KR102222771B1 - Catalyst for oxidative dehydrogenation, method of preparing the same and method for preparing butadien using the same - Google Patents
Catalyst for oxidative dehydrogenation, method of preparing the same and method for preparing butadien using the same Download PDFInfo
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- KR102222771B1 KR102222771B1 KR1020160181432A KR20160181432A KR102222771B1 KR 102222771 B1 KR102222771 B1 KR 102222771B1 KR 1020160181432 A KR1020160181432 A KR 1020160181432A KR 20160181432 A KR20160181432 A KR 20160181432A KR 102222771 B1 KR102222771 B1 KR 102222771B1
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- catalyst
- oxidative dehydrogenation
- butene
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- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 title claims abstract description 83
- 239000003054 catalyst Substances 0.000 title claims abstract description 57
- 238000005839 oxidative dehydrogenation reaction Methods 0.000 title claims abstract description 38
- 238000000034 method Methods 0.000 title claims abstract description 23
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 claims abstract description 43
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims abstract description 41
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 37
- 238000004519 manufacturing process Methods 0.000 claims abstract description 19
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 10
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 8
- 229910052738 indium Inorganic materials 0.000 claims abstract description 6
- 239000007809 chemical reaction catalyst Substances 0.000 claims abstract description 5
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 5
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 5
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 4
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 4
- 229910052788 barium Inorganic materials 0.000 claims abstract description 4
- 229910052790 beryllium Inorganic materials 0.000 claims abstract description 4
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 4
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 4
- 229910052733 gallium Inorganic materials 0.000 claims abstract description 4
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 4
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 4
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 4
- 229910052712 strontium Inorganic materials 0.000 claims abstract description 4
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 42
- 239000002243 precursor Substances 0.000 claims description 21
- 239000002904 solvent Substances 0.000 claims description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 8
- 239000001301 oxygen Substances 0.000 claims description 8
- 229910052760 oxygen Inorganic materials 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 239000002994 raw material Substances 0.000 claims description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims description 5
- 239000012453 solvate Substances 0.000 claims description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 4
- 239000007795 chemical reaction product Substances 0.000 claims description 4
- 235000019441 ethanol Nutrition 0.000 claims description 4
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 4
- 238000009835 boiling Methods 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 3
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Natural products CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 claims description 2
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 claims 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims 1
- 235000019445 benzyl alcohol Nutrition 0.000 claims 1
- 239000011701 zinc Substances 0.000 abstract description 21
- 230000000694 effects Effects 0.000 abstract description 19
- 229910052751 metal Inorganic materials 0.000 abstract description 17
- 239000002184 metal Substances 0.000 abstract description 16
- 229910052725 zinc Inorganic materials 0.000 abstract description 9
- 229910052742 iron Inorganic materials 0.000 abstract description 8
- 239000002245 particle Substances 0.000 abstract description 8
- 230000009257 reactivity Effects 0.000 abstract description 7
- 150000002739 metals Chemical class 0.000 abstract description 5
- 238000009826 distribution Methods 0.000 abstract description 4
- -1 zinc metals Chemical class 0.000 abstract description 4
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 15
- 229910052596 spinel Inorganic materials 0.000 description 15
- 239000011029 spinel Substances 0.000 description 15
- 238000000975 co-precipitation Methods 0.000 description 10
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 238000002441 X-ray diffraction Methods 0.000 description 8
- 239000011572 manganese Substances 0.000 description 8
- 239000000843 powder Substances 0.000 description 8
- 229910002651 NO3 Inorganic materials 0.000 description 6
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 6
- 150000004820 halides Chemical class 0.000 description 6
- 239000012071 phase Substances 0.000 description 6
- 239000000376 reactant Substances 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 5
- 239000007789 gas Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000001308 synthesis method Methods 0.000 description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 4
- 229910000859 α-Fe Inorganic materials 0.000 description 4
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- 229910001308 Zinc ferrite Inorganic materials 0.000 description 3
- 159000000021 acetate salts Chemical class 0.000 description 3
- 150000003863 ammonium salts Chemical class 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- WGEATSXPYVGFCC-UHFFFAOYSA-N zinc ferrite Chemical compound O=[Zn].O=[Fe]O[Fe]=O WGEATSXPYVGFCC-UHFFFAOYSA-N 0.000 description 3
- 239000011787 zinc oxide Substances 0.000 description 3
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 2
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 2
- 239000012697 Mn precursor Substances 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 235000002867 manganese chloride Nutrition 0.000 description 2
- 239000011565 manganese chloride Substances 0.000 description 2
- 229940099607 manganese chloride Drugs 0.000 description 2
- 238000000634 powder X-ray diffraction Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 241000894007 species Species 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- 235000005074 zinc chloride Nutrition 0.000 description 2
- 239000011592 zinc chloride Substances 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 241000721701 Lynx Species 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 229940040526 anhydrous sodium acetate Drugs 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- IAQRGUVFOMOMEM-ARJAWSKDSA-N cis-but-2-ene Chemical compound C\C=C/C IAQRGUVFOMOMEM-ARJAWSKDSA-N 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- XNMQEEKYCVKGBD-UHFFFAOYSA-N dimethylacetylene Natural products CC#CC XNMQEEKYCVKGBD-UHFFFAOYSA-N 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- IAQRGUVFOMOMEM-ONEGZZNKSA-N trans-but-2-ene Chemical compound C\C=C\C IAQRGUVFOMOMEM-ONEGZZNKSA-N 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 239000006200 vaporizer Substances 0.000 description 1
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- B01J35/19—
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/0006—Catalysts containing parts with different compositions
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/005—Spinels
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/06—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of zinc, cadmium or mercury
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/745—Iron
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
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- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/009—Preparation by separation, e.g. by filtration, decantation, screening
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C11/00—Aliphatic unsaturated hydrocarbons
- C07C11/12—Alkadienes
- C07C11/16—Alkadienes with four carbon atoms
- C07C11/167—1, 3-Butadiene
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
- C07C5/327—Formation of non-aromatic carbon-to-carbon double bonds only
- C07C5/333—Catalytic processes
- C07C5/3332—Catalytic processes with metal oxides or metal sulfides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
- C07C2523/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36
- C07C2523/80—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36 with zinc, cadmium or mercury
Abstract
본 기재는 부텐의 산화적 탈수소화 반응 촉매, 이의 제조방법 및 부타디엔의 제조방법에 관한 것으로, 보다 상세하게는 하기 화학식 1로 표시되는 금속 산화물로, 부텐의 산화적 탈수소화 반응에 사용되는 반응 촉매, 이의 제조방법 및 부타디엔의 제조방법에 관한 것이다.
[화학식 1]
AxZn1 - xFe2O4
(상기 A는 Cu, Ra, Ba, Sr, Ca, Be, Fe(Ⅱ), Mg, Mn, Co, Ni, Al, Cr, Si, V, Ga, In, La 및 Ce로 이루어진 군으로부터 선택된 1종 이상이고, 상기 x는 0≤x<1을 만족한다.)
