TWI618577B - 金屬碳酸鹽之製造方法及其所用之觸媒 - Google Patents
金屬碳酸鹽之製造方法及其所用之觸媒 Download PDFInfo
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 28
- 239000002184 metal Substances 0.000 title claims abstract description 28
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 25
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 title claims abstract description 13
- 239000003054 catalyst Substances 0.000 title abstract description 5
- 239000000203 mixture Substances 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 18
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 8
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 8
- 229910052742 iron Inorganic materials 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 30
- 150000001875 compounds Chemical class 0.000 claims description 28
- 239000000243 solution Substances 0.000 claims description 11
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 9
- 239000001257 hydrogen Substances 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 229910052725 zinc Inorganic materials 0.000 claims description 7
- 150000002431 hydrogen Chemical class 0.000 claims description 5
- IOIYXVPXUACSAK-UHFFFAOYSA-N N'-[2-[2-(dimethylamino)ethyl-methylamino]ethyl]-N,N,N'-trimethylethane-1,2-diamine Chemical compound CN(CCN(CCN(CCN(C)C)C)C)C.CN(CCN(CCN(CCN(C)C)C)C)C IOIYXVPXUACSAK-UHFFFAOYSA-N 0.000 claims description 4
- 125000006273 (C1-C3) alkyl group Chemical group 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims 1
- 238000001914 filtration Methods 0.000 claims 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 23
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 abstract 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 15
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 description 10
- DWFKOMDBEKIATP-UHFFFAOYSA-N n'-[2-[2-(dimethylamino)ethyl-methylamino]ethyl]-n,n,n'-trimethylethane-1,2-diamine Chemical compound CN(C)CCN(C)CCN(C)CCN(C)C DWFKOMDBEKIATP-UHFFFAOYSA-N 0.000 description 10
- 235000004416 zinc carbonate Nutrition 0.000 description 10
- 239000011667 zinc carbonate Substances 0.000 description 9
- 229910000010 zinc carbonate Inorganic materials 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 8
- 239000007789 gas Substances 0.000 description 8
- 239000002904 solvent Substances 0.000 description 7
- 239000011701 zinc Substances 0.000 description 7
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 229910002091 carbon monoxide Inorganic materials 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 238000004817 gas chromatography Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 3
- RAQDACVRFCEPDA-UHFFFAOYSA-L ferrous carbonate Chemical compound [Fe+2].[O-]C([O-])=O RAQDACVRFCEPDA-UHFFFAOYSA-L 0.000 description 3
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 229960001124 trientine Drugs 0.000 description 3
