JP6267238B2 - グリセリン脱水反応用触媒、その製造方法およびアクロレインの製造方法 - Google Patents
グリセリン脱水反応用触媒、その製造方法およびアクロレインの製造方法 Download PDFInfo
- Publication number
- JP6267238B2 JP6267238B2 JP2015557962A JP2015557962A JP6267238B2 JP 6267238 B2 JP6267238 B2 JP 6267238B2 JP 2015557962 A JP2015557962 A JP 2015557962A JP 2015557962 A JP2015557962 A JP 2015557962A JP 6267238 B2 JP6267238 B2 JP 6267238B2
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- zeolite
- dehydration reaction
- glycerin
- acrolein
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 title claims description 174
- 239000003054 catalyst Substances 0.000 title claims description 94
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 title claims description 92
- 238000006297 dehydration reaction Methods 0.000 title claims description 63
- 238000004519 manufacturing process Methods 0.000 title claims description 36
- 235000011187 glycerol Nutrition 0.000 claims description 73
- 239000002184 metal Substances 0.000 claims description 54
- 229910052751 metal Inorganic materials 0.000 claims description 54
- 229910021536 Zeolite Inorganic materials 0.000 claims description 48
- 239000010457 zeolite Substances 0.000 claims description 46
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 41
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 37
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 20
- 150000003467 sulfuric acid derivatives Chemical class 0.000 claims description 11
- 230000018044 dehydration Effects 0.000 claims description 10
- -1 CuSO 4 Substances 0.000 claims description 8
- 150000002739 metals Chemical class 0.000 claims description 8
- 239000007809 chemical reaction catalyst Substances 0.000 claims description 5
- 239000006069 physical mixture Substances 0.000 claims 1
- 238000000034 method Methods 0.000 description 27
- 238000006243 chemical reaction Methods 0.000 description 25
- 230000000052 comparative effect Effects 0.000 description 21
- 239000000203 mixture Substances 0.000 description 21
- 239000006227 byproduct Substances 0.000 description 16
- 239000000843 powder Substances 0.000 description 15
- 239000004570 mortar (masonry) Substances 0.000 description 14
- 238000001354 calcination Methods 0.000 description 13
- XLSMFKSTNGKWQX-UHFFFAOYSA-N hydroxyacetone Chemical compound CC(=O)CO XLSMFKSTNGKWQX-UHFFFAOYSA-N 0.000 description 13
- 239000003153 chemical reaction reagent Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 229910052791 calcium Inorganic materials 0.000 description 5
- 239000011575 calcium Substances 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 5
- 229910017052 cobalt Inorganic materials 0.000 description 5
- 239000010941 cobalt Substances 0.000 description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 5
- 229910052802 copper Inorganic materials 0.000 description 5
- 239000010949 copper Substances 0.000 description 5
- 229910052742 iron Inorganic materials 0.000 description 5
- 229910052725 zinc Inorganic materials 0.000 description 5
- 239000011701 zinc Substances 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- 229910004298 SiO 2 Inorganic materials 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 229910000365 copper sulfate Inorganic materials 0.000 description 3
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 3