본 기재에 따르면, 철과 아연 금속 이의의 금속을 포함하면서도 균일한 입도 분포를 갖고, 종래기술 대비 낮은 온도에서 높은 반응성을 가지며, 또한 이로 인해 높은 부타디엔 수율, 촉매 수명 연장 및 에너지 비용 저감 효과를 가져오는 부텐의 산화적 탈수소화 반응 촉매, 이의 제조방법 및 이를 이용한 부타디엔의 제조방법을 제공하는 효과가 있다. The present description relates to a catalyst for oxidative dehydrogenation of butene, a method for preparing the same, and a method for preparing butadiene, and more particularly, a metal oxide represented by the following formula (1), a reaction catalyst used in the oxidative dehydrogenation reaction of butene , It relates to a method for producing the same, and a method for producing butadiene.
[Formula 1]
A x Zn 1 - x Fe 2 O 4
(A is 1 selected from the group consisting of Cu, Ra, Ba, Sr, Ca, Be, Fe(II), Mg, Mn, Co, Ni, Al, Cr, Si, V, Ga, In, La, and Ce Species or more, and x satisfies 0≦x<1.)
According to the present description, it has a uniform particle size distribution while containing metals of iron and zinc metals, and has high reactivity at a lower temperature compared to the prior art, and thereby has a high butadiene yield, extended catalyst life, and reduced energy cost. Coming has an effect of providing a catalyst for oxidative dehydrogenation of butene, a method for producing the same, and a method for producing butadiene using the same.
Description
본 기재는 부텐의 산화적 탈수소화 반응 촉매, 이의 제조방법 및 이를 이용한 부타디엔의 제조방법에 관한 것으로, 보다 상세하게는 철과 아연 금속 이의의 금속을 포함하면서도 균일한 입도 분포를 갖고, 종래기술 대비 낮은 온도에서 높은 반응성을 가지며, 또한 이로 인해 높은 부타디엔 수율, 촉매 수명 연장 및 에너지 비용 저감 효과를 가져오는 부텐의 산화적 탈수소화 반응 촉매, 이의 제조방법 및 이를 이용한 부타디엔의 제조방법에 관한 것이다. The present disclosure relates to a catalyst for oxidative dehydrogenation of butene, a method for preparing the same, and a method for producing butadiene using the same, and in more detail, it has a uniform particle size distribution while including metals of iron and zinc metals, compared to the prior art. The present invention relates to a catalyst for oxidative dehydrogenation of butene that has high reactivity at a low temperature, and thus results in high butadiene yield, prolonged catalyst life, and reduced energy cost, a method for preparing the same, and a method for producing butadiene using the same.
종래에 부텐의 산화탈수소화 반응을 통한 부타디엔 제조를 위해 페라이트 계열 촉매를 사용하였다. Conventionally, a ferrite catalyst was used to prepare butadiene through oxidative dehydrogenation of butene.
상기 페라이트 계열의 촉매, 특히 아연페라이트 촉매는 공침법을 이용하여 합성하는데, 수율 개선 등을 목적으로 아연과 철 이외의 금속을 추가로 첨가할 경우 균일한 ZnFe2O4 상를 얻기 어려워 오히려 전환율과 선택도가 감소하는 현상이 있었다. The ferrite catalyst, especially zinc ferrite catalyst, is synthesized using a coprecipitation method.When a metal other than zinc and iron is added for the purpose of improving the yield, it is difficult to obtain a uniform ZnFe 2 O 4 phase. There was a phenomenon that the degree decreased.
또한, 공침법으로 합성된 페라이트 계열의 촉매는 높은 반응온도로 인하여 촉매 수명이 짧고 에너지 비용이 크다는 단점이 있었다.In addition, the ferrite-based catalyst synthesized by the co-precipitation method has a disadvantage in that the catalyst life is short and the energy cost is high due to the high reaction temperature.
따라서, 아연과 철 이외의 금속을 추가하여도 균일한 입자를 가지는 촉매를 제조하여, 부타디엔 수율을 개선하고, 종래 기술 대비 낮은 온도에서도 높은 반응성을 가지는 촉매 개발이 필요한 실정이다.Accordingly, there is a need to develop a catalyst having uniform particles even when metals other than zinc and iron are added to improve butadiene yield, and to develop a catalyst having high reactivity even at a lower temperature than in the prior art.
상기와 같은 종래기술의 문제점을 해결하고자, 본 기재는 철과 아연 금속 이의의 금속을 포함하면서도 균일한 입도 분포를 갖고, 종래기술 대비 낮은 온도에서도 높은 반응성을 가지며, 또한 이로 인해 높은 부타디엔 수율, 촉매 수명 연장 및 에너지 비용 저감 효과를 가져오는 부텐의 산화적 탈수소화 반응 촉매, 이의 제조방법 및 이를 이용한 부타디엔의 제조방법을 제공하는 것을 목적으로 한다. In order to solve the problems of the prior art as described above, the substrate has a uniform particle size distribution while containing metals of iron and zinc metals, and has high reactivity even at a lower temperature than the prior art, and thus, a high butadiene yield, a catalyst An object of the present invention is to provide a catalyst for oxidative dehydrogenation of butene, which has an effect of extending life and reducing energy costs, a method for preparing the same, and a method for producing butadiene using the same.
본 기재의 상기 목적 및 기타 목적들은 하기 설명된 본 기재에 의하여 모두 달성될 수 있다.All of the above and other objects of the present description can be achieved by the present description described below.
상기의 목적을 달성하기 위하여, 본 기재는 하기 화학식 1로 표시되는 금속 산화물로, 부텐의 산화적 탈수소화 반응에 사용되는 반응 촉매를 제공한다.In order to achieve the above object, the present disclosure provides a reaction catalyst used in the oxidative dehydrogenation reaction of butene as a metal oxide represented by the following formula (1).
[화학식 1][Formula 1]
AxZn1 - xFe2O4 A x Zn 1 - x Fe 2 O 4
(상기 A는 Cu, Ra, Ba, Sr, Ca, Be, Fe(Ⅱ), Mg, Mn, Co, Ni, Al, Cr, Si, V, Ga, In, La 및 Ce로 이루어진 군으로부터 선택된 1종 이상이고, 상기 x는 0≤x<1을 만족한다.)(A is 1 selected from the group consisting of Cu, Ra, Ba, Sr, Ca, Be, Fe(II), Mg, Mn, Co, Ni, Al, Cr, Si, V, Ga, In, La, and Ce Species or more, and x satisfies 0≦x<1.)
또한, 본 기재는 ⅰ) Fe(Ⅲ) 전구체, Zn 전구체 및 A 전구체를 몰비 2:x-1:x(여기에서 x는 0≤x<1을 만족한다)로 끓는점이 99 내지 250 ℃인 유기용매에 Fe3+의 몰 농도가 0.05 내지 10 mol/L가 되도록 투입하고 녹여 반응액을 제조하는 단계; ⅱ) 상기 반응액을 200 내지 300 ℃ 하에서 3 내지 12 시간 동안 반응시키는 용매열 반응 단계; 및 ⅲ) 상기 용매열 반응 후 반응 생성물을 분리, 세척 및 건조하는 단계;를 포함하는 것을 특징으로 하는 부텐의 산화적 탈수소화 반응 촉매의 제조방법을 제공한다. In addition, the present substrate is an organic material having a boiling point of 99 to 250°C in a molar ratio of 2:x-1:x (where x satisfies 0≦x<1), i) a Fe(III) precursor, a Zn precursor, and a precursor A. Injecting and dissolving Fe 3+ in a solvent so that the molar concentration is 0.05 to 10 mol/L to prepare a reaction solution; Ii) a solvate reaction step of reacting the reaction solution at 200 to 300° C. for 3 to 12 hours; And iii) separating, washing, and drying the reaction product after the solvent heat reaction.