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 2
- 239000003674 animal food additive Substances 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 239000001095 magnesium carbonate Substances 0.000 description 2
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 2
- -1 nitrosonium tetrafluoroborate Chemical compound 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- XEZNGIUYQVAUSS-UHFFFAOYSA-N 18-crown-6 Chemical compound C1COCCOCCOCCOCCOCCO1 XEZNGIUYQVAUSS-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 206010048259 Zinc deficiency Diseases 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 238000005273 aeration Methods 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000003212 astringent agent Substances 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- YPJCVYYCWSFGRM-UHFFFAOYSA-H iron(3+);tricarbonate Chemical group [Fe+3].[Fe+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O YPJCVYYCWSFGRM-UHFFFAOYSA-H 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000005120 petroleum cracking Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
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- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G9/00—Compounds of zinc
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- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/02—Iron compounds
- C07F15/025—Iron compounds without a metal-carbon linkage
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0235—Nitrogen containing compounds
- B01J31/0237—Amines
-
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- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/009—Compounds containing, besides iron, two or more other elements, with the exception of oxygen or hydrogen
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/20—Carbon compounds
- B01J27/232—Carbonates
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0235—Nitrogen containing compounds
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1616—Coordination complexes, e.g. organometallic complexes, immobilised on an inorganic support, e.g. ship-in-a-bottle type catalysts
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
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- C01B32/00—Carbon; Compounds thereof
- C01B32/60—Preparation of carbonates or bicarbonates in general
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- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
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Abstract
本發明揭示一種金屬碳酸鹽之製造方法。本發明方法包含先提供一第一混合物,第一混合物包含金屬以及一具有鐵,含氮螯合基,及NO基之觸媒;之後以二氧化碳與第一混合物反應形成一第二混合物,並得到產物。本發明可以改善生產金屬碳酸鹽的產率以及成本。
Description
本發明係關於碳酸鹽的製造方法,特別是關於金屬碳酸鹽之製造方法。
金屬碳酸鹽化合物(metal carbonate)為一重要之原料,應用在醫藥、防火材料、動物食物添加物及工業用原料等,例如:碳酸鋅可供做人類鋅之補充藥物,避免鋅缺乏疾病,且可供做殺菌及收斂劑,防火材料,橡膠混合物,同時也是石油裂解過程中排放之硫化氫的吸附劑。又如碳酸鐵可利用為石油裂解過程排放之硫化氫的吸收劑及動物食物之添加劑。
