調節至13%固體含量，接著在100μm篩網上過篩。
在配備有通氣攪動器(gassing agitator)、用以將二氧化碳/空氣氣流引導至葉輪之不鏽鋼碳酸化管及用於監測懸浮液之pH值及電導率之探針的1000公升擋板式圓柱形不鏽鋼反應器中進行A-PCC晶種沉澱。
向碳酸化反應器中添加調節至60℃之溫度的800公升上述熟化步驟中得到之氫氧化鈣懸浮液。接著在1480rpm之漿液攪動下，使6體積% CO2/空氣氣體以100m3/h之速率向上鼓泡通過漿液15分鐘(自開始引入CO2氣體時計算)。此後，將氣體中之CO2體積分數擴增至24%，且將氣體流速擴增至200m3/h。在此速率下維持CO2體積分數及氣體流速直至反應結束。在碳酸化期間，不控制反應混合物之溫度，且該溫度因放熱沉澱反應所產生之熱而升高。在電導率對應於Ca(OH)2全部轉化成PCC達到最小值之後，再繼續通氣8分鐘，接著停止引入氣體。自開始引入氣體至電導率最小之時間所計算的碳酸化時間為84分鐘。接著在45μm篩網上使A-PCC晶種漿液過篩，且回收呈A-PCC晶種之水性漿液形式的過篩產物。如表2之A欄中所示，在添加以乾CaO計2% SrO(對應於以乾石灰乳計1.51% SrO)下A-PCC晶種碳酸化得到具有97.4%文石之A-PCC晶種漿液。
雖然並不需要，但在此實施例中進行A-PCC晶種漿液之後處理。詳言之，使物質脫水並研磨以得到具有17.4m2/g之SSA及0.23μm之中值直徑的粒子。
階段2：A-PCC產物
以與上述階段1中所述相同之方式進行熟化及碳酸化，但不添加SrO且在碳酸化之前向石灰乳中添加2.5%重量百分比(以氫氧化鈣之乾重計，以乾碳酸鈣計算)之階段1中形成的經研磨A-PCC晶種。對最終A-PCC產物進行之測試指示87.7%之產物為文石晶體。此外，如上述階段1中所述進行後處理，得到具有11.7m2/g之SSA及0.41μm之中值直徑的粒子。
實施例2
階段1：A-PCC晶種
以與上述實施例1中所述相同之方式進行A-PCC晶種碳酸化，但在熟化之前不向CaO中添加SrO。為形成A-PCC晶種，在碳酸化之前向石灰乳中添加5.0%重量百分比之Sr(OH)2．8H2O(以氫氧化鈣之乾重計)。如表2之B欄中所示，在添加5.0% Sr(OH)2．8H2O下A-PCC晶種碳酸化得到具有96.1%文石之A-PCC晶種漿液。
雖然並不需要，但在此實施例中進行A-PCC晶種漿液之後處理。詳言之，使物質脫水並研磨以得到具有20.6m2/g之SSA及0.22μm之中值直徑的粒子。
階段2：A-PCC產物
以與上述階段1中所述相同之方式進行熟化及碳酸化，但不添加Sr(OH)2．8H2O且在碳酸化之前向石灰乳中添加2.5%重量百分比(以氫氧化鈣之乾重計，以乾碳酸鈣計算)之階段1中形成的經研磨A-PCC晶種。對最終A-PCC產物進行之測試指示77.6%之產物為文石晶體。
實施例3
階段1：A-PCC晶種
以與上述實施例1中所述相同之方式進行A-PCC晶種碳酸化，但在熟化之前不向CaO中添加SrO。為形成A-PCC晶種，在碳酸化之前向石灰乳中添加7.5%重量百分比之Sr(OH)2．8H2O(以氫氧化鈣之乾重計)。如表2之C欄中所示，在添加7.5% Sr(OH)2．8H2O下A-PCC晶種碳酸化得到具有97.6%文石之A-PCC晶種漿液。
雖然並不需要，但在此實施例中進行A-PCC晶種漿液之後處理。詳言之，使物質脫水並研磨以得到具有22.5m2/g之SSA及0.21μm之中值直徑的粒子。
階段2：A-PCC產物
以與上述階段1中所述相同之方式進行熟化及碳酸化，但不添加Sr(OH)2．8H2O且在碳酸化之前向石灰乳中添加2.5%重量百分比(以氫氧化鈣之乾重計，以乾碳酸鈣計算)之階段1中形成的經研磨A-PCC晶種。對最終A-PCC產物進行之測試指示77.4%之產物為文石晶體。
比較實施例1
以與上述實施例1中所述相同之方式進行A-PCC晶種碳酸化，但在熟化前不向CaO中添加SrO。為形成A-PCC晶種，在碳酸化之前向石灰乳中添加3.5%重量百分比之SrCl2．6H2O(以氫氧化鈣之乾重計)。如表2之D欄中所示，該方法得到僅具有61.7%文石之A-PCC。如上文所論述，此等結果證實，當以類似添加率(莫耳鍶/乾公噸A-PCC晶種)添加時，高度可溶性鍶鹽(諸如SrCl2)不如Sr(OH)2(或向水中添加SrO所得之Sr(OH)2)一般有效，儘管氯化鍶在水中之溶解度比氫氧化鍶大。
比較實施例2