또한, 본 기재는 부텐을 포함하는 원료 물질을 촉매 하에 산화적 탈수소화 반응시켜 부타디엔을 제조하되, 상기 촉매는 본 기재의 산화적 탈수소화 반응 촉매인 것을 특징으로 하는 부타디엔의 제조방법을 제공한다.In addition, the present disclosure provides a method for producing butadiene by subjecting a raw material containing butene to an oxidative dehydrogenation reaction under a catalyst to produce butadiene, wherein the catalyst is an oxidative dehydrogenation reaction catalyst according to the present disclosure.
본 기재에 따르면 철과 아연 금속 이의의 금속을 포함하면서도 균일한 입도 분포를 갖고, 종래기술 대비 낮은 온도에서 높은 반응성을 가지며, 또한 이로 인해 높은 부타디엔 수율, 촉매 수명 연장 및 에너지 비용 저감 효과를 가져오는 부텐의 산화적 탈수소화 반응 촉매, 이의 제조방법 및 이를 이용한 부타디엔의 제조방법을 제공하는 효과가 있다. According to the present description, it has a uniform particle size distribution while containing metals of iron and zinc metals, and has high reactivity at a lower temperature compared to the prior art, and this results in high butadiene yield, extension of catalyst life, and energy cost reduction. There is an effect of providing a catalyst for oxidative dehydrogenation of butene, a method for producing the same, and a method for producing butadiene using the same.
도 1 내지 5는 각각 실시예 1-2 및 비교예 1-3에서 제조된 페라이트계 촉매의 XRD 데이터이다.1 to 5 are XRD data of the ferritic catalysts prepared in Examples 1-2 and 1-3, respectively.
이하 본 기재의 부텐의 산화적 탈수소화 반응 촉매, 이의 제조방법 및 이를 이용한 부타디엔의 제조방법을 상세하게 설명한다. Hereinafter, the catalyst for oxidative dehydrogenation of butene of the present disclosure, a method for preparing the same, and a method for preparing butadiene using the same will be described in detail.
본 발명자들은 용매열 합성법으로 합성한 페라이트계 촉매를 부텐의 산화적 탈수소화 반응에 적용하는 경우, 종래 합성법인 공침법으로 제조한 페라이트계 촉매 대비 높은 전환율, 부타디엔 수율 및 선택도를 얻을 수 있을 뿐만 아니라, 상대적으로 저온의 반응온도에서도 높은 촉매 활성을 유지하며, 촉매 내에 Zn와 Fe 이외의 금속 원소를 추가하여도 반응성이 저하되지 않음을 확인하고, 이를 토대로 연구에 더욱 매진한 결과 본 기재를 완성하게 되었다. When the present inventors apply the ferritic catalyst synthesized by the solvent heat synthesis method to the oxidative dehydrogenation reaction of butene, it is possible to obtain a higher conversion rate, butadiene yield and selectivity compared to the ferritic catalyst prepared by the conventional coprecipitation method. In addition, it was confirmed that high catalytic activity was maintained even at a relatively low temperature reaction, and the reactivity did not decrease even when metal elements other than Zn and Fe were added to the catalyst. Was done.
본 기재의 부텐의 산화적 탈수소화 반응 촉매는 하기 화학식 1로 표시되는 금속 산화물을 포함하는 것을 특징으로 한다.The catalyst for oxidative dehydrogenation of butene of the present disclosure is characterized in that it contains a metal oxide represented by the following formula (1).
[화학식 1][Formula 1]
AxZn1 - xFe2O4 A x Zn 1 - x Fe 2 O 4
(상기 A는 Cu, Ra, Ba, Sr, Ca, Be, Fe(Ⅱ), Mg, Mn, Co, Ni, Al, Cr, Si, V, Ga, In, La 및 Ce로 이루어진 군으로부터 선택된 1종 이상이고, 상기 x는 0≤x<1을 만족한다.)(A is 1 selected from the group consisting of Cu, Ra, Ba, Sr, Ca, Be, Fe(II), Mg, Mn, Co, Ni, Al, Cr, Si, V, Ga, In, La, and Ce Species or more, and x satisfies 0≦x<1.)
본 기재의 부텐의 산화적 탈수소화 반응 촉매의 제조방법은 ⅰ) Fe(Ⅲ) 전구체, Zn 전구체 및 A 전구체를 금속 기준 몰비 2:x-1:x(여기에서 x는 0≤x<1을 만족한다.)로 끓는점이 190 내지 250 ℃인 유기용매에 Fe3 +의 몰 농도가 0.05 내지 10 mol/L가 되도록 투입하고 녹여 반응액을 제조하는 단계; ⅱ) 상기 반응액을 200 내지 300 ℃ 하에서 3 내지 12 시간 동안 반응시키는 용매열 반응 단계; 및 ⅲ) 상기 용매열 반응 후 반응 생성물을 분리, 세척 및 건조하는 단계;를 포함하는 것을 특징으로 한다.The preparation method of the catalyst for oxidative dehydrogenation of butene of the present disclosure includes: i) Fe(III) precursor, Zn precursor, and A precursor in a metal-based molar ratio of 2:x-1:x (where x is 0≦x<1). To prepare a reaction solution by adding and dissolving Fe 3 + so that the molar concentration of Fe 3 + is 0.05 to 10 mol/L in an organic solvent having a boiling point of 190 to 250 °C; Ii) a solvate reaction step of reacting the reaction solution at 200 to 300° C. for 3 to 12 hours; And iii) separating, washing and drying the reaction product after the solvent heat reaction.
상기 반응 촉매는 일례로 스피넬상(AFe2O4) 70 내지 99.9 중량%, 산화철(∝-Fe2O3) 0 내지 20 중량%, 및 산화아연(ZnO) 0 내지 10 중량%를 포함할 수 있고, 이 범위 내에서 촉매 활성이 뛰어난 효과가 있다.The reaction catalyst may include, for example, spinel phase (AFe 2 O 4 ) 70 to 99.9 wt%, iron oxide (∝-Fe 2 O 3 ) 0 to 20 wt%, and zinc oxide (ZnO) 0 to 10 wt% And there is an effect excellent in catalytic activity within this range.
또 다른 예로, 상기 금속 산화물은 스피넬상(AFe2O4) 80 내지 99.9 중량%, 산화철(∝-Fe2O3) 0.1 내지 11 중량%, 및 산화아연(ZnO) 0 내지 9 중량%를 포함할 수 있고, 이 범위 내에서 부타디엔 선택도가 높은 효과가 있다.In another example, the metal oxide comprises a spinel phase (AFe 2 O 4 ) 80 to 99.9 wt%, iron oxide (∝-Fe 2 O 3 ) 0.1 to 11 wt%, and zinc oxide (ZnO) 0 to 9 wt% In this range, butadiene selectivity has a high effect.
또 다른 예로, 상기 금속 산화물은 스피넬상(AFe2O4) 98 내지 99.9 중량%, 산화철(∝-Fe2O3) 0.1 내지 2 중량%, 및 산화아연(ZnO) 0 중량%를 포함할 수 있고, 이 범위 내에서 부타디엔 선택도가 높은 효과가 있다.In another example, the metal oxide may include spinel phase (AFe 2 O 4 ) 98 to 99.9 wt%, iron oxide (∝-Fe 2 O 3 ) 0.1 to 2 wt%, and zinc oxide (ZnO) 0 wt% In addition, there is an effect of high butadiene selectivity within this range.