碳酸鋅可由數種已知的方法所製造而成。例如目前很多的碳酸鋅係依下列合成路徑所製造合成(揭示於U.S.Pat.No.1944415):3ZnO+2CH3COOH+CO2+H2O→ZnCO3.Zn(OH)2.ZnO+2CH3COOH
前述合成路徑的製造方式,所得到的產物為碳酸鋅,Zn(OH)2及ZnO混合物,後續再經分離純化可得到碳酸鋅。然而,現今的金屬碳酸鹽化合物或碳酸鋅的製造方法大多需要複雜步驟來完成,而且多是高耗能的製程。甚至反應後尚需要額外的分離或純化步驟以應付高純度的應用。
因此,亟需要一種改良的碳酸鹽的製造方法來改善以上所述之缺點。
為解決上述之問題,本發明係提供一種簡化之金屬碳酸鹽之製造方法,以節省耗損能量,並改善產率。
本發明並提供一種簡化之金屬碳酸鹽之製造方法,以於室溫下製造金屬碳酸鹽。
本發明並提供一種新穎之化合物。
本發明金屬碳酸鹽之製造方法,包含以下步驟:(A)先提供一第一混合物,且該第一混合物包含金屬及如式(I)所示化合物溶液:(Fe(NO)2)2 L (I)
其中L為如式(II)所示之螯合基;(R1R2)N-(CH2)2-N(R3)-(CH2)2-N(R4)-(CH2)2-N(R5R6) (II)
其中每一R1,R2,R3,R4,R5,及R6獨立地為氫,或C1-C3烷基;以及(B)將二氧化碳與第一混合物混合反應以形成一第二混合物,並得到一產物。
本發明之化合物,係為如式(I)所示化合物:(Fe(NO)2)2 L (I)
其中L為如式(II)所示之螯合基;(R1R2)N-(CH2)2-N(R3)-(CH2)2-N(R4)-(CH2)2-N(R5R6) (II)
其中每一R1,R2,R3,R4,R5,及R6獨立地為氫,或C1-C3烷基。
本發明中之R1及R2可為相同或相異,較佳為R1及R2相同。本發明中之R3及R4可為相同或相異,較佳為R3及R4相同。本發明中之R5及R6可為相同
或相異,較佳為R5及R6相同。本發明之每一R1,R2,R3,R4,R5,及R6,如前所述,獨立地為氫,或C1-C3烷基,較佳為R1,R2,R3,R4,R5,及R6為甲基或氫。更佳為L是1,1,4,7,10,10-六甲基三亞乙基四胺(1,1,4,7,10,10-hexamethyltriethylenetetramine)或三亞乙基四胺(triethylene-tetramine)。本發明中之金屬無特殊之限制,本發明中之金屬較佳為Na,Mg,Zn,Fe,或其混合物。本發明之化合物較佳係用以作為催化生產金屬碳酸鹽之反應之觸媒。更佳為本發明之化合物較佳係用以作為催化生產碳酸鈉,碳酸鎂,碳酸鋅,碳酸鐵,或前述之碳酸混合物之反應之觸媒。
本發明之方法可選擇性地於步驟(B)後更包含步驟(C)乾燥或過濾該第二混合物,以收集步驟(B)之產物。本發明方法實施之溫度無特殊之限制,較佳為於250℃以下溫度進行,更佳為室溫溫度進行。本發明方法步驟(A)中之化合物溶液無限制,較佳為步驟(A)之該化合物溶液為水溶液,或有機溶液。
本發明之方法係利用如式(I)所示化合物進行反應,而本發明之方法之反應可約略以式(III)所示之反應式表示:
其中M為金屬。
藉由前述本發明化合物之協助,本發明製造方法可以節省耗損能量,並改善產率情形下,合成製造金屬碳酸鹽。
圖1為實施例1-1錯合物之紅外線光譜圖。
本發明可由以下諸實施例說明其製程,但本發明之範圍並非侷限在以下所述之實施例:
實施例1-1 [(HMTETA)(Fe(NO)2)2]錯合物之合成(HMTETA:1,1,4,7,10,10-六甲基三亞乙基四胺(1,1,4,7,10,10-Hexamethyl-triethylenetetramine))
秤取化合物[Na][NO2](10.0mmol,0.690g)及18-冠-6-醚(18-crown-6-ether)(10.0mmol,2.643g)溶解於燒瓶中之THF,於0℃下將[Fe(CO)5](10.0mmol,1.348mL)加入此THF混合物中。室溫下整夜攪拌該混合物。該反應以FTIR監看,IR光譜(IR 1983 m,1877 s(υCO),1647 m(υNO)cm-1(THF))顯示[Na-18-crown-6-ether][Fe(CO)3(NO)]形成。之後加入己烷得黃色沈澱固體[Na-18-crown-6-ether][Fe(CO)3(NO)](3.885g,85%)。
秤取[18-crown-6-ether-Na][Fe(CO)3NO](1.828g,3mmol),[NO][BF4](nitrosonium tetrafluoroborate;0.467g,3mmol)於50mL Schlenk flask中,加入約20mL的THF溶劑,於常溫下攪拌反應約20分鐘,生成Fe(CO)2(NO)2(IR:2088 s,2037s,(νCO),1808 s,1760 s(νNO)cm-1(THF))。然後以塑膠針筒打入1,1,4,7,10,10-Hexamethyltriethylene-tetramine(HMTETA)(0.408mL,1.5mmol)於反應溶液中,攪拌反應30分鐘後,測其IR振動頻率在1693 s,1634 s cm-1(νNO)(THF),證實形成[(HMTETA)(Fe(NO)2)2]。加入hexane置於上層(hexane:THF體積比約4:1),靜置約三天可得到深褐色晶體,並進行X-ray單晶繞射實驗鑑定結構。IR(νNO):1693,1634cm-1(THF)(圖1)。
實施例1-2 [(TETA)(Fe(NO)2)2]錯合物之合成(TETA:三亞乙基四胺(triethylenetetramine))
秤取[18-crown-6-ether-Na][Fe(CO)3NO](1.828g,3mmol),[NO][BF4](nitrosonium tetrafluoroborate;0.467g,3mmol)於50mL Schlenk flask中,加入約20mL的THF溶劑,於常溫下攪拌反應約20分鐘,生成Fe(CO)2(NO)2(IR:2088 s,2037s,(νCO),1808 s,1760 s(νNO)cm-1(THF))。然後以塑膠針筒打入triethylenetetramine(TETA)(0.223mL,1.5mmol)於反應溶液中,攪拌反應30分鐘後,測其IR振動頻率在1688 s,1630 s cm-1(νNO)(THF),推測形成[(TETA)(Fe(NO)2)2]。加入hexane置於上層(hexane:THF體積比約4:1),靜置約三天可得到深褐色固體。IR(νNO):1688,1630cm-1(THF).
