KR20120008989A - Method for producing 1,2-Propylene glycol using bio-glycerin - Google Patents
Method for producing 1,2-Propylene glycol using bio-glycerin Download PDFInfo
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- KR20120008989A KR20120008989A KR1020100070544A KR20100070544A KR20120008989A KR 20120008989 A KR20120008989 A KR 20120008989A KR 1020100070544 A KR1020100070544 A KR 1020100070544A KR 20100070544 A KR20100070544 A KR 20100070544A KR 20120008989 A KR20120008989 A KR 20120008989A
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- propylene glycol
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- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 title claims abstract description 92
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 28
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims abstract description 81
- 239000003054 catalyst Substances 0.000 claims abstract description 46
- 238000006243 chemical reaction Methods 0.000 claims abstract description 44
- 235000011187 glycerol Nutrition 0.000 claims abstract description 40
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 15
- 150000004706 metal oxides Chemical group 0.000 claims abstract description 15
- 239000000126 substance Substances 0.000 claims abstract description 10
- 239000002243 precursor Substances 0.000 claims description 29
- 229910052751 metal Inorganic materials 0.000 claims description 22
- 239000002184 metal Substances 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 19
- 239000000243 solution Substances 0.000 claims description 15
- 239000000843 powder Substances 0.000 claims description 12
- 239000012691 Cu precursor Substances 0.000 claims description 9
- 239000007864 aqueous solution Substances 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 238000005984 hydrogenation reaction Methods 0.000 claims description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 239000012695 Ce precursor Substances 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 238000010304 firing Methods 0.000 claims description 4
- 229910001960 metal nitrate Inorganic materials 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 3
- 229960004063 propylene glycol Drugs 0.000 claims 10
- 239000003225 biodiesel Substances 0.000 abstract description 5
- -1 1,2-propylene Chemical group 0.000 abstract description 3
- 239000006227 byproduct Substances 0.000 abstract description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 abstract 4
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 abstract 4
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 abstract 2
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 abstract 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 12
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 11
- 239000011651 chromium Substances 0.000 description 10
- 239000010949 copper Substances 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 239000002994 raw material Substances 0.000 description 6
- 239000011787 zinc oxide Substances 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
- 229910052802 copper Inorganic materials 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 238000006722 reduction reaction Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 229910052804 chromium Inorganic materials 0.000 description 3
- 239000002638 heterogeneous catalyst Substances 0.000 description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 238000010531 catalytic reduction reaction Methods 0.000 description 2
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 2
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002431 hydrogen Chemical group 0.000 description 2
- NJTGANWAUPEOAX-UHFFFAOYSA-N molport-023-220-454 Chemical compound OCC(O)CO.OCC(O)CO NJTGANWAUPEOAX-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000035484 reaction time Effects 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
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 239000004909 Moisturizer Substances 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- RFHOKFXRZASHTN-UHFFFAOYSA-N [Ce].[Cu].[Zr] Chemical compound [Ce].[Cu].[Zr] RFHOKFXRZASHTN-UHFFFAOYSA-N 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 230000002528 anti-freeze Effects 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- XUZDJUDKWXESQE-UHFFFAOYSA-N chromium copper zinc Chemical compound [Cr].[Zn].[Cu] XUZDJUDKWXESQE-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-NJFSPNSNSA-N chromium-54 Chemical compound [54Cr] VYZAMTAEIAYCRO-NJFSPNSNSA-N 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000003925 fat Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000000887 hydrating effect Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 229910001463 metal phosphate Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000001333 moisturizer Effects 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- UJVRJBAUJYZFIX-UHFFFAOYSA-N nitric acid;oxozirconium Chemical compound [Zr]=O.O[N+]([O-])=O.O[N+]([O-])=O UJVRJBAUJYZFIX-UHFFFAOYSA-N 0.000 description 1
- 150000002826 nitrites Chemical class 0.000 description 1
- 230000009965 odorless effect Effects 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- VSZWPYCFIRKVQL-UHFFFAOYSA-N selanylidenegallium;selenium Chemical compound [Se].[Se]=[Ga].[Se]=[Ga] VSZWPYCFIRKVQL-UHFFFAOYSA-N 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 230000009967 tasteless effect Effects 0.000 description 1
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
- C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
- C07C29/14—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group
- C07C29/141—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group with hydrogen or hydrogen-containing gases
-
- 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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
- B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
-
- 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
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
-
- 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
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/86—Chromium
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C31/00—Saturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
- C07C31/18—Polyhydroxylic acyclic alcohols
- C07C31/20—Dihydroxylic alcohols
-
- 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
본 발명은 바이오 글리세린으로 1,2-프로필렌 글리콜을 제조하는 방법에 관한 것으로, 보다 상세하게는 반응 원료로 글리세린의 함유량이 82%이하인 바이오 글리세린에 신규한 비균질 촉매를 적용한 고정층 반응기를 도입하여 높은 수율 및 낮은 비용으로 제조되는 1,2-프로필렌 글리콜의 제조방법에 관한 것이다. The present invention relates to a method for producing 1,2-propylene glycol from bioglycerin, and more particularly, by introducing a fixed bed reactor in which a novel heterogeneous catalyst is applied to bioglycerin having a glycerin content of 82% or less as a reaction raw material, high yield. And a process for producing 1,2-propylene glycol produced at low cost.