상기 A는 바람직하게는 Mn, Ni 및 Cu로 이루어진 군으로부터 선택된 1종 이상이고, 보다 바람직하게는 Mn이며, 이 경우 부텐으로부터 부타디엔 제조 시 전환율, 부타디엔 수율 및 선택도가 뛰어난 효과가 있다.The A is preferably at least one selected from the group consisting of Mn, Ni, and Cu, and more preferably Mn. In this case, the conversion rate, butadiene yield, and selectivity are excellent when preparing butadiene from butene.
상기 x는 바람직하게는 0<x≤1이고, 보다 바람직하게는 0.01≤x≤0.5이며, 가장 바람직하게는 0.01≤x≤0.3이고, 이 범위 내에서 아연 대체 효과 및 높은 촉매 활성이 우수한 효과가 있다.The x is preferably 0<x≦1, more preferably 0.01≦x≦0.5, most preferably 0.01≦x≦0.3, and within this range, the effect of replacing zinc and high catalytic activity is excellent. have.
본 기재에서 x값은 금속 산화물 촉매의 원소분석에 의해 측정하거나, 금속 원소의 유실이 거의 없어 금속 전구체의 투입량을 환산하여 측정할 수 있다.In the present description, the x value can be measured by elemental analysis of a metal oxide catalyst, or by converting the input amount of the metal precursor since there is little loss of the metal element.
이하에 본 기재의 부텐의 산화적 탈수소화 반응 촉매의 제조방법을 단계별로 상세히 살펴본다.Hereinafter, a method for preparing the catalyst for oxidative dehydrogenation of butene according to the present disclosure will be described in detail step by step.
ⅰ) 반응액 제조 단계Ⅰ) Step of preparing reaction solution
상기 Fe(Ⅲ) 전구체는 일례로 옥살레이트염(oxalate), 아세테이트염(acetate), 아세틸아세토네이트(acetylacetonate), 질산염(nitrate), 암모늄염(ammonium salt), 황산염(sulfate) 및 할로젠화물(halide)로부터 선택된 1종 이상일 수 있고, 바람직하게는 질산염, 할로젠화물 또는 아세테이트염이며, 이 경우 용매열 반응이 용이한 효과가 있다.The Fe(III) precursor is, for example, oxalate, acetate, acetylacetonate, nitrate, ammonium salt, sulfate, and halide. ) May be one or more selected from, preferably a nitrate, a halide, or an acetate salt, and in this case, the solvent heat reaction has an easy effect.
상기 Zn 전구체는 일례로 옥살레이트염(oxalate), 아세테이트염(acetate), 아세틸아세토네이트(acetylacetonate), 질산염(nitrate), 암모늄염(ammonium salt), 황산염(sulfate) 및 할로젠화물(halide)로부터 선택된 1종 이상일 수 있고, 바람직하게는 질산염, 할로젠화물 또는 아세테이트염이며, 이 경우 용매열 반응이 용이한 효과가 있다.The Zn precursor is selected from, for example, oxalate, acetate, acetylacetonate, nitrate, ammonium salt, sulfate, and halide. It may be one or more, and preferably a nitrate, a halide, or an acetate salt, and in this case, there is an effect that the solvent heat reaction is easy.
상기 A 전구체는 일례로 옥살레이트염(oxalate), 아세테이트염(acetate), 아세틸아세토네이트(acetylacetonate), 질산염(nitrate), 암모늄염(ammonium salt), 황산염(sulfate) 및 할로젠화물(halide)로부터 선택된 1종 이상일 수 있고, 바람직하게는 질산염, 할로젠화물 또는 아세테이트염이며, 이 경우 용매열 반응이 용이한 효과가 있다.The A precursor is selected from, for example, oxalate, acetate, acetylacetonate, nitrate, ammonium salt, sulfate, and halide. It may be one or more, and preferably a nitrate, a halide, or an acetate salt, and in this case, there is an effect that the solvent heat reaction is easy.
상기 x는 일례로 0<x<1, 0.01≤x<0.5, 또는 0.01≤x<0.3일 수 있고, 이 범위 내에서 Zn Fe2O4의 스피넬 구조가 유지되면서 선택도가 증가하는 효과가 있다.The x may be, for example, 0<x<1, 0.01≦x<0.5, or 0.01≦x<0.3, and there is an effect of increasing selectivity while maintaining the spinel structure of Zn Fe2O4 within this range.
상기 용매는 일례로 에틸렌 글리콜, 1,4-부탄디올, 벤질알콜 및The solvent is, for example, ethylene glycol, 1,4-butanediol, benzyl alcohol, and
헥산올로부터 선택된 1종 이상일 수 있고, 이 경우 ZnFe2O4 구조 형성에 용이한 효과가 있다.It may be one or more selected from hexanol, and in this case, there is an easy effect in forming a ZnFe 2 O 4 structure.
상기 유기용매에 Fe3 +의 몰 농도는 일례로 0.01 내지 30 mol/L, 0.05 내지 20 mol/L, 또는 0.01 내지 10 mol/L일 수 있고, 이 범위 내에서 ZnFe2O4 입자가 형성되기 용이한 효과가 있다. The molar concentration of Fe 3 + in the organic solvent may be, for example, 0.01 to 30 mol/L, 0.05 to 20 mol/L, or 0.01 to 10 mol/L, and within this range, ZnFe2O4 particles are easily formed. There is.
상기 반응액은 일례로 상온, 20 내지 25 ℃, 또는 22 내지 23 ℃에서 모든 전구체를 투입한 후, 교반 속도 50 내지 400 rpm, 60 내지 3 00 rpm, 또는 100 내지 200 rpm로, 2 내지 36 시간, 3 내지 24 시간, 또는 5 내지 12 시간 동안 교반하여 완전히 용해시켜 제조할 수 있고, 이 경우 용매열 반응이 용이한 효과가 있다.The reaction solution is, for example, after adding all the precursors at room temperature, 20 to 25 °C, or 22 to 23 °C, stirring
ⅱ) Ii) 용매열Solvent heat 반응 단계 Reaction stage
상기 용매열 반응은 일례로 100 내지 350 ℃, 150 내지 320 ℃, 또는 200 내지 300 ℃ 하에서 1 내지 36 시간, 2 내지 24 시간, 또는 3 내지 12 동안 실시할 수 있고, 이 범위 내에서 고체 입자 형성에 용이한 효과가 있다.The solvate reaction may be carried out for 1 to 36 hours, 2 to 24 hours, or 3 to 12 hours under 100 to 350°C, 150 to 320°C, or 200 to 300°C, for example, and solid particles are formed within this range. Has an easy effect on.
상기 용매열 반응이 종료된 후 반응 생성물을 5 내지 50 ℃, 또는 20After the solvate reaction is completed, the reaction product is 5 to 50°C, or 20
내지 35 ℃로 특별한 처리 없이 반응물을 상온에 방치하여 냉각시킬 수 있고, 이 경우 고체 입자 형성에 용이한 효과가 있다.The reactant can be cooled by allowing it to stand at room temperature without any special treatment at to 35° C., and in this case, there is an easy effect in forming solid particles.