- 239000002803 fossil fuel Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000003225 biodiesel Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000013537 high throughput screening Methods 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 1
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000005341 cation exchange Methods 0.000 description 1
- 235000015872 dietary supplement Nutrition 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000006052 feed supplement Substances 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- AVFBYUADVDVJQL-UHFFFAOYSA-N phosphoric acid;trioxotungsten;hydrate Chemical compound O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O AVFBYUADVDVJQL-UHFFFAOYSA-N 0.000 description 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 235000013772 propylene glycol Nutrition 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
- B01J29/46—Iron group metals or copper
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/053—Sulfates
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/053—Sulfates
- B01J27/055—Sulfates with alkali metals, copper, gold or silver
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/064—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof containing iron group metals, noble metals or copper
- B01J29/072—Iron group metals or copper
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
- B01J29/7215—Zeolite Beta
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
- B01J29/76—Iron group metals or copper
- B01J29/7615—Zeolite Beta
-
- 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
- B01J37/0027—Powdering
- B01J37/0036—Grinding
-
- 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
- B01J37/04—Mixing
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/51—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition
- C07C45/52—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition by dehydration and rearrangement involving two hydroxy groups in the same molecule
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C47/00—Compounds having —CHO groups
- C07C47/20—Unsaturated compounds having —CHO groups bound to acyclic carbon atoms
- C07C47/21—Unsaturated compounds having —CHO groups bound to acyclic carbon atoms with only carbon-to-carbon double bonds as unsaturation
- C07C47/22—Acryaldehyde; Methacryaldehyde
-
- 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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/20—After treatment, characterised by the effect to be obtained to introduce other elements in the catalyst composition comprising the molecular sieve, but not specially in or on the molecular sieve itself
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/405—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/7007—Zeolite Beta
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/7049—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
- B01J29/7057—Zeolite Beta
-
- 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
- B01J35/19—Catalysts containing parts with different compositions
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Crystallography & Structural Chemistry (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
[実施例1]