근래, 지구 온난화를 억제하는 대책의 하나로서, 식물 또는 동물의 유지를 원료로 한 바이오 디젤(bio diesel)이라고 불리고 있는 디젤엔진(diesel-engine)용 연료가 개발되고 있다. 바이오 디젤(bio diesel)의 제조 과정에서는 글리세린(glycerin)이 원료 유지에 대하여 약 10%정도 부생하고 있고, 그 글리세린(lycerin)의 유효 활용이 활발하게 연구 되고 있다.In recent years, as a countermeasure against global warming, a fuel for diesel-engine called bio diesel, which is derived from fats and oils of plants or animals, has been developed. In the manufacturing process of biodiesel, glycerin (glycerin) is by-produced by about 10% in the maintenance of raw materials, and the effective utilization of the glycerin (lycerin) has been actively studied.
한편, 프로필렌 글리콜(propylene glycol)은 글리세린(glycerin)의 수산기 하나가 수소로 치환되는 화합물이지만, 생물에서 독성이 낮고 무미, 무취여서 보습제, 윤활제, 유화제, 부동액, 용매 등으로 사용되며, 넓게는 의약품이나 화장품, 식료품 등의 분야에서 사용된다. 일반적으로 프로필렌 글리콜(propylene glycol)은 화석 원료인 석유로부터 유도되는 프로필렌(propylene)을 산화하여 프로필렌옥시드를 만들고 그것을 수화하여 제조된다.On the other hand, propylene glycol is a compound in which one hydroxyl group of glycerin is replaced with hydrogen, but it is low toxicity and tasteless and odorless in living organisms, so it is used as a moisturizer, lubricant, emulsifier, antifreeze, solvent, etc. It is also used in the fields of cosmetics and foodstuffs. In general, propylene glycol is prepared by oxidizing propylene derived from petroleum, a fossil raw material, to produce propylene oxide and hydrating it.
여기에서, 상기의 글리세린(glycerin)의 유효 활용에 관해서, 각종 촉매를 사용하고 글리세린(glycerin)을 프로필렌 글리콜(propylene glycol)에 변환하는 것이 알려져 있다. 예를 들면, 코발트(cobalt), 구리(copper), 망간(manganese), 몰리브덴(molybdenum)의 촉매를 사용하고 20중량%이하의 물을 포함하는 글리세린(glycerin)을 촉매적 수소화 반응하여 프로필렌 글릴콜(propylene glycol)을 제조하는 방법이 미국 특허 제5616817호에 기재되어 있다. 그러나 200~250℃의 온도, 200~325bar(20~32.5Mpa)의 압력으로 반응을 실시한 것으로, 고온 및 고압에 의해 장치 운전의 안정성 면에서 불리하다.Here, it is known to convert glycerin into propylene glycol using various catalysts with respect to the above-mentioned effective utilization of glycerin. For example, propylene glycol is obtained by catalytic hydrogenation of glycerin containing up to 20% by weight of water using a catalyst of cobalt, copper, manganese and molybdenum. A process for preparing (propylene glycol) is described in US Pat. No. 5616817. However, the reaction was carried out at a temperature of 200 to 250 ° C. and a pressure of 200 to 325 bar (20 to 32.5 Mpa), which is disadvantageous in terms of stability of device operation due to high temperature and high pressure.
또한, 산화구리 및 산화 아연을 포함하는 촉매의 존재하에 글리세린(glycerin)과 수소를 반응시키고 글리세린(glycerin)을 프로필렌 글리콜(proplyeneglycol) 및 에틸렌 글리콜(ethylene glycol)로 변환하는 방법이 미국특허 제 5214219호에 기재되어 있다. In addition, a method of reacting glycerin with hydrogen in the presence of a catalyst containing copper oxide and zinc oxide and converting glycerin into propylene glycol and ethylene glycol is disclosed in US Pat. No. 5,214,219. It is described in.
유럽 특허출원 공개 제0523015호 공보에는 Cu/Zn 촉매에 의한 글리세린의 수소 첨가가 기재되어 있지만, 그때 상당히 희석되는 수용액을 이용하여 실시하고 있다. 그러므로 1,2-프로필렌 글리콜의 생산을 위해서는 제품으로부터 대량의 물을 제거하지 않으면 안되고, 이것은 높은 에너지 소비를 의미하기 때문에 비경제적인 방법이 된다. European Patent Application Publication No. 0523015 describes hydrogenation of glycerin with a Cu / Zn catalyst, but is carried out using an aqueous solution which is significantly diluted at that time. Therefore, a large amount of water must be removed from the product for the production of 1,2-propylene glycol, which is an uneconomical method because it means high energy consumption.