ⅲ) 후처리 단계(분리, 세척 및 건조 단계)Iii) Post-treatment steps (separation, washing and drying steps)
상기 분리는 일례로 원심 분리기를 사용하여 실시하는 것일 수 있고, 이 경우 분리 효율 및 부산물 제거율이 높은 효과가 있다.The separation may be performed using a centrifugal separator as an example, and in this case, there is an effect of high separation efficiency and by-product removal rate.
상기 세척은 일례로 물, 에탄올, 아세톤 및 이소프로필알콜로부터 선택된 1종 이상으로 실시할 수 있고, 바람직하게는 물 또는 에탄올이며, 이 경우 불순물은 잘 씻겨 나가면서도 촉매 손실은 최소화되는 효과가 있다.The washing may be performed with one or more selected from water, ethanol, acetone and isopropyl alcohol, for example, and preferably water or ethanol, in which case impurities are well washed away while minimizing catalyst loss.
상기 세척은 고형분 100 중량부 대비 세척액 200 내지 2000 중량부 또는 300 내지 1000 중량부로, 1 내지 5 회 또는 2 내지 3 회 실시할 수 있고, 이 범위 내에서 불순물은 잘 씻겨 나가면서도 촉매 손실은 최소화되는 효과가 있다.The washing may be performed 1 to 5 times or 2 to 3 times, with 200 to 2000 parts by weight or 300 to 1000 parts by weight of the washing liquid relative to 100 parts by weight of the solid content, and within this range, impurities are well washed away while minimizing catalyst loss. It works.
상기 건조는 일례로 70 내지 200 ℃에서 3 내지 24 시간 동안 실시할 수 있고, 이 범위 내에서 건조 효율 및 촉매 활성이 우수한 효과가 있다.The drying may be performed at 70 to 200° C. for 3 to 24 hours, for example, and within this range, drying efficiency and catalytic activity are excellent.
또 다른 예로, 상기 건조는 80 내지 150 ℃에서 10 내지 15 시간 동안 실시할 수 있고, 이 범위 내에서 건조 효율이 우수한 효과가 있다.As another example, the drying may be performed at 80 to 150° C. for 10 to 15 hours, and within this range, drying efficiency is excellent.
본 기재의 부타디엔의 제조방법은 부텐을 포함하는 원료 물질을 촉매 하에 산화적 탈수소화 반응시켜 부타디엔을 제조하되, 상기 촉매는 본 기재의 부텐의 산화적 탈수소화 반응 촉매인 것을 특징으로 한다.In the method for producing butadiene of the present disclosure, a raw material including butene is subjected to an oxidative dehydrogenation reaction under a catalyst to produce butadiene, wherein the catalyst is a catalyst for oxidative dehydrogenation of butene according to the present disclosure.
본 기재에서 부텐의 산화적 탈수소화 반응은 금속 산화물 촉매 존재 하에 부텐과 산소가 반응하여 부타디엔과 물을 생성하는 반응을 의미한다.In the present description, the oxidative dehydrogenation reaction of butene refers to a reaction in which butene and oxygen react in the presence of a metal oxide catalyst to produce butadiene and water.
상기 원료 물질은 부텐을 50 부피% 이상 포함하는 원료인 경우 특별히 제한되지 않으나, 일례로 라피네이트일 수 있고, 이 경우 경제성이 우수한 효과가 있다.The raw material is not particularly limited in the case of a raw material containing 50% by volume or more of butene, but may be a raffinate as an example, and in this case, there is an effect of excellent economic efficiency.
상기 산화적 탈수소화 반응은 일례로 산소, 질소 및 스팀을 포함하여 수행될 수 있고, 이 경우 전환율, 부타디엔 수율 및 선택도가 뛰어나고, 반응 장치 운전에 용이한 효과가 있다.The oxidative dehydrogenation reaction may be performed including oxygen, nitrogen, and steam, for example, and in this case, the conversion rate, butadiene yield and selectivity are excellent, and there is an effect that is easy to operate the reaction device.
상기 산소, 질소 및 스팀은 일례로 부피비가 1~10 : 1~10 : 1~10, 또는 1~5 : 1~5 : 1~5일 수 있고, 이 범위 내에서 전환율, 부타디엔 수율 및 선택도가 뛰어나고, 반응 장치 운전에 용이한 효과가 있다.For example, the oxygen, nitrogen and steam may have a volume ratio of 1 to 10: 1 to 10: 1 to 10, or 1 to 5: 1 to 5: 1 to 5, and within this range, the conversion rate, butadiene yield and selectivity Is excellent, and there is an effect that is easy to operate the reaction device.
상기 산화적 탈수소화 반응은 일례로 280 내지 500 ℃, 290 내지 400 ℃, 290 내지 360 ℃, 290 내지 330 ℃, 또는 320 내지 360 ℃에서 실시될 수 있고, 이 범위 내에서 부타디엔으로 전환이 활성화되며 COx로의 부반응이 가장 최소화되어 부텐 전환율 및 부타디엔 선택도가 우수한 효과가 있다.The oxidative dehydrogenation reaction may be carried out at, for example, 280 to 500°C, 290 to 400°C, 290 to 360°C, 290 to 330°C, or 320 to 360°C, and conversion to butadiene is activated within this range. Since side reactions to COx are minimized, the butene conversion rate and butadiene selectivity are excellent.
상기 산화적 탈수소화 반응은 일례로 반응 압력이 10 bar 이하, 5 bar 이하, 0.5 내지 3 bar, 또는 1 내지 3 bar일 수 있다.The oxidative dehydrogenation reaction may be, for example, a reaction pressure of 10 bar or less, 5 bar or less, 0.5 to 3 bar, or 1 to 3 bar.
상기 산화적 탈수소화 반응은 일례로 기체공간속도(GHSV)가 반응물(원료 물질 + 산소) 기준 20 내지 1000 h-1, 50 내지 750 h-1, 80 내지 650 h-1, 또는 450 내지 650 h-1일 수 있다.The oxidative dehydrogenation reaction is, for example, the gas space velocity (GHSV) based on the reactant (raw material + oxygen) 20 to 1000 h -1 , 50 to 750 h -1 , 80 to 650 h -1 , or 450 to 650 h May be -1.
상기 산화적 탈수소화 반응에서 부텐 전환율이 일례로 25 % 이상, 60 % 이상, 75 % 이상, 80 % 이상, 또는 85 % 이상일 수 있다.In the oxidative dehydrogenation reaction, the butene conversion rate may be 25% or more, 60% or more, 75% or more, 80% or more, or 85% or more, for example.
상기 산화적 탈수소화 반응에서 1,3-부타디엔 선택도는 일례로 80 %이상, 85 % 이상, 또는 88 % 이상일 수 있다.In the oxidative dehydrogenation reaction, the 1,3-butadiene selectivity may be, for example, 80% or more, 85% or more, or 88% or more.
상기 산화적 탈수소화 반응에 사용되는 반응기는 산화적 탈수소화 반응에 사용될 수 있는 반응기인 경우 특별히 제한되지 않으나, 일례로 설치된 촉매층의 반응온도가 일정하게 유지되고, 반응물이 촉매층을 연속적으로 통과하면서 산화적 탈수소화 반응이 진행되는 반응기일 수 있고, 구체적인 예로, 관형 반응기, 조형 반응기, 유동상 반응기 또는 고정상 반응기일 수 있으며, 상기 고정상 반응기는 일례로 다관식 반응기 또는 플레이트식 반응기일 수 있다.The reactor used for the oxidative dehydrogenation reaction is not particularly limited if it is a reactor that can be used for the oxidative dehydrogenation reaction, but as an example, the reaction temperature of the installed catalyst layer is kept constant, and the reactants are oxidized while continuously passing through the catalyst layer. It may be a reactor in which the red dehydrogenation reaction proceeds, and a specific example may be a tubular reactor, a tank reactor, a fluidized bed reactor or a fixed bed reactor, and the fixed bed reactor may be, for example, a multi-tubular reactor or a plate reactor.