實施例2 金屬碳酸鹽錯合物之合成
秤取鈉金屬條(0.069g,3mmol)於100mL Schlenk flask中,並將此反應瓶送入手套箱(充滿氮氣),於手套箱內秤取鐵金屬錯合物[(HMTETA)(Fe(NO)2)2](0.0138g,0.03mmol),之後加入約20mL的THF溶劑,再通入二氧化碳氣體(約73.5mL,3mmol),即可密封好不再通氣,攪拌反應約三天後可看到反應瓶內生成白色的碳酸鈉(Na2CO3)。三天後以氣相層析儀(gas chromatography)檢測上層氣體,可測到一氧化碳的峰值。另外將THF溶劑抽乾後,再回溶水,將此溶液過濾,並靜置數天,等水自然蒸發後,可得碳酸鈉的晶體(0.144g,90% yield),並進行X-ray單晶繞射實驗鑑定結構。碳酸鈉FTIR(IR: CO3 1456cm-1(KBr))。
實施例3-1至3-4
如表1的3-1所示,在空氣下秤取鋅金屬粉末(0.6538g,10mmol)置於500mL玻璃反應瓶中,並將此反應瓶送入手套箱(充滿氮氣),於手套箱內秤取錯合物[(HMTETA)(Fe(NO)2)2](0.046g,0.1mmol)置於此玻璃反應瓶中,之後加入約100mL的水溶劑,於常溫常壓下,再通入二氧化碳氣體(490mL,20mmol),並於常溫常壓下,攪拌反應15小時後,即可看到反應瓶內生成純白色的碳酸鋅(ZnCO3)。產率經過計算為1.125g(89.7%)(表1,3-1)。以氣相層析儀(gas chromatography)檢測上層氣體,可測到一氧化碳的峰值。之後我們以相同之過程,但不同比例的鋅金屬粉末及錯合物[(HMTETA)(Fe(NO)2)2],即可建構出表1。隨著鋅金屬比例的不斷上升,所需通入的二氧化碳量也隨著比例上升,直到反應瓶內的化合物全變白色的碳酸鋅,我們將之視為反應完成。純白色的碳酸鋅進行FTIR(IR: CO3 1445cm-1(KBr))及元素分析實驗(Calc.C 9.58%,found C,9.55%)鑑定。
實施例4
在空氣下秤取鎂金屬粉末(0.243g,10mmol)置於500mL玻璃反應瓶中,並將此反應瓶送入手套箱(充滿氮氣),於手套箱內秤取錯合物[(HMTETA)(Fe(NO)2)2](0.046g,0.1mmol)置於此玻璃反應瓶中,之後加入約100
mL的水溶劑,於常溫常壓下,再通入二氧化碳氣體(490mL,20mmol),並於常溫常壓下,攪拌反應20小時後,即可看到反應瓶內生成純白色的碳酸鎂(MgCO3)。產率經過計算為0.674g(80%)。以氣相層析儀(gas chromatography)檢測上層氣體,可測到一氧化碳的峰值。純白色的碳酸鎂進行FTIR(IR: CO3 1486,1424cm-1(KBr))。
實施例5
在空氣下秤取鐵金屬粉末(0.559g,10mmol)置於500mL玻璃反應瓶中,並將此反應瓶送入手套箱(充滿氮氣),於手套箱內秤取錯合物[(HMTETA)(Fe(NO)2)2](0.046g,0.1mmol)置於此玻璃反應瓶中,之後加入約100mL的水溶劑,於常溫常壓下,再通入二氧化碳氣體(490mL,20mmol),並於常溫常壓下,攪拌反應72小時後,即可看到反應瓶內生成紅褐色的碳酸鐵(FeCO3)。產率經過計算為0.928g(80%)。以氣相層析儀(gas chromatography)檢測上層氣體,可測到一氧化碳的峰值。紅褐色的碳酸鐵進行FTIR(IR: CO3 1419cm-1(KBr))。
由以上實施例可知,於本發明方法中,金屬碳酸鹽可以在常溫常壓(例如約1大氣壓)下製成。且透過本發明方法及化合物,金屬碳酸鹽之製備無須額外之電能或光照。再者,本發明方法可以在觸媒化合物存在下,於水溶液或有機溶液中反應而成,較諸目前所知之技術,明顯具有簡單,省能,及便宜之優點。以上較佳實施例僅為說明本發明之技術,其仍可為不偏離本發明技術精神下做修改及變化。