또한, 팔라듐(palladium), 니켈(nickel), 로듐(rhodium), 구리(copper), 아연, 크롬(chrome) 및 그것들을 혼합한 그룹으로부터 선택되는 촉매의 존재하에 150~250℃의 온도, 1~25bar(0.1~2.5MPa)의 압력, 2~96시간의 반응시간, 원료 글리세린(glycerin) 수용액의 농도가 50중량%이상인 것과 비교적 온화한 조건으로 반응을 하는 방법에 미국 특허출원 공개 제2005/0244312호에 기재되어 있다. 그러나, 이러한 조건에서는 반응 시간을 길게 해도 원료 글리세린(glycerin)의 변환율이 낮고 프로필렌 글리콜(propylene glycol)의 수율도 낮아, 효율성 면에서 불리하며, 반응 과정은 소위 반응증류식조형 반응 프로세스여서 반응기 내에 경시적으로 축적되는 반응 잔사 및 떨어진 촉매 등을 계속적으로 골라내는 조작이 필요하여 장기적인 연속 운전에는 불리하다는 단점이 있다.In addition, in the presence of a catalyst selected from the group consisting of palladium, nickel, rhodium, copper, zinc, chromium and mixtures thereof, a temperature of 150 to 250 ° C, 1 to 1 U.S. Patent Application Publication No. 2005/0244312 for pressures of 25 bar (0.1 to 2.5 MPa), reaction time of 2 to 96 hours, concentration of aqueous solution of glycerin (glycerin) of 50% by weight or more, and reaction under relatively mild conditions. It is described in. However, under these conditions, even if the reaction time is extended, the conversion rate of the raw glycerin is low and the yield of propylene glycol is low, which is disadvantageous in terms of efficiency, and the reaction process is a reaction distillation type reaction process. There is a disadvantage in that it is disadvantageous for long-term continuous operation because it is necessary to continuously select the reaction residues and catalysts that have accumulated accumulated.
따라서, 본 발명은 전술한 바와 같은 종래 기술의 문제점을 개선하기 위한 것으로서, 본 발명의 목적은 바이오 디젤 생산 시 부생되는 미정제의 글리세린을 사용하여 신규한 비균질 촉매 존재 하에 고정층 반응기를 도입하여 수소화 반응하는 것으로, 신규한 비균질 촉매로서 구리-아연-크롬 또는 구리-세륨-지르코늄의 삼성분계 촉매를 사용하여 글리세린의 전환율을 높이고, 1,2-프로필렌 글리콜에 대한 선택도를 높이므로서 경제성 있게 대량생산 할 수 있는 1,2-프로필렌 글리콜의 제조방법을 제공하는 것이다.Accordingly, the present invention is to improve the problems of the prior art as described above, an object of the present invention is to introduce a hydrogenation reaction by introducing a fixed bed reactor in the presence of a novel heterogeneous catalyst using crude glycerin by-produced in the production of biodiesel As a novel heterogeneous catalyst, a ternary catalyst of copper-zinc-chromium or copper-cerium-zirconium is used to increase the conversion of glycerin and increase the selectivity to 1,2-propylene glycol, thereby mass production economically. It is to provide a method for producing 1,2-propylene glycol.
상기 목적을 달성하기 위하여 본 발명은 구리계 촉매의 존재 하에서 글리세린을 기상 수소화 반응하여 1,2-프로필렌 글리콜을 제조하는 방법을 제공하고자 한다.In order to achieve the above object, the present invention is to provide a method for producing 1,2-propylene glycol by gas phase hydrogenation of glycerin in the presence of a copper-based catalyst.
본 발명의 촉매를 이용하여 글리세린으로부터 수소화 반응에 의한 1,2-프로필렌 글리콜을 제조함에 있어서, 부 반응물의 생성물을 억제하며, 글리세린의 전환율, 1,2-프로필렌 글리콜의 선택도 및 수율의 효과를 향상시킬 수 있는 방법을 제공하고자 한다.In preparing 1,2-propylene glycol by hydrogenation reaction from glycerin using the catalyst of the present invention, the product of the side reaction product is suppressed, and the effects of the conversion rate of glycerin, the selectivity and yield of 1,2-propylene glycol are affected. We want to provide a way to improve it.
이하, 본 발명을 좀 더 구체적으로 살펴보면 다음과 같다.Hereinafter, the present invention will be described in more detail.
본 발명의 촉매는 하기 화학식 1 또는 화학식 2로 표시되며, 제 1 양태로서 구리(Cu), 아연(Zn) 및 크롬(Cr)으로 이루어진 삼성분계 촉매이거나, 제 2 양태로서 구리(Cu), 세륨(Ce) 및 지르코늄(Zr)으로 이루어진 삼성분계 촉매이다. 즉, 글리세린에 하기 화학식 1 또는 화학식 2로 표시되는 삼성분계 금속 산화물 촉매를 이용하여 제조된 1,2-프로필렌 글리콜의 제조방법에 관한 것이다.The catalyst of the present invention is represented by the following formula (1) or (2), and is a ternary catalyst composed of copper (Cu), zinc (Zn), and chromium (Cr) as a first embodiment, or copper (Cu), cerium as a second embodiment. It is a ternary catalyst consisting of (Ce) and zirconium (Zr). That is, the present invention relates to a method for preparing 1,2-propylene glycol prepared using a ternary metal oxide catalyst represented by Formula 1 or Formula 2 below.
[화학식 1][Formula 1]
[CuO][ZnO][Cr2O3][CuO] [ZnO] [Cr 2 O 3 ]
[화학식 2][Formula 2]
[CuO][CeO2][ZrO2][CuO] [CeO 2 ] [ZrO 2 ]
[상기 화학식 1 에서, 중량비로 CuO : ZnO : Cr2O3는 13-22중량% : 30-40중량% : 42-52 중량%이고;[In Formula 1, CuO: ZnO: Cr 2 O 3 is 13-22% by weight: 30-40% by weight: 42-52% by weight;
상기 화학식 2에서, 중량비로 CuO : CeO2 : ZrO2 는 35-45중량% : 2-12중량% : 48-58중량%이다.]
In Formula 2, CuO: CeO 2 : ZrO 2 is 35-45% by weight: 2-12% by weight: 48-58% by weight.]