이하, 본 기재의 이해를 돕기 위하여 바람직한 실시예를 제시하나, 하기 실시예는 본 기재를 예시하는 것일 뿐 본 기재의 범주 및 기술사상 범위 내에서 다양한 변경 및 수정이 가능함은 당업자에게 있어서 명백한 것이며, 이러한 변형 및 수정이 첨부된 특허청구범위에 속하는 것도 당연한 것이다.Hereinafter, preferred embodiments are presented to aid in the understanding of the present description, but the following examples are only illustrative of the present description, and that various changes and modifications are possible within the scope of the present description and the scope of the technical idea will be apparent to those skilled in the art, It is natural that such modifications and modifications fall within the appended claims.
[실시예][Example]
실시예Example 1 ( One ( ZnFeZnFe 22 OO 44 을of 용매열Solvent heat 합성법으로 제조) Manufactured by synthetic method)
2.646g 염화철 및 0.642g 염화아연을 6 0ml 에틸렌 글리콜과 혼합한 다음 충분히 교반하였다. 이때 용액 중에 Fe3 + 몰 농도는 0 .15 mol/L이다.2.646 g iron chloride and 0.642 g zinc chloride were mixed with 60 ml ethylene glycol and then sufficiently stirred. At this time, the molar concentration of Fe 3 + in the solution is 0 .15 mol/L.
상기 용액에 다시 11g 무수 아세트산 나트륨을 첨가하고, 회전 속도 500 rpm으로 30분 동안 교반기를 이용하여 완전히 용해시킨 다음, 내구성을 가지는 용기에 옮겨 담고 밀폐한 후, 200 ℃에서 12 시간 동안 300 rpm으로 교반하면서 반응시켰다.11g anhydrous sodium acetate was again added to the solution, completely dissolved with a stirrer at a rotation speed of 500 rpm for 30 minutes, transferred to a durable container, sealed, and stirred at 200° C. for 12 hours at 300 rpm. While reacting.
상기 반응 후 원심분리기로 액상을 제거한 다음, 증류수와 무수 에틸알코올로 각각 1회씩 세척하였고, 이후 남은 고형분을 80 ℃ 하에서 12 시간 동안 건조하여 ZnFe2O4 분말을 얻었다. 수득된 ZnFe2O4 분말은 X선 회절 패턴으로부터 스피넬 구조(스피넬상 98 몰%와 산화철 2 몰%)를 가지는 것을 확인하였다(하기 도 1 참조).After the reaction, the liquid phase was removed with a centrifuge, and then washed once each with distilled water and anhydrous ethyl alcohol, and then the remaining solid was dried at 80° C. for 12 hours to obtain ZnFe 2 O 4 powder. It was confirmed that the obtained ZnFe 2 O 4 powder had a spinel structure (98 mol% spinel and 2 mol% iron oxide) from the X-ray diffraction pattern (see FIG. 1 below).
실시예Example 2 ( 2 ( MnxZnMnxZn 1One -- xx FeFe 22 OO 44 을of 용매열Solvent heat 합성법으로 제조) Manufactured by synthetic method)
상기 실시예 1에서 Mn 전구체로 염화망간을 0.12 g 더 투입한 것을 제외하고는 상기 실시예 1과 동일한 방법으로 실시하여 Mn1 - xZnxFe2O4(여기에서 x는 0.8이다) 분말을 얻었다. 수득된 Mn1 - xZnxFe2O4 분말은 X선 회절 패턴으로부터 스피넬 구조(스피넬상 89 몰%와 산화철 11 몰%)를 가지는 것을 확인하였다(하기 도 2 참조).The (a, where x is 0.8) x Zn x Fe 2 O 4 powder with manganese chloride to a Mn precursor in Example 1, 0.12 g, and is carried out as Example 1 except that no input by Mn 1 Got it. The resulting Mn 1 - x Zn x Fe 2 O 4 spinel structure powder X-ray diffraction pattern was found to have the (spinel phase 89 mol% of iron oxide and 11 mol%) (see Figure 2).
비교예Comparative example 1 ( One ( ZnFeZnFe 22 OO 44 을of 공침법으로By coprecipitation 제조) Produce)
제1단계로서, 염화아연(ZnCl2,6H2O) 3.5g 및 염화제이철(FeCl3) 14g을 증류수 250ml에 용해시켜 철-금속 전구체 수용액 267.6g을 준비하였다.As a first step, 3.5 g of zinc chloride (ZnCl 2 , 6H 2 O) and 14 g of ferric chloride (FeCl 3 ) were dissolved in 250 ml of distilled water to prepare 267.6 g of an iron-metal precursor aqueous solution.
이때, 상기 철-금속 전구체 수용액에 포함된 금속 성분들의 원자수 비는 Fe:Zn=2:1이었다.At this time, the atomic ratio of the metal components included in the iron-metal precursor aqueous solution was Fe:Zn=2:1.
제2단계로서, 물 250 ml가 채워진 공침조에 상기 철-금속 전구체 수용액을 투입한 다음, 여기에 농도 25%의 암모니아수 5 g을 투입하고, 이후 공침이 충분히 이루어지도록 1시간 동안 교반 스터러를 사용하여 교반하였다.As a second step, the iron-metal precursor aqueous solution was added to a coprecipitation tank filled with 250 ml of water, and then 5 g of ammonia water having a concentration of 25% was added thereto, and then a stirring stirrer was used for 1 hour to sufficiently coprecipitate. And stirred.
이후, 공침 용액을 감압 여과기를 이용하여 감압 여과하여 여과액을 배출하고, 잔류 여과물을 수세 후처리를 수행하지 않고 철-금속 산화물의 슬러리를 수득하였다.Thereafter, the coprecipitation solution was filtered under reduced pressure using a vacuum filter to discharge the filtrate, and the residual filtrate was not washed with water and a slurry of iron-metal oxide was obtained.
제3단계로서, 상기 철-금속 산화물의 슬러리를 90 ℃에서 16시간 동안 건조한 뒤, 건조된 공침물을 소성로에 넣어 650 ℃의 온도에서 6시간 동안 열처리하여 ZnFe2O4 분말을 얻었다. 수득된 ZnFe2O4 분말은 X선 회절 패턴으로부터 스피넬 구조(스피넬상 96 몰%와 산화철 4 몰%)를 가지는 것을 확인하였다(하기 도 3 참조).As a third step, the iron-metal oxide slurry was dried at 90° C. for 16 hours, and then the dried co-precipitate was put in a sintering furnace and heat-treated at 650° C. for 6 hours to obtain ZnFe2O4 powder. It was confirmed that the obtained ZnFe 2 O 4 powder had a spinel structure (96 mol% spinel and 4 mol% iron oxide) from the X-ray diffraction pattern (see FIG. 3 below).