物理的混合方法を通じてCuSO4+Bゼオライト(B−Zeolite)基盤の混合触媒を製造して使用した。物理的混合による触媒はCuSO4とBゼオライト(B−Zeolite)を8:2の重量比で混合した後、すり鉢を用いて混合物が細かいパウダーになるまですって約250μm大きさに成形した後に脱水反応用触媒として使用した。触媒は別途の焼成過程は経なかった。
物理的混合方法を通じてCuSO4+ZSM−5混合触媒を製造して使用した。物理的混合によるCuSO4とZSM−5を8:2の重量比で混合した後、すり鉢を用いて混合物が細かいパウダーになるまですって約250μm大きさに成形した後に脱水反応用触媒として使用した。触媒は別途の焼成過程は経なかった。
物理的混合方法を通じてCuSO4+Fe2(SO4)3+Bゼオライト(B−Zeolite)混合触媒を製造して使用した。物理的混合によるCuSO4とFe2(SO4)3およびBゼオライト(B−Zeolite)を1:1.25:4の重量比で混合した後、すり鉢を用いて混合物が細かいパウダーになるまですって約250μm大きさに成形した後に脱水反応用触媒として使用した。触媒は別途の焼成過程は経なかった。
物理的混合方法を通じてCuSO4+Fe2(SO4)3+ZSM−5混合触媒を製造して使用した。物理的混合によるCuSO4とFe2(SO4)3およびZSM−5を1:1.25:4の重量比で混合した後、すり鉢を用いて混合物が細かいパウダーになるまですって約250μm大きさに成形した後に脱水反応用触媒として使用した。触媒は別途の焼成過程は経なかった。
物理的混合方法を通じてCuSO4+ZnSO4+Bゼオライト(B−Zeolite)混合触媒を製造して使用した。物理的混合によるCuSO4とZnSO4およびBゼオライト(B−Zeolite)を1:1.25:4の重量比で混合した後、すり鉢を用いて混合物が細かいパウダーになるまですって約250μm大きさに成形した後に脱水反応用触媒として使用した。触媒は別途の焼成過程は経なかった。
物理的混合方法を通じてCuSO4+CaSO4+Bゼオライト(B−Zeolite)混合触媒を製造して使用した。物理的混合によるCuSO4とCaSO4およびBゼオライト(B−Zeolite)を1:1.25:4の重量比で混合した後、すり鉢を用いて混合物が細かいパウダーになるまですって約250μm大きさに成形した後に脱水反応用触媒として使用した。触媒は別途の焼成過程は経なかった。
物理的混合方法を通じてCuSO4+CaSO4+ZSM−5混合触媒を製造して使用した。物理的混合によるCuSO4とCaSO4およびZSM−5を1:1.25:4の重量比で混合した後、すり鉢を用いて混合物が細かいパウダーになるまですって約250μm大きさに成形した後に脱水反応用触媒として使用した。触媒は別途の焼成過程は経なかった。
物理的混合方法を通じてCuSO4+CoSO4+Bゼオライト(B−Zeolite)混合触媒を製造して使用した。物理的混合によるCuSO4とCoSO4およびBゼオライト(B−Zeolite)を1:1.25:4の重量比で混合した後、すり鉢を用いて混合物が細かいパウダーになるまですって約250μm大きさに成形した後に脱水反応用触媒として使用した。触媒は別途の焼成過程は経なかった。
CuSO4の場合、大井化金株式会社で販売する試薬をすり鉢を用いて細かいパウダー形態になるまですって約250μm大きさに成形した後に脱水反応用触媒として使用した。触媒は別途の焼成過程は経なかった。
Fe2(SO4)3の場合、大井化金株式会社で販売する試薬をすり鉢を用いて細かいパウダー形態になるまですって約250μm大きさに成形した後に脱水反応用触媒として使用した。触媒は別途の焼成過程は経なかった。
ZnSO4の場合、大井化金株式会社で販売する試薬をすり鉢を用いて細かいパウダー形態になるまですって約250μm大きさに成形した後に脱水反応用触媒として使用した。触媒は別途の焼成過程は経なかった。
Bゼオライト(B−Zeolite)の場合、ゼオライト株式会社で販売する試薬をすり鉢を用いて細かいパウダー形態になるまですって約250μm大きさに成形した後に脱水反応用触媒として使用した。触媒は700℃の空気雰囲気で5時間焼成した。
ZSM−5の場合、ゼオライト株式会社で販売する試薬をすり鉢を用いて細かいパウダー形態になるまですって約250μm大きさに成形した後に脱水反応用触媒として使用した。触媒は700℃の空気雰囲気で5時間焼成した。
CuSO4+SiO2の場合、CuSO4は大井化金株式会社で販売する試薬を使用し、SiO2はsylopol 925Xを使用して重量比を2:8にして、すり鉢を用いて細かいパウダー形態になるまですって約250μm大きさに成形した後に脱水反応用触媒として使用した。触媒は別途の焼成過程は経なかった。
H3PW12O40の場合、Wako社から12−tungsto(VI) phosphoric acid n−hydrate(99%)を購入して使用し、触媒は300℃の空気雰囲気で4時間焼成後に使用した。焼成後の触媒は約250μm大きさに成形した後に脱水反応用触媒として使用した。
BPO4の場合、H3BO3とH3PO4試薬を使用して1:1のモル比で溶媒としては蒸留水を使用して60℃の温度で加熱して水分を除去し、得られた粉末を100℃オーブンで一晩乾燥し、700℃の空気雰囲気で4時間焼成後に使用した。焼成後の触媒は約250μm大きさに成形した後に脱水反応用触媒として使用した。
Claims (10)
- 金属硫酸塩とゼオライトの物理的混合物からなるグリセリン脱水反応用触媒であって、
前記金属硫酸塩は、CuSO 4 、Fe 2 (SO 4 ) 3 、ZnSO 4 、CaSO 4 、およびCoSO 4 からなる群より選択された1種以上を含むグリセリン脱水反応用触媒。 - 前記ゼオライトは、ベータゼオライト(β−Zeolite)、およびZSM−5からなる群より選択された1種以上を含む、請求項1に記載のグリセリン脱水反応用触媒。
- 前記金属硫酸塩とゼオライトは、1:3乃至10:1の質量比で含まれる、請求項1に記載のグリセリン脱水反応用触媒。
- 前記金属硫酸塩は、互いに異なる金属を含む硫酸塩2種を1:1乃至1:5の質量比で含む、請求項1に記載のグリセリン脱水反応用触媒。
- 請求項1から4のいずれか一項に規定のグリセリン脱水反応用触媒の製造方法であって、金属硫酸塩とゼオライトを物理混合する段階を含み、
前記金属硫酸塩は、CuSO 4 、Fe 2 (SO 4 ) 3 、ZnSO 4 、CaSO 4 、およびCoSO 4 からなる群より選択された1種以上を含む、グリセリン脱水反応用触媒の製造方法。 - 前記ゼオライトは、ベータゼオライト(β−Zeolite)、およびZSM−5からなる群より選択された1種以上を含む、請求項5に記載のグリセリン脱水反応用触媒の製造方法。
- 前記金属硫酸塩とゼオライトは、1:3乃至10:1の質量比で物理混合する、請求項5に記載のグリセリン脱水反応用触媒の製造方法。
- 請求項1のグリセリン脱水反応用触媒の存在下に、グリセリンを反応させる段階を含む、アクロレインの製造方法。
- 前記グリセリン脱水反応用触媒は、10乃至300mmol/h・gcatの重量空間速度で充填する、請求項8に記載のアクロレインの製造方法。
- 前記グリセリンを反応させる段階は、200乃至400℃の温度で行われる、請求項8に記載のアクロレインの製造方法。
Applications Claiming Priority (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR10-2013-0139992 | 2013-11-18 | ||