본 발명의 상기 화학식 1로 표시되는 촉매는, 더욱 바람직하게 중량비로 CuO : ZnO : Cr2O3가 16-20중량% : 33-37중량% : 45-49 중량%를 갖도록 포함하는 것이 좋다. 본 발명의 촉매에 있어서, 수소화 반응에 효과를 나타내어, 글리세린을 이용하여 1,2-프로필렌 글리콜을 제조하는데 매우 효과적이다.More preferably, the catalyst represented by Chemical Formula 1 of the present invention includes CuO: ZnO: Cr 2 O 3 in a weight ratio of 16-20% by weight: 33-37% by weight: 45-49% by weight. In the catalyst of the present invention, it has an effect on the hydrogenation reaction and is very effective in producing 1,2-propylene glycol using glycerin.
본 발명의 상기 화학식 2로 표시되는 촉매는, 더욱 바람직하게 중량비로 CuO : CeO2 : ZrO2는 38-42중량% : 5-9중량% : 51-55중량%를 갖도록 포함하는 것이 좋다. More preferably, the catalyst represented by Chemical Formula 2 of the present invention includes CuO: CeO 2 : ZrO 2 in a weight ratio of 38-42% by weight: 5-9% by weight: 51-55% by weight.
본 발명은 상기 화학식 1 및 화학식 2로 표시되는 삼성분계 금속 산화물 촉매의 제조방법을 제공한다.The present invention provides a process for preparing a ternary metal oxide catalyst represented by Formula 1 and Formula 2.
본 발명의 상기 화학식 1로 표시되는 삼성분계 금속 산화물 촉매는 Cu 전구체, Cr 전구체 및 Zn 전구체를 Cu 전구체: Cr 전구체 : Zn 전구체 기준으로 23-33중량% : 13-23중량% : 49-59 중량% 의 중량비가 되도록 수용액에 용해시켜 금속 전구체 용액을 제조하는 단계;The ternary metal oxide catalyst represented by Chemical Formula 1 of the present invention is a Cu precursor, Cr precursor, and Zn precursor based on Cu precursor: Cr precursor: Zn precursor 23-33% by weight: 13-23% by weight: 49-59 weight % Preparing a metal precursor solution by dissolving in an aqueous solution so as to have a weight ratio of;
상기 금속 전구체 용액을 건조하여 분말로 제조하는 단계; 및Drying the metal precursor solution to prepare a powder; And
건조된 분말을 300 내지 500℃에서 소성 하는 단계;Firing the dried powder at 300 to 500 ° C .;
로 부터 제조된 것을 특징으로 한다.Characterized in that manufactured from.
즉, 상기 화학식 1의 제조를 위한 금속 전구체 용액은 50 내지 150℃에서 2시간 내지 24시간 동안 건조시킨 후 공기분위기 하에서 300 내지 500℃조건으로 4시간 이상 소성 시킨다.That is, the metal precursor solution for the preparation of Formula 1 is dried for 2 hours to 24 hours at 50 to 150 ℃ and then fired for 4 hours or more under 300 to 500 ℃ conditions in an air atmosphere.
또한 본 발명의 상기 화학식 2로 표시되는 삼성분계 금속 산화물 촉매는 Cu 전구체, Ce 전구체 및 Zr 전구체를 Cu 전구체: Ce 전구체: Zr 전구체 기준으로 32-42중량% : 1-10중량% : 53-63중량%의 중량비가 되도록 수용액에 용해시켜 금속 전구체 용액을 제조하는 단계;In addition, the ternary metal oxide catalyst represented by Chemical Formula 2 of the present invention may include a Cu precursor, a Ce precursor, and a Zr precursor, based on a Cu precursor: Ce precursor: Zr precursor, 32-42 wt%: 1-10 wt%: 53-63 Preparing a metal precursor solution by dissolving in an aqueous solution to a weight ratio of weight percent;
상기 금속 전구체 용액을 건조하여 분말로 제조하는 단계; 및Drying the metal precursor solution to prepare a powder; And
건조된 분말을 300 내지 500℃에서 소성하는 단계;Firing the dried powder at 300 to 500 ° C .;
로 부터 제조되는 것을 특징으로 한다.Characterized in that manufactured from.
즉, 상기 화학식 2의 제조를 위한 금속 전구체 용액은 50 내지 150℃에서 2시간 내지 24시간 동안 건조시킨 후 공기분위기 하에서 300 내지 500℃조건으로 4시간 이상 소성 시킨다.
That is, the metal precursor solution for the preparation of Formula 2 is dried for 2 hours to 24 hours at 50 to 150 ℃ and then fired for 4 hours or more under 300 to 500 ℃ conditions in an air atmosphere.
본 발명에 따른 상기 금속 전구체 용액은 금속 산화물, 금속 질산염, 금속 아질산염, 금속 황산염, 금속 수산화물, 금속 인산염, 금속 할로겐염, 금속 아세트산염 또는 금속 탄산염을 이용하여 제조할 수 있고, 바람직하게는 금속 염산염, 금속 질산염 또는 금속 아세트산염을 들 수 있고, 특히 금속 질산염이 바람직하다.The metal precursor solution according to the present invention may be prepared using metal oxides, metal nitrates, metal nitrites, metal sulfates, metal hydroxides, metal phosphates, metal halide salts, metal acetates or metal carbonates, preferably metal hydrochloride , Metal nitrate or metal acetate, and metal nitrate is particularly preferable.