비교예Comparative example 2 ( 2 ( MnxZn1MnxZn1 -- xFe2O4을xFe2O4 공침법으로By coprecipitation 제조) Produce)
상기 비교예 1에서 Mn 전구체로 염화망간을 1.1 g 더 투입한 것을 제외하고는 상기 실시예 1과 동일한 방법으로 실시하여 Mn1 - xZnxFe2O4(여기에서 x는 0.8이다) 분말을 얻었다. 수득된 Mn1 - xZnxFe2O4 분말은 X선 회절 패턴으로부터 스피넬 구조(스피넬상 76 몰%와 산화철 24 몰%)를 가지는 것을 확인하였다(하기 도 4 참조). In Comparative Example 1, Mn 1 - x Zn x Fe 2 O 4 (where x is 0.8) powder was carried out in the same manner as in Example 1, except that 1.1 g of manganese chloride was further added as the Mn precursor. Got it. The resulting Mn 1 - x Zn x Fe 2 O 4 spinel structure powder X-ray diffraction pattern was found to have the (spinel phase 76 mol% of iron oxide and 24 mol%) (see Figure 4).
비교예Comparative example 3( 3( ZnFeZnFe 22 OO 44 을of 용매열합성법으로By solvent thermosynthesis 제조) Produce)
상기 실시예 1에서 Zn 와 Fe의 전구체로 질산아연 0.88g, 질산철 2.4g을 사용한 것을 제외하고는 상기 실시예 1과 동일한 방법으로 실시하여 ZnFe2O4 분말을 얻었다. 수득된 ZnFe2O4 분말은 X선 회절 패턴으로부터 스피넬 구조(스피넬상 91 몰%와 산화아연 7 몰%와 산화철 1.8 몰%)를 가지는 것을 확인하였다(하기 도 5 참조). In Example 1, ZnFe 2 O 4 powder was obtained in the same manner as in Example 1, except that 0.88 g of zinc nitrate and 2.4 g of iron nitrate were used as precursors of Zn and Fe. It was confirmed that the obtained ZnFe 2 O 4 powder had a spinel structure (91 mol% spinel, 7 mol% zinc oxide, and 1.8 mol% iron oxide) from the X-ray diffraction pattern (see FIG. 5 below).
[시험예 1][Test Example 1]
상기 실시예 1-2 및 비교예 1-3에서 제조된 페라이트계 촉매의 조성과 구조 및 원소비를 하기의 방법으로 측정하였고, 그 결과를 하기 도 1 내지 5 및 표 1에 각각 나타내었다.The composition, structure, and element ratio of the ferritic catalysts prepared in Examples 1-2 and 1-3 were measured by the following method, and the results are shown in FIGS. 1 to 5 and Table 1, respectively.
* 촉매 구조: 상기 실시예와 비교예에서 제조한 촉매의 구조적 특징을 비교 분석하기 위하여, X선 회절분석(XRD)을 실시하였으며, X선 회절분석은 Bruker AXS D4 E ndeavor XRD (전압 40 kV, 전류 40mA, Cu-target tube, 파장 1.5418Å, Lynx Eye posi tion sen sitive d etector (3. 7° slit))을 사용하였으며 FDS 0.5를 이용, 2 theta 5~80 도 영역을 매 0.02도 마다 1초씩 측정하였다.* Catalyst structure: In order to compare and analyze the structural characteristics of the catalysts prepared in Examples and Comparative Examples, X-ray diffraction analysis (XRD) was performed, and X-ray diffraction analysis was performed by Bruker AXS D4 E ndeavor XRD (voltage 40 kV, Current 40mA, Cu-target tube, wavelength 1.5418Å, Lynx Eye posi tion sensor (3. 7° slit)) was used, and FDS 0.5 was used, 2 theta 5~80 degrees for 1 second every 0.02 degrees. It was measured.
상기 표 1에 나타낸 바와 같이, 본 기재에 따른 용매열 합성법으로 제조된 페라이트계 촉매(실시예 1, 2)는 종래의 공침법에 의해 제조된 페라이트계 촉매(비교예 1, 2) 대비 합성 과정 중 금속 이온의 손실이 적으며, 스피넬상 구조의 함유율이 높은 것을 확인할 수 있었다.As shown in Table 1, the ferritic catalyst prepared by the solvent heat synthesis method according to the present disclosure (Examples 1 and 2) was synthesized compared to the ferritic catalyst prepared by the conventional coprecipitation method (Comparative Examples 1 and 2). It was confirmed that the loss of heavy metal ions was small, and the content rate of the spinel structure was high.
또한, 용매열 합성법으로 제조되되 망간, 즉 제3의 금속을 포함하지 않는 페라이트계 촉매(비교예 3)는 ZnO 함량이 크게 증가하는 것을 확인할 수 있었다.In addition, it was confirmed that the ZnO content was significantly increased in the ferritic catalyst (Comparative Example 3) prepared by the solvent heat synthesis method but did not contain manganese, that is, a third metal.
[시험예 2][Test Example 2]
상기 실시예 1 및 2에서 용매열 합성법에 의해 합성된 페라이트계 촉매와 비교예 1 및 2에서 공침법에 의해 합성된 페라이트계 촉매를 사용하여 하기 산화적 탈수소화 반응을 거쳐 부타디엔을 생성하였으며, 그 결과를 하기 표 2에 나타내었다.Using the ferritic catalyst synthesized by the solvent heat synthesis method in Examples 1 and 2 and the ferritic catalyst synthesized by the coprecipitation method in Comparative Examples 1 and 2, butadiene was produced through the following oxidative dehydrogenation reaction. The results are shown in Table 2 below.
반응기로서 지름 1.8 cm의 금속 관형 반응기에 실시예 또는 비교예에서 제조된 촉매를 촉매층 부피 30cc로 고정하고, 반응물로 시스-2-부텐 40 중량%, 트랜스-2-부텐 60 중량%의 2-부텐 혼합물과 산소를 사용하였고 질소와 스팀을 유입시켰다. 상기 반응물 비는 산소/부텐 0.75, 스팀/부텐 12 및 질소/부텐 3의 몰비로 셋팅하였고, 스팀은 물을 340 ℃의 기화기에서 기화시켜 반응물과 함께 반응기에 유입시켰다.As a reactor, the catalyst prepared in Examples or Comparative Examples was fixed in a catalyst bed volume of 30 cc in a metal tubular reactor having a diameter of 1.8 cm, and as reactants, cis-2-butene 40% by weight and trans-2-butene 60% by weight 2-butene A mixture and oxygen were used, and nitrogen and steam were introduced. The reactant ratio was set to a molar ratio of oxygen/butene 0.75, steam/butene 12, and nitrogen/butene 3, and steam was introduced into the reactor together with the reactants by vaporizing water in a vaporizer at 340°C.
부텐 혼합물의 양은 액체용 질량유속조절기를 사용하여 0.625 cc/min으로 제어하였고, 산소 및 질소는 기체용 질량유속조절기를 사용하여 제어하였으며, 스팀의 양은 액체 펌프를 이용해 주입 속도를 제어하였다. 상기 반응기의 기상 공간속도(GHSV, gas hourly space velocity)는 500 h-1로 설정하고 상압(압력 게이지 0), 표 2에 개시된 온도의 조건하에 반응시켰다.The amount of the butene mixture was controlled at 0.625 cc/min using a liquid mass flow controller, oxygen and nitrogen were controlled using a gas mass flow controller, and the amount of steam was controlled using a liquid pump. The gas hourly space velocity (GHSV, gas hourly space velocity) of the reactor was set to 500 h -1 and reacted under the conditions of atmospheric pressure (pressure gauge 0) and the temperature disclosed in Table 2.