在單階段A-PCC方法中，在碳酸化之前向Ca(OH)2中添加0.1% w/w Sr(OH)2．8H2O。以與上述實施例1階段2中所述相同之方式進行熟化及碳酸化，但不添加A-PCC晶種，而替代地在碳酸化之前向石灰乳中添加0.1% w/w Sr(OH)2．8H2O(以氫氧化鈣之乾重計)。如表2之E欄中可見，所得A-PCC產物僅含有53.8%文石。
比較實施例3
在單階段A-PCC方法中，在碳酸化之前向Ca(OH)2中添加0.2% w/w Sr(OH)2．8H2O。以與上述實施例1階段2中所述相同之方式進行熟化及碳酸化，但不添加A-PCC晶種，而替代地在碳酸化之前向石灰乳中添加0.2% w/w Sr(OH)2．8H2O(以氫氧化鈣之乾重計)。如表2之F欄中可見，所得A-PCC產物僅含有46.4%文石。
比較實施例4
在單階段A-PCC方法中，在碳酸化之前向Ca(OH)2中添加0.07% w/w SrCl2．6H2O。以與上述實施例1階段2中所述相同之方式進行熟化及碳酸化，但不添加A-PCC晶種，而替代地在碳酸化之前向石灰乳中添加0.07% w/w SrCl2．6H2O(以氫氧化鈣之乾重計)。如表2之G欄中可見，所得A-PCC產物僅含有49.8%文石。
利用氫氧化鍶產生A-PCC產物的本發明兩階段方法提供先前由在碳酸化期間僅利用鍶化合物作為添加劑的先前技術方法無法得到的高文石產率。實際上，藉由在氫氧化鍶存在下首先產生A-PCC晶種，可始終得到具有高於60%文石含量的A-PCC產物。此外，與氯化鍶相比，使用
氫氧化鍶顯著增加文石晶體生長，同時降低製造成本。
鑒於已詳細描述本發明之各種具體實例，各種修改及改良將為熟習此項技術者顯而易知。因此，本發明具體實例應視為在所有方面皆為說明性而非限制性的，本發明之範疇由隨附申請專利範圍所指示，且處於申請專利範圍之等效含義及範圍內的所有變化由此欲涵蓋在內。
Claims (13)
- 一種沉澱的碳酸鈣產物的用途，該沉澱的碳酸鈣產物係由包含以下步驟的方法所產生：(a)藉由在每莫耳Ca(OH)2 0.005至0.030莫耳呈Sr(OH)2形式之Sr存在下使Ca(OH)2懸浮液碳酸化來製備沉澱的碳酸鈣晶種之水性懸浮液；及(b)藉由在以乾重計0.5%至5%該等沉澱的碳酸鈣晶種存在下使Ca(OH)2漿液碳酸化來形成沉澱的碳酸鈣產物之水性懸浮液，其中該等沉澱的碳酸鈣晶種之D50小於該沉澱的碳酸鈣產物之D50，且該等沉澱的碳酸鈣晶種之文石多形物含量大於或等於該沉澱的碳酸鈣產物之文石多形物含量，其係用於製造食品，其中步驟(b)中得到之該沉澱的碳酸鈣產物含有以乾重計大於60%之文石多形物含量。
- 如申請專利範圍第1項之用途，其中步驟(a)中之該Ca(OH)2懸浮液係在每莫耳Ca(OH)2 0.01至0.02莫耳之Sr存在下碳酸化。
- 如申請專利範圍第1項之用途，其中步驟(a)中之該Sr(OH)2係藉由添加包含SrO之礦物質而就地形成。
- 如申請專利範圍第3項之用途，其中該包含SrO之礦物質係藉由煅燒包含SrCO3之礦物質而得到。
- 如申請專利範圍第1項至第4項中任一項之用途，其進一步包含以下步驟：對步驟(a)中製備之該等沉澱的碳酸鈣晶種進行脫水、分散或研磨中之一或多者，以得到D50小於或等於0.1至0.3μm且BET SSA為10至30m2/g之沉澱的碳酸鈣晶種之水性懸浮液。
- 如申請專利範圍第1項至第4項中任一項之用途，其中步驟(a)中 形成之沉澱的碳酸鈣晶種之水溶液具有以乾重計大於85%之文石多形物含量。
- 如申請專利範圍第1項至第4項中任一項之用途，其中步驟(a)中形成之沉澱的碳酸鈣晶種之水溶液具有以乾重計大於90%之文石多形物含量。
- 如申請專利範圍第1項至第4項中任一項之用途，其中步驟(a)中形成之沉澱的碳酸鈣晶種之水溶液具有以乾重計大於95%之文石多形物含量。
- 如申請專利範圍第1項至第4項中任一項之用途，其中該等沉澱的碳酸鈣晶種係在碳酸化之前添加至步驟(b)中之該Ca(OH)2漿液中。
- 如申請專利範圍第1項至第4項中任一項之用途，其進一步包含以下步驟：對步驟(b)中得到之該沉澱的碳酸鈣產物進行脫水、分散或研磨中之一或多者，以得到D50為0.35至0.4微米且BET SSA為8至20m2/g之沉澱的碳酸鈣產物。
- 如申請專利範圍第1項至第4項中任一項之用途，其中步驟(b)中得到之該沉澱的碳酸鈣產物具有0.2至15莫耳/乾公噸之總鍶量。
- 如申請專利範圍第1項至第4項中任一項之用途，其中步驟(b)中得到之該沉澱的碳酸鈣產物具有1至5莫耳/乾公噸之總鍶量。
- 如申請專利範圍第1項至第4項中任一項之用途，其中步驟(b)中得到之該沉澱的碳酸鈣產物含有以乾重計大於70%之文石多形物含量。
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