본 발명의 촉매의 제조방법은 구리 전구체를 포함하는 수용액을 제조하고 여기에 다른 전구체 수용액을 첨가하여 혼합하거나, 또는 상기의 전구체들을 동시에 한꺼번에 혼합하여 제조할 수 있으며, 각 조성물을 고르게 분포할 수 있는 혼합 방법이라면, 공지의 어떠한 방법을 사용하여도 무방하다.
In the method of preparing the catalyst of the present invention, an aqueous solution containing a copper precursor may be prepared and mixed by adding another precursor aqueous solution thereto, or the precursors may be mixed and mixed at the same time, and each composition may be evenly distributed. If it is a mixing method, you may use any well-known method.
또한 본 발명의 원료인 상기 글리세린은 함유량이 82중량% 이하인 바이오 글리세린인 것을 사용하며, 상기 글리세린은 물 10-18 중량%를 더 포함하는 것을 특징으로 한다.In addition, the glycerin which is a raw material of the present invention is a bioglycerin having a content of 82% by weight or less, and the glycerin is characterized in that it further comprises 10-18% by weight of water.
본 발명의 촉매를 이용하여 글리세린을 수소화 반응하여 1,2-프로필렌 글리콜을 제조하는 반응 조건은 하기와 같다.Reaction conditions for producing 1,2-propylene glycol by hydrogenation of glycerin using the catalyst of the present invention are as follows.
본 발명에 따른 삼성분계 금속 산화물 촉매를 200~300℃의 수소 분위기 하에서 환원하는 단계;Reducing the ternary metal oxide catalyst according to the present invention under a hydrogen atmosphere at 200 to 300 ° C .;
상기 환원된 촉매의 존재 하에, 120-250℃의 반응온도 및 1~10 kg/cm2 G의 반응 압력에서 글리세린을 기상 수소화 반응하여 1,2-프로필렌 글리콜을 생성하는 단계를 포함한다.In the presence of the reduced catalyst, gas phase hydrogenation of glycerine at a reaction temperature of 120-250 ° C. and a reaction pressure of 1-10 kg / cm 2 G to produce 1,2-propylene glycol.
즉, 상기 금속 산화물 촉매의 환원 단계는 고정층(Fixed bed) 반응기에 분말 형태로 충진한 후 보다 바람직하게 230~270℃의 온도 및 질소로 희석된 5%수소 분위기 하에서 3~5시간 환원하여 촉매를 활성화 시킨다. That is, the reduction step of the metal oxide catalyst is filled in a fixed bed (Fixed bed) reactor in the form of a powder, and more preferably reduced to 3 to 5 hours under a 5% hydrogen atmosphere diluted with nitrogen and a temperature of 230 ~ 270 ℃ Activate it.
상기 환원된 촉매에 상기 바이오 글리세린을 첨가하여 보다 바람직하게는 반응온도 160-200℃, 반응압력 2 kg/cm2 G 내지 4 kg/cm2 G 및 수소 1,000 sccm(Standard Cubic Centimeter per Minute) 하에서 반응하여 1,2-프로필렌 글리콜의 제조 하였다. 또한 이때 촉매에 대한 글리세린의 무게 공간속도(Weight Hourly Space Velocity, h-1)는 3.12h- 1 로 실시하였다.More preferably, the bioglycerin is added to the reduced catalyst, and the reaction is performed under a reaction temperature of 160-200 ° C., a reaction pressure of 2 kg / cm 2 G to 4 kg / cm 2 G and 1,000 sccm (Standard Cubic Centimeter per Minute) of hydrogen. 1,2-propylene glycol was prepared. Also this time the weight space velocity of the glycerol to the catalyst (Weight Hourly Space Velocity, h -1 ) is 3.12h - it was carried out to 1. The
상기 반응온도는 160-200℃가 더욱 바람직하며, 160℃ 이하이면 반응 전환율이 낮고, 200℃보다 높은 온도에서는 부산물 증가하여 반응 선택도가 낮아진다.The reaction temperature is more preferably 160-200 ° C., if the temperature is 160 ° C. or lower, the reaction conversion rate is low, and at a temperature higher than 200 ° C., by-products increase to decrease the reaction selectivity.
또한 상기 반응온도 및 반응압력의 범위 안에서, 온도 및 압력이 높을수록 글리세린의 전환율 및 1,2-프로필렌 글리콜의 선택도의 결과가 더 높다는 것을 것을 확인할 수 있었다. In addition, it was confirmed that within the range of the reaction temperature and the reaction pressure, the higher the temperature and the pressure, the higher the results of the conversion of glycerin and the selectivity of 1,2-propylene glycol.
또한 본 발명의 압력단위로써 kg/cm2 G를 사용하고, kg/cm2 G는 압력게이지 상의 압력이며, 1kg/cm2 은 0.97 기압(atm)을 의미한다. In addition, kg / cm 2 G is used as the pressure unit of the present invention, kg / cm 2 G is the pressure on the pressure gauge, 1kg / cm 2 means 0.97 atm (atm).
본 발명의 촉매를 이용하여 글리세린으로부터 1,2-프로필렌을 제조한 결과, 글리세린의 전환율은 92-100 몰% 및 1,2-프로필렌 글리콜의 선택도는 70-97 몰%로 얻을 수 있었다. As a result of preparing 1,2-propylene from glycerin using the catalyst of the present invention, the conversion of glycerin was 92-100 mol% and the selectivity of 1,2-propylene glycol was obtained at 70-97 mol%.