반응 후 생성물을 가스 크로마토그래피(GC)로 분석하였고, 혼합물 내각 부텐의 전환율(X), 1,3-부타디엔 선택도(S-BD), 1,3-부타디엔 수율(Y), CO2 선택도(S_CO2), 및 CO 선택도(S_CO)를 하기 수식 1 내지 5에 따라 계산하였다.After the reaction, the product was analyzed by gas chromatography (GC), and the conversion of butene in the mixture (X), 1,3-butadiene selectivity (S-BD), 1,3-butadiene yield (Y), CO 2 selectivity (S_CO 2 ), and CO selectivity (S_CO) were calculated according to Equations 1 to 5 below.
[수학식 1][Equation 1]
전환율(%)=(반응한 부텐의 몰수/공급된 부텐의 몰수)x100Conversion rate (%) = (number of moles of reacted butene/number of moles of supplied butene) x 100
[수학식 2][Equation 2]
부타디엔 선택도(%)=(생성된 1,3-부타디엔의 몰수/반응한 부텐의 몰수)x100Butadiene selectivity (%) = (number of moles of 1,3-butadiene produced/number of moles of reacted butene) x 100
[수학식 3][Equation 3]
수율(%)=(생성된 1,3-부타디엔의 몰수/공급된 부텐의 몰수)x100Yield (%) = (number of moles of 1,3-butadiene produced/number of moles of supplied butene) x 100
[수학식 4][Equation 4]
CO2 선택도(%)=(생성된 CO2의 몰수/반응한 부텐의 몰수)x100CO 2 selectivity (%) = (number of moles of CO 2 produced/number of moles of reacted butene) x 100
[수학식 5][Equation 5]
CO 선택도(%)=(생성된 CO의 몰수/반응한 부텐의 몰수)x100CO selectivity (%) = (number of moles of CO produced/number of moles of reacted butene) x 100
상기 표 1에 나타낸 바와 같이, 본 기재에 따른 용매열 반응으로 제조된 페라이트계 촉매를 사용하여 부타디엔을 제조하는 경우(실시예 1, 2) 종래의 공침법에 의해 제조된 페라이트계 촉매(비교예 1, 2)를 사용하는 경우 대비 부텐 전환율, 부타디엔 선택도 및 수율이 월등히 우수하고, 특히 낮은 온도에서도 높은 촉매 활성 및 반응성을 가짐을 확인할 수 있었다.As shown in Table 1 above, in the case of preparing butadiene using a ferritic catalyst prepared by a solvent heat reaction according to the present disclosure (Examples 1 and 2), a ferritic catalyst prepared by a conventional coprecipitation method (Comparative Example Compared to the case of using 1 and 2), it was confirmed that the butene conversion rate, butadiene selectivity, and yield were remarkably excellent, and in particular, it had high catalytic activity and reactivity even at low temperatures.
Claims (14)
ⅱ) 상기 반응액을 200 내지 300 ℃ 하에서 3 내지 12 시간 동안 반응시키는 용매열 반응 단계; 및
ⅲ) 상기 용매열 반응 후 반응 생성물을 분리, 세척 및 건조하는 단계;를 포함하되,
상기 Fe(Ⅲ) 전구체, Zn 전구체 및 A 전구체는 각각 염화물이고,
하기 화학식 1로 표시되는 금속 산화물을 포함하는 것을 특징으로 하는
부텐의 산화적 탈수소화 반응 촉매의 제조방법.
[화학식 1]
AxZn1-xFe2O4
(상기 A는 Cu, Ra, Ba, Sr, Ca, Be, Fe(Ⅱ), Mg, Mn, Co, Ni, Al, Cr, Si, V, Ga, In, La 및 Ce로 이루어진 군으로부터 선택된 1종 이상이고, 상기 x는 0<x<1을 만족한다.)
Ⅰ) Fe(III) precursor, Zn precursor, and A precursor are respectively mixed in a molar ratio of 2:x-1:x (where x satisfies 0<x<1) in an organic solvent having a boiling point of 190 to 250°C. Adding and dissolving the molar concentration of 3+ to be 0.05 to 10 mol/L to prepare a reaction solution;
Ii) a solvate reaction step of reacting the reaction solution at 200 to 300° C. for 3 to 12 hours; And
Iii) separating, washing and drying the reaction product after the solvent heat reaction; including,
The Fe(III) precursor, the Zn precursor and the A precursor are each chloride,
Characterized in that it comprises a metal oxide represented by the following formula (1)
Method for producing a catalyst for oxidative dehydrogenation of butene.
[Formula 1]
A x Zn 1-x Fe 2 O 4
(A is 1 selected from the group consisting of Cu, Ra, Ba, Sr, Ca, Be, Fe(II), Mg, Mn, Co, Ni, Al, Cr, Si, V, Ga, In, La, and Ce Is more than a species, and x satisfies 0<x<1.)
상기 용매는 에틸렌 글리콜, 1,4-부탄디올, 벤질알콜 및 헥산올로부터 선택된 1종 이상인 것을 특징으로 하는
부텐의 산화적 탈수소화 반응 촉매의 제조방법.
The method of claim 3,
The solvent is characterized in that at least one selected from ethylene glycol, 1,4-butanediol, benzyl alcohol and hexanol
Method for producing a catalyst for oxidative dehydrogenation of butene.
상기 분리는 원심 분리기를 사용하여 실시하는 것을 특징으로 하는
부텐의 산화적 탈수소화 반응 촉매의 제조방법.
The method of claim 3,
The separation is characterized in that carried out using a centrifugal separator
Method for producing a catalyst for oxidative dehydrogenation of butene.
상기 세척은 물, 에탄올, 아세톤 및 이소프로필알코올로부터 선택된 1종 이상으로 실시하는 것을 특징으로 하는
부텐의 산화적 탈수소화 반응 촉매의 제조방법.The method of claim 3,
The washing is characterized in that carried out with one or more selected from water, ethanol, acetone and isopropyl alcohol.
Method for producing a catalyst for oxidative dehydrogenation of butene.
상기 건조는 70 내지 200 ℃에서 3 내지 24 시간 동안 실시하는 것을 특징으로 하는
부텐의 산화적 탈수소화 반응 촉매의 제조방법.
The method of claim 3,
The drying is characterized in that carried out for 3 to 24 hours at 70 to 200 ℃
Method for producing a catalyst for oxidative dehydrogenation of butene.
상기 산화적 탈수소화 반응은 290 내지 330 ℃에서 실시되는 것을 특징으로 하는
부타디엔의 제조방법.
A raw material containing butene is subjected to an oxidative dehydrogenation reaction under a catalyst to produce butadiene, wherein the catalyst is an oxidative dehydrogenation reaction catalyst prepared according to claim 3,
The oxidative dehydrogenation reaction is characterized in that carried out at 290 to 330 ℃
Method for producing butadiene.
상기 원료 물질은 라피네이트인 것을 특징으로 하는
부타디엔의 제조방법.
The method of claim 11,
The raw material is characterized in that the raffinate
Method for producing butadiene.
상기 산화적 탈수소화 반응은 산소, 질소 및 스팀을 포함하여 수행되는 것을 특징으로 하는
부타디엔의 제조방법.
The method of claim 11,
The oxidative dehydrogenation reaction is characterized in that it is carried out including oxygen, nitrogen and steam
Method for producing butadiene.
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