Claims (20)
- 一種金屬碳酸鹽之製造方法,包含以下步驟:(A)提供一第一混合物,且該第一混合物包含金屬及如式(I)所示化合物溶液:(Fe(NO)2)2 L (I)其中L為如式(II)所示之螯合基;(R1R2)N-(CH2)2-N(R3)-(CH2)2-N(R4)-(CH2)2-N(R5R6) (II)其中每一R1,R2,R3,R4,R5,及R6獨立地為氫,或C1-C3烷基;以及(B)將二氧化碳與第一混合物混合反應以形成一第二混合物,並得到一產物。
- 如申請專利範圍第1項之製造方法,其更包含步驟(C)乾燥或過濾該第二混合物,以收集步驟(B)之產物。
- 如申請專利範圍第1項之製造方法,其中該金屬為Na,Mg,Zn,Fe,或其混合物。
- 如申請專利範圍第1項之製造方法,其中步驟(B)係於室溫下進行。
- 如申請專利範圍第1項之製造方法,其中R1及R2相同。
- 如申請專利範圍第1項之製造方法,其中R3及R4相同。
- 如申請專利範圍第1項之製造方法,其中R5及R6相同。
- 如申請專利範圍第1項之製造方法,其中R1,R2,R3,R4,R5,及R6為甲基或氫。
- 如申請專利範圍第1項之製造方法,其中L為1,1,4,7,10,10-六甲基三亞乙基四胺(1,1,4,7,10,10-hexamethyltriethylenetetramine)。
- 如申請專利範圍申請專利範圍第1項之製造方法,其中L為三亞乙基四胺(triethylenetetramine)。
- 如申請專利範圍第1項之製造方法,其中步驟(A)之該化合物溶液為水溶液,或有機溶液。
- 一種如式(I)所示化合物:(Fe(NO)2)2 L (I)其中L為如式(II)所示之螯合基;(R1R2)N-(CH2)2-N(R3)-(CH2)2-N(R4)-(CH2)2-N(R5R6) (II)其中每一R1,R2,R3,R4,R5,及R6獨立地為氫,或C1-C3烷基。
- 如申請專利範圍第12項之化合物,其中R1及R2相同。
- 如申請專利範圍第12項之化合物,其中R3及R4相同。
- 如申請專利範圍第12項之化合物,其中R5及R6相同。
- 如申請專利範圍第12項之化合物,其中R1,R2,R3,R4,R5,及R6為甲基或氫。
- 如申請專利範圍第12項之化合物,其中L為1,1,4,7,10,10-六甲基三亞乙基四胺(1,1,4,7,10,10-hexamethyltriethylenetetramine)。
- 如申請專利範圍第12項之化合物,其中L為三亞乙基四胺(triethylenetetramine)。
- 一種化合物之用途,其係用以催化生產金屬碳酸鹽之反應,其中該化合物係為如申請專利範圍第12至18項任一項所述之化合物。
- 如申請專利範圍第19項之用途,其中金屬為Na,Mg,Zn,Fe,或其混合物。
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US15/067,961 US9802835B2 (en) | 2016-02-01 | 2016-03-11 | Method for producing metal carbonate and catalyst for producing the same |
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US20170217786A1 (en) | 2017-08-03 |
TW201728534A (zh) | 2017-08-16 |
PH12016000350A1 (en) | 2018-04-11 |
BR102016025786A2 (pt) | 2017-08-08 |
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