본 발명에 따른 바이오 글리세린으로 1,2-프로필렌 글리콜을 제조하는 방법은 바이오 디젤 생산 시 부생되는 미정제의 글리세린을 사용하여 신규한 삼성분계 금속 산화물 촉매 존재 하에 고정층 반응기를 도입하여 수소화 반응하는 것으로, 신규한 삼성분계 금속 산화물 촉매를 사용하므로서 반응의 안정성 및 글리세린의 전환율을 높이고, 1,2-프로필렌 글리콜에 대한 선택도를 높이므로서 경제성 있게 대량생산 할 수 있어 생산효율을 극대화할 수 있다. 또한 원료로 사용되는 글리세린이 미정제의 바이오 글리세린으로서, 원료 사용의 폭을 다양화하여 제품 생산의 제약조건을 최소화하였다. 본 발명에 따른 1,2-프로필렌 글리콜의 제조방법은 기존의 제조방법에 비하여 단시간 내에 복잡한 공정의 변화 없이 용이하게 고수율로 목적물을 생산할 수 있으며, 또한 상업적 규모의 생산에서 공정의 단순화 및 수율의 향상을 얻을 수 있다.Method for producing 1,2-propylene glycol with bioglycerin according to the present invention is to introduce a hydrogenated reaction by introducing a fixed bed reactor in the presence of a novel ternary metal oxide catalyst using crude glycerin by-produced in the production of biodiesel, By using the new ternary metal oxide catalyst, the stability of the reaction and the conversion rate of glycerin are increased, and the selectivity for 1,2-propylene glycol can be increased to economically mass-produce and maximize the production efficiency. In addition, glycerin used as a raw material is a crude bioglycerin, which minimizes the constraints of product production by varying the width of the raw material used. The production method of 1,2-propylene glycol according to the present invention can easily produce the target product in a high yield without a complicated process change in a short time compared to the conventional manufacturing method, and also in the production of commercial scale of the simplification and yield of the process You can get an improvement.
이하, 실시예를 들어 본 발명을 더욱 상세하게 설명하나, 하기 실시예는 본 발명을 예시하기 위한 것으로서, 본 발명이 하기 실시예에 한정되는 것은 아니다.
Hereinafter, the present invention will be described in more detail with reference to Examples, but the following Examples are for illustrating the present invention, and the present invention is not limited to the following Examples.
[실시예 1] Example 1
질산구리(Copper Nitrate) 28 중량%, 질산크롬(Chrome Nitrate) 18 중량%, 질산아연(Zinc Nitrate) 54 중량%을 혼합한 혼합물을 증류수에 용해시켜 금속전구체 용액을 제조한 후, 온도 70℃에서 진공 건조한다. 건조된 분말을 500℃, 공기분위기에서 4시간 동안 소성시킨다. A metal precursor solution was prepared by dissolving a mixture of 28% by weight of copper nitrate, 18% by weight of chromium nitrate, and 54% by weight of zinc nitrate in distilled water to prepare a metal precursor solution. Dry in vacuo. The dried powder is calcined at 500 ° C. in an air atmosphere for 4 hours.
그 결과 얻어진 촉매의 조성은 산화물 형태로 얻어지며 각 성분의 조성비는 CuO 18중량%, ZnO 35중량%, Cr2O3 47중량%였다.The composition of the resulting catalyst was obtained in the form of an oxide, and the composition ratio of each component was 18 wt% CuO, 35 wt% ZnO, and 47 wt% Cr 2 O 3 .
내경 1/24인치 또는 1/2인치(inch) SUS(stanless)재질의 고정층 반응기에 상기의 촉매 5g을 제조된 상태의 분말 형태로 충진한 후, 환원온도 250℃에서 질소로 희석된 5%수소로 4시간 동안 환원반응을 진행하였다. 촉매 환원 후 반응온도 160℃, 촉매에 대한 바이오 글리세린(글리세린 함량: <82 wt%)의 무게 공간속도를 3.12 h-1, 반응압력 2 kg/cm2 G 수소 1,000 sccm을 송입하면서 반응하였다. 생성물은 불꽃이온화 검출기가 부착된 가스크로마토그래피로 분석하였고, 그 결과 글리세린 전환율 92.2 몰%, 1,2-프로필렌 글리콜(PG) 선택도 73.5 몰%를 나타내었다.
5 g of the catalyst was charged in a powder form in a prepared state to a fixed bed reactor made of 1/24 inch or 1/2 inch SUS (stanless) inner diameter, and then 5% hydrogen diluted with nitrogen at a reduction temperature of 250 ° C. Reduction was carried out for 4 hours. The reaction temperature after the reduction of the catalyst 160 ℃, the weight space velocity of the bioglycerin (glycerine content: <82 wt%) to the catalyst 3.12 h -1 , the reaction pressure 2 kg / cm 2 G The reaction was carried out while feeding 1,000 sccm of hydrogen. The product was analyzed by gas chromatography with a flame ionization detector, which showed 92.2 mol% glycerin conversion and 73.5 mol% 1,2-propylene glycol (PG) selectivity.
[실시예 2-6] Example 2-6
실시예 1의 촉매를 사용하여, 촉매 환원 후 반응온도 및 반응압력을 하기 표 1의 조건으로 한 것을 제외하고는 실시예 1과 동일한 방법으로 반응을 수행하였고, 그 결과를 표 1에 나타내었다.
Using the catalyst of Example 1, the reaction was carried out in the same manner as in Example 1 except that the reaction temperature and the reaction pressure after the reduction of the catalyst under the conditions of Table 1, the results are shown in Table 1.
[실시예 7] Example 7
질산구리(Copper Nitrate) 40 중량%, 질산세륨(Cerium Nitrate) 7 중량%, 질산지르코닐( Zirconyl Nitrate Hydrate) 53 중량% 혼합한 혼합물을 증류수에 용해시켜 금속 전구체 용액을 제조한 후에 70℃에서 진공 건조한다. 건조된 분말을 500℃, 공기분위기에서 4시간 동안 소성 시킨다. A mixture of 40% by weight of copper nitrate, 7% by weight of cerium nitrate, and 53% by weight of zirconyl nitrate hydrate was dissolved in distilled water to prepare a metal precursor solution, followed by vacuum at 70 ° C. To dry. The dried powder is calcined at 500 ° C. in an air atmosphere for 4 hours.
열처리에 의해 촉매의 조성은 산화물 형태로 얻어지며 각 금속 성분의 조성비는 CuO 40 중량%, CeO2 7 중량%, ZrO2 53 중량%였다. The composition of the catalyst was obtained in the form of oxide by heat treatment, and the composition ratio of each metal component was 40 wt% CuO, 7 wt% CeO 2 , and 53 wt% ZrO 2 .
촉매 환원 후 반응은 실시예 1과 동일한 방법으로 반응을 수행하였고, 그 결과는 표 1에 나타내었다.
After the catalytic reduction, the reaction was carried out in the same manner as in Example 1, and the results are shown in Table 1.
[실시예 8-12] Example 8-12
실시예 7의 촉매를 사용하여, 촉매 환원 후 반응온도 및 반응압력을 하기 표 1의 조건으로 한 것을 제외하고는 실시예 1과 동일한 방법으로 반응을 수행하였고, 그 결과를 표 1에 나타내었다.
Using the catalyst of Example 7, the reaction was carried out in the same manner as in Example 1, except that the reaction temperature and the reaction pressure after the catalytic reduction were the conditions of Table 1, and the results are shown in Table 1.
본 발명의 실시예에 따른 글리세린의 전환율 및 1,2-프로필렌 글리콜(PG)의 선택도를 표 1 및 표2에 정리하였다.
The conversion rate of glycerin and the selectivity of 1,2-propylene glycol (PG) according to the embodiment of the present invention are summarized in Table 1 and Table 2.
[표 1] 촉매 [CuO][ZnO][Cr2O3]에 따른 실시예 1 내지 실시예 6의 글리세린 전환율 및 PG선택도Table 1 Glycerine Conversion and PG Selectivity of Examples 1 to 6 According to Catalyst [CuO] [ZnO] [Cr 2 O 3 ]
[표 2] 촉매 [CuO][CeO2][ZrO2]에 따른 실시예 7 내지 실시예 12의 글리세린 전환율 및 PG선택도Table 2 Glycerine Conversion and PG Selectivity of Examples 7-12 According to Catalyst [CuO] [CeO 2 ] [ZrO 2 ]
상기 표 1 및 표2의 실시예 결과로부터, 본 발명의 삼성분계 금속 산화물 촉매를 이용하여 제조하면, 글리세린의 전환율을 높이고 1,2-프로필렌 글리콜의 선택성을 높여 제조할 수 있다는 것을 확인할 수 있다.From the results of the examples of Table 1 and Table 2, it can be confirmed that when prepared using the ternary metal oxide catalyst of the present invention, the conversion of glycerin and the selectivity of 1,2-propylene glycol can be increased.
Claims (9)
[화학식 1]
[CuO][ZnO][Cr2O3]
[화학식 2]
[CuO][CeO2][ZrO2]
[상기 화학식 1에서, 중량비로 CuO : ZnO : Cr2O3는 13-22중량% : 30-40중량% : 42-52 중량%이고;
상기 화학식 2에서, 중량비로 CuO : CeO2 : ZrO2 는 35-45중량% : 2-12중량% : 48-58중량%이다.]Method for preparing 1,2-propylene glycol prepared using glycerin based metal oxide catalyst represented by the following formula (1) or (2).
[Formula 1]
[CuO] [ZnO] [Cr 2 O 3 ]
(2)
[CuO] [CeO 2 ] [ZrO 2 ]
[In Formula 1, CuO: ZnO: Cr 2 O 3 is 13-22% by weight: 30-40% by weight: 42-52% by weight in the weight ratio;
In Formula 2, CuO: CeO 2 : ZrO 2 is 35-45% by weight: 2-12% by weight: 48-58% by weight.]
상기 화학식 1에서 중량비로 CuO : ZnO : Cr2O3는 16-20중량% : 33-37중량% : 45-49 중량%인 것을 특징으로 하는 1,2-프로필렌 글리콜의 제조방법.The method of claim 1,
CuO: ZnO: Cr 2 O 3 in the weight ratio in the formula 1 is 16-20% by weight: 33-37% by weight: 45-49% by weight of the production method of 1,2-propylene glycol.
상기 화학식 2에서 중량비로 CuO : CeO2 : ZrO2는 38-42중량% : 5-9중량% : 51-55중량%인 것을 특징으로 하는 1,2-프로필렌 글리콜의 제조방법. The method of claim 1,
Formula 2 in a weight ratio of CuO in: CeO 2: ZrO 2 is 38-42% by weight: 5-10% by weight: 51-55 of a method for producing 1, 2-propylene glycol, characterized in that% by weight.