KR20130139992 | 2013-11-18 | ||
KR10-2014-0160193 | 2014-11-17 | ||
KR1020140160193A KR101629003B1 (ko) | 2013-11-18 | 2014-11-17 | 글리세린 탈수반응용 촉매, 이의 제조 방법 및 아크롤레인의 제조 방법 |
PCT/KR2014/011079 WO2015072813A1 (ko) | 2013-11-18 | 2014-11-18 | 글리세린 탈수반응용 촉매, 이의 제조 방법 및 아크롤레인의 제조 방법 |
Publications (2)
Publication Number | Publication Date |
---|---|
JP2016513009A JP2016513009A (ja) | 2016-05-12 |
JP6267238B2 true JP6267238B2 (ja) | 2018-01-24 |
Family
ID=53392706
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2015557962A Active JP6267238B2 (ja) | 2013-11-18 | 2014-11-18 | グリセリン脱水反応用触媒、その製造方法およびアクロレインの製造方法 |
Country Status (5)
Country | Link |
---|---|
US (1) | US9527065B2 (ja) |
EP (1) | EP2913106B1 (ja) |
JP (1) | JP6267238B2 (ja) |
KR (1) | KR101629003B1 (ja) |
WO (1) | WO2015072813A1 (ja) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US10647928B2 (en) | 2017-11-20 | 2020-05-12 | Ecolab Usa Inc. | In-line chemical heating for in-situ generation of active chemicals |
Family Cites Families (21)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20050221457A1 (en) | 2002-03-25 | 2005-10-06 | Paraskevas Tsobanakis | Methods of manufacturing derivatives of beta-hydroxycarboxylic acids |
EP1732874A1 (en) * | 2004-04-02 | 2006-12-20 | Ciba Speciality Chemicals Water Treatments Limited | Preparation of acrylic acid derivatives from alpha or beta-hydroxy carboxylic acids |
FR2882052B1 (fr) | 2005-02-15 | 2007-03-23 | Arkema Sa | Procede de deshydratation du glycerol en acroleine |
JP4791246B2 (ja) * | 2006-05-12 | 2011-10-12 | 株式会社日本触媒 | グリセリン脱水用触媒、およびアクロレインの製造方法 |
DE102006039205A1 (de) * | 2006-08-22 | 2008-03-20 | Stockhausen Gmbh | Auf nachwachsenden Rohstoffen basierende Acrylsäure und wasserabsorbierende Polymergebilde sowie Verfahren zu deren Herstellung mittels Dehydratisierung |
DE102006054519A1 (de) * | 2006-11-20 | 2008-05-21 | Evonik Degussa Gmbh | Verfahren zur Herstellung von Fettsäurealkylestern und Acrolein aus Triglyceriden |
KR100835476B1 (ko) | 2006-12-29 | 2008-06-09 | 주식회사 효성 | 1,4-부탄디올로부터 테트라하이드로퓨란의 제조방법 |
KR101002761B1 (ko) * | 2007-12-03 | 2010-12-21 | 주식회사 엘지화학 | 아크릴산의 제조방법 |
FR2931820B1 (fr) * | 2008-06-03 | 2010-05-14 | Arkema France | Procede de fabrication d'acroleine par deshydratation du glycerol |
JP5134443B2 (ja) * | 2008-06-05 | 2013-01-30 | 昭和電工株式会社 | アクロレイン及びアクリル酸の製造方法 |
CN101298393A (zh) * | 2008-06-17 | 2008-11-05 | 郭瑞 | 挤压造粒无烘干生产硫酸钾镁肥的工艺 |
BRPI0806337A2 (pt) * | 2008-06-24 | 2010-03-09 | Suzano Petroquimica S A | preparação de catalisadores heterogêneos utilizados na hidrogenação seletiva de glicerina a propeno e processo para hidrogenação seletiva de glicerina a propeno |
WO2010052208A2 (en) | 2008-11-05 | 2010-05-14 | Biofuel-Solution Ab | A process for preparing lower hydrocarbons from glycerol |
CN101745398B (zh) | 2008-12-10 | 2013-01-09 | 中国石油化工股份有限公司 | 非晶态合金及其制备、催化剂以及合成气转化的方法 |
EP2477736A1 (en) | 2009-09-18 | 2012-07-25 | Nippon Kayaku Kabushiki Kaisha | Catalyst and process for preparing acrolein and/or acrylic acid by dehydration reaction of glycerin |
JP2012157794A (ja) * | 2011-01-29 | 2012-08-23 | Hokkaido Univ | グリセリン脱水用触媒、その製造方法並びに該触媒を用いたアクロレインの製造方法 |
KR101322678B1 (ko) * | 2011-04-14 | 2013-10-30 | 서울대학교산학협력단 | 글리세롤의 탈수반응을 통한 아크롤레인 생산 반응용 촉매 및 그 제조방법 |