상기 화학식 1로 표시되는 삼성분계 금속 산화물 촉매는 Cu 전구체, Cr 전구체 및 Zn 전구체를 Cu 전구체: Cr 전구체 : Zn 전구체 기준으로 23-33중량% : 13-23중량% : 49-59 중량% 의 중량비가 되도록 수용액에 용해시켜 금속 전구체 용액을 제조하는 단계;
상기 금속 전구체 용액을 건조하여 분말로 제조하는 단계; 및
건조된 분말을 300 내지 500℃에서 소성하는 단계;
로 부터 제조된 것을 특징으로 하는 1,2-프로필렌 글리콜의 제조방법.The method of claim 1,
The ternary metal oxide catalyst represented by Chemical Formula 1 may include a Cu precursor, a Cr precursor, and a Zn precursor, based on a Cu precursor: Cr precursor: Zn precursor, 23-33 wt%: 13-23 wt%: 49-59 wt% Preparing a metal precursor solution by dissolving in an aqueous solution so as to have a weight ratio of;
Drying the metal precursor solution to prepare a powder; And
Firing the dried powder at 300 to 500 ° C .;
Method for producing 1,2-propylene glycol, characterized in that prepared from.
상기 화학식 2로 표시되는 삼성분계 금속 산화물 촉매는 Cu 전구체, Ce 전구체 및 Zr 전구체를 Cu 전구체: Ce 전구체: Zr 전구체 기준으로 32-42중량% : 1-10중량% : 53-63중량%의 중량비가 되도록 수용액에 용해시켜 금속 전구체 용액을 제조하는 단계;
상기 금속 전구체 용액을 건조하여 분말로 제조하는 단계; 및
건조된 분말을 300 내지 500℃에서 소성하는 단계;
로 부터 제조된 것을 특징으로 하는 1,2-프로필렌 글리콜의 제조방법.The method of claim 1,
The ternary metal oxide catalyst represented by Chemical Formula 2 may include a Cu precursor, a Ce precursor, and a Zr precursor in a weight ratio of 32-42 wt%: 1-10 wt%: 53-63 wt% based on Cu precursor: Ce precursor: Zr precursor Dissolving in aqueous solution to prepare a metal precursor solution;
Drying the metal precursor solution to prepare a powder; And
Firing the dried powder at 300 to 500 ° C .;
Method for producing 1,2-propylene glycol, characterized in that prepared from.
상기 금속 전구체 용액은 금속 질산염을 이용하여 제조되는 것을 특징으로 하는 1,2-프로필렌 글리콜의 제조방법.The method according to claim 4 or 5,
The metal precursor solution is a method for producing 1,2-propylene glycol, characterized in that prepared using metal nitrate.
상기 글리세린은 함유량이 82중량% 이하인 바이오 글리세린인 것을 특징으로 하는 1,2-프로필렌 글리콜의 제조방법.The method of claim 1,
The glycerin is a method for producing 1,2-propylene glycol, characterized in that the content is bioglycerin of 82% by weight or less.
상기 글리세린은 물 10-18 중량%를 더 포함하는 것을 특징으로 하는 1,2-프로필렌 글리콜의 제조방법.The method of claim 7, wherein
The glycerin is a method for producing 1,2-propylene glycol, characterized in that it further comprises 10-18% by weight of water.
상기 삼성분계 금속 산화물 촉매를 200~300℃의 수소 분위기 하에서 환원하는 단계;
상기 환원된 촉매의 존재 하에, 120-250℃의 반응온도 및 1~10 kg/cm2 G의 반응압력에서 글리세린을 기상 수소화 반응하여 1,2-프로필렌 글리콜을 생성하는 것을 특징으로 하는 1,2-프로필렌 글리콜의 제조방법.The method of claim 1,
Reducing the ternary metal oxide catalyst under a hydrogen atmosphere at 200 ° C. to 300 ° C .;
1,2 characterized in that 1,2-propylene glycol is produced by gas phase hydrogenation of glycerin at a reaction temperature of 120-250 ° C. and a reaction pressure of 1-10 kg / cm 2 G in the presence of the reduced catalyst. Process for the preparation of propylene glycol.
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| KR101533541B1 (en) * | 2014-12-19 | 2015-07-03 | 성균관대학교산학협력단 | Metal catalyst loaded in the mixed metal oxide support comprising ceria-zirconia for preparing glycols from sorbitol |
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| US20090156866A1 (en) * | 2007-12-13 | 2009-06-18 | Lanzhou Institute of Chemical Physics, Chinese Academy of Science | Method for producing 1,2-propylene glycol using bio-based glycerol |
| WO2009151021A1 (en) * | 2008-06-13 | 2009-12-17 | 三井化学株式会社 | Method for producing propylene glycol |
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| WO2009151021A1 (en) * | 2008-06-13 | 2009-12-17 | 三井化学株式会社 | Method for producing propylene glycol |
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| KR101386077B1 (en) * | 2013-02-25 | 2014-04-16 | 조선대학교산학협력단 | Preparation method of methanol from glyceline by liquid phase catalytic radical reaction |
| KR101533541B1 (en) * | 2014-12-19 | 2015-07-03 | 성균관대학교산학협력단 | Metal catalyst loaded in the mixed metal oxide support comprising ceria-zirconia for preparing glycols from sorbitol |
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