JP5754734B2 (ja) * | 2011-09-08 | 2015-07-29 | 国立大学法人 千葉大学 | 1,2−ジオールからの低級飽和アルデヒド製造方法 |
CN102513137B (zh) | 2011-12-07 | 2014-12-03 | 北京化工大学 | 乳酸或乳酸酯脱水制取丙烯酸和/或丙烯酸酯的催化剂 |
KR101337301B1 (ko) * | 2012-03-28 | 2013-12-05 | 서울대학교산학협력단 | 3차원의 열린 기공 구조를 갖는 알루미노실리케이트 구형 나노 입자, 그 제조방법 및 상기 나노 입자를 이용하여 글리세롤로부터 아크릴산을 제조하는 방법 |
CN103242149B (zh) * | 2013-05-15 | 2015-07-15 | 常州工学院 | 一种选择性制备丙烯醛和羟基丙酮的方法 |
-
2014
- 2014-11-17 KR KR1020140160193A patent/KR101629003B1/ko active IP Right Grant
- 2014-11-18 WO PCT/KR2014/011079 patent/WO2015072813A1/ko active Application Filing
- 2014-11-18 JP JP2015557962A patent/JP6267238B2/ja active Active
- 2014-11-18 EP EP14861693.1A patent/EP2913106B1/en active Active
- 2014-11-18 US US14/653,670 patent/US9527065B2/en active Active
Also Published As
Publication number | Publication date |
---|---|
WO2015072813A1 (ko) | 2015-05-21 |
JP2016513009A (ja) | 2016-05-12 |
US9527065B2 (en) | 2016-12-27 |
EP2913106A1 (en) | 2015-09-02 |
KR20150058037A (ko) | 2015-05-28 |
KR101629003B1 (ko) | 2016-06-09 |
US20150343430A1 (en) | 2015-12-03 |
EP2913106A4 (en) | 2017-03-01 |
EP2913106B1 (en) | 2021-03-03 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP6417009B2 (ja) | グリセリン脱水反応用触媒、その製造方法およびアクロレインの製造方法 | |
CN107107042B (zh) | 制备乙二醇醚用的催化剂及其制备方法和应用 | |
JP2018500148A (ja) | グリセリン脱水反応用触媒、その製造方法および前記触媒を用いたアクロレインの製造方法 | |
JP6267238B2 (ja) | グリセリン脱水反応用触媒、その製造方法およびアクロレインの製造方法 | |
JP6084336B2 (ja) | アリルアルコールの製造方法及びこれにより製造されたアリルアルコール | |
JP6806899B2 (ja) | アクリル酸及びアクリル酸メチルの製造方法 | |
CN108097286B (zh) | 一种制备丙烯酸和丙烯酸甲酯的催化剂 | |
EA035233B1 (ru) | Способ получения алкилового эфира низшей жирной кислоты | |
KR101805086B1 (ko) | 글리세린 탈수 반응용 촉매의 제조 방법, 이를 이용하여 제조된 글리세린 탈수 반응용 촉매 및 아크롤레인의 제조 방법 | |
US9259718B1 (en) | Method for preparing catalyst for glycerin dehydration, and method for preparing acrolein | |
JP6533621B2 (ja) | グリセリン脱水反応用触媒、その製造方法および前記触媒を利用したアクロレインの製造方法 | |
KR101606191B1 (ko) | 글리세린 탈수반응용 촉매, 이의 제조 방법 및 아크롤레인의 제조 방법 | |
WO2014024782A2 (ja) | グリセリンからアクリル酸を製造するための触媒とその製造方法 | |
KR101745677B1 (ko) | 글리세린 탈수반응용 촉매, 이의 제조 방법 및 아크롤레인의 제조 방법 | |
KR102118501B1 (ko) | 글리세롤로부터 아크롤레인의 제조 방법 | |
JP2013121946A (ja) | イソブタノールからメタクロレイン及びメタクリル酸を製造する方法並びに製造装置 | |
KR102164613B1 (ko) | 글리세린 탈수 반응용 촉매, 이의 제조 방법 및 상기 촉매를 이용한 아크롤레인의 제조 방법 | |
CN108097289B (zh) | 一种用于制备丙烯酸和/或丙烯酸甲酯的催化剂的再生方法 | |
CN112672823A (zh) | 用于由合成气产生醇和醚的催化剂 | |
KR20160074287A (ko) | 글리세린 탈수반응용 촉매 및 아크롤레인의 제조 방법 | |
KR20170075638A (ko) | 글리세린 탈수 반응용 촉매의 제조 방법 및 아크롤레인의 제조 방법 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20160812 |
|
A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20160916 |
|
A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20161213 |
|
A02 | Decision of refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A02 Effective date: 20170619 |
|
A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20171019 |
|
A911 | Transfer to examiner for re-examination before appeal (zenchi) |
Free format text: JAPANESE INTERMEDIATE CODE: A911 Effective date: 20171106 |
|
TRDD | Decision of grant or rejection written | ||
A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20171127 |
|
R150 | Certificate of patent or registration of utility model |
Ref document number: 6267238 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |