WO2014061569A1 - メチルアミン類製造用触媒の製造方法及びメチルアミン類の製造方法 - Google Patents
メチルアミン類製造用触媒の製造方法及びメチルアミン類の製造方法 Download PDFInfo
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- WO2014061569A1 WO2014061569A1 PCT/JP2013/077706 JP2013077706W WO2014061569A1 WO 2014061569 A1 WO2014061569 A1 WO 2014061569A1 JP 2013077706 W JP2013077706 W JP 2013077706W WO 2014061569 A1 WO2014061569 A1 WO 2014061569A1
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- Prior art keywords
- producing
- catalyst
- sapo
- molecular sieve
- crystalline silicoaluminophosphate
- Prior art date
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- BAVYZALUXZFZLV-UHFFFAOYSA-N mono-methylamine Natural products NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 title claims abstract description 125
- 239000003054 catalyst Substances 0.000 title claims abstract description 64
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 48
- -1 methylamine compound Chemical class 0.000 title abstract description 5
- 239000002808 molecular sieve Substances 0.000 claims abstract description 53
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 53
- 238000000034 method Methods 0.000 claims abstract description 49
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 31
- 150000003839 salts Chemical class 0.000 claims abstract 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 72
- 238000006243 chemical reaction Methods 0.000 claims description 54
- 150000003956 methylamines Chemical class 0.000 claims description 48
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 26
- 239000007789 gas Substances 0.000 claims description 22
- 229910021529 ammonia Inorganic materials 0.000 claims description 13
- 239000011261 inert gas Substances 0.000 claims description 6
- 229910052719 titanium Inorganic materials 0.000 claims description 5
- 229910052726 zirconium Inorganic materials 0.000 claims description 5
- 230000003750 conditioning effect Effects 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 229910052749 magnesium Inorganic materials 0.000 claims description 4
- 229910052748 manganese Inorganic materials 0.000 claims description 4
- 229910052718 tin Inorganic materials 0.000 claims description 4
- 229910052727 yttrium Inorganic materials 0.000 claims description 4
- 229910052796 boron Inorganic materials 0.000 claims description 3
- 229910052791 calcium Inorganic materials 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 229910052733 gallium Inorganic materials 0.000 claims description 3
- 229910052732 germanium Inorganic materials 0.000 claims description 3
- 229910052738 indium Inorganic materials 0.000 claims description 3
- 229910052741 iridium Inorganic materials 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 229910052758 niobium Inorganic materials 0.000 claims description 3
- 229910052763 palladium Inorganic materials 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- 229910052703 rhodium Inorganic materials 0.000 claims description 3
- 229910052707 ruthenium Inorganic materials 0.000 claims description 3
- 229910052712 strontium Inorganic materials 0.000 claims description 3
- 229910052720 vanadium Inorganic materials 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims 1
- 238000010438 heat treatment Methods 0.000 abstract description 46
- 241000269350 Anura Species 0.000 description 85
- 238000003786 synthesis reaction Methods 0.000 description 38
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 32
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 26
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 24
- 238000002407 reforming Methods 0.000 description 20
- 230000000052 comparative effect Effects 0.000 description 14
- 230000000694 effects Effects 0.000 description 13
- 229910052757 nitrogen Inorganic materials 0.000 description 13
- 230000001143 conditioned effect Effects 0.000 description 11
- 239000011148 porous material Substances 0.000 description 10
- 238000001179 sorption measurement Methods 0.000 description 9
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 7
- 229910052782 aluminium Inorganic materials 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 229910000323 aluminium silicate Inorganic materials 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000007323 disproportionation reaction Methods 0.000 description 5
- 230000007774 longterm Effects 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 229910052698 phosphorus Inorganic materials 0.000 description 5
- 239000011574 phosphorus Substances 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010457 zeolite Substances 0.000 description 4
- 229910021536 Zeolite Inorganic materials 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 229910052675 erionite Inorganic materials 0.000 description 2
- 238000004231 fluid catalytic cracking Methods 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 230000020169 heat generation Effects 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- 238000010335 hydrothermal treatment Methods 0.000 description 2
- 229910052680 mordenite Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 150000003377 silicon compounds Chemical class 0.000 description 2
- 229910017090 AlO 2 Inorganic materials 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000012824 chemical production Methods 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 229910001657 ferrierite group Inorganic materials 0.000 description 1
- 238000000769 gas chromatography-flame ionisation detection Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 150000003961 organosilicon compounds Chemical class 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000006884 silylation reaction Methods 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 1
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 1
Classifications
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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
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- 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
- B01J29/82—Phosphates
- B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
- B01J29/85—Silicoaluminophosphates [SAPO compounds]
-
- 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
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
-
- 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
- B01J37/0063—Granulating
-
- 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
- B01J37/08—Heat treatment
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/04—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups
- C07C209/14—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of hydroxy groups or of etherified or esterified hydroxy groups
- C07C209/16—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of hydroxy groups or of etherified or esterified hydroxy groups with formation of amino groups bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/64—Preparation of compounds containing amino groups bound to a carbon skeleton by disproportionation
-
- 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
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
- B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
-
- 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
- B01J2229/30—After treatment, characterised by the means used
- B01J2229/36—Steaming
-
- 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
- B01J2229/30—After treatment, characterised by the means used
- B01J2229/40—Special temperature treatment, i.e. other than just for template removal
Definitions
- the present invention relates to a method for producing a catalyst for producing methylamines comprising a modified crystalline silicoaluminophosphate molecular sieve, and a method for producing methylamines using the catalyst obtained by the method.
- Methylamines are usually produced from methanol and ammonia at a temperature of around 400 ° C. using a solid acid catalyst such as silica-alumina.
- a silica-alumina catalyst is used, the product follows a thermodynamic equilibrium, and among the three types of methylamines of mono, di, and tri, trimethylamine, which is the least in demand, is the main product. Become. However, most of the demand for methylamines is biased toward dimethylamine, and trimethylamine, which is less demanded, is distilled and separated from the reaction product and then recycled to the reaction system, resulting in very large energy consumption. For this reason, in recent years, development of a selective dimethylamine production method exceeding the thermodynamic equilibrium composition has been advanced.
- Such methods include, for example, zeolite A (for example, see Patent Document 1), FU-1 (for example, see Patent Document 2), ZSM-5 (for example, see Patent Document 3), ferrierite and erionite (for example, (See Patent Document 4), ZK-5, Rho, shabasite and erionite (see, for example, Patent Document 5), and mordenite (see, for example, Patent Documents 6, 7, 8, and 9) (crystalline aluminosilicates). And a method using a molecular sieve).
- zeolites with a small pore inlet diameter are further subjected to ion exchange, dealumination treatment, addition of a specific element or silylation treatment, etc., to control the pore inlet diameter or to adjust the outer surface acidic point.
- ion exchange dealumination treatment
- addition of a specific element or silylation treatment etc.
- dimethylamine selectivity and catalytic activity are improved.
- Patent Document 10 a method for producing methylamines exceeding the thermodynamic equilibrium composition using crystalline silicoaluminophosphate molecular sieve.
- Patent Document 10 a method for producing methylamines exceeding the thermodynamic equilibrium composition using crystalline silicoaluminophosphate molecular sieve.
- the present inventors have formed silica-modified SAPO, SAPO modified with various oxides, and an amorphous oxide layer with an appropriate thickness on the crystal particle surface. It has been found that the SAPO produced exhibits high activity and high dimethylamine selectivity compared to the prior art catalysts (for example, see Patent Documents 11, 12, 13, and 14).
- Patent Document 11 also describes production of dimethylamine by disproportionation of monomethylamine.
- Crystalline aluminosilicate molecular sieves and crystalline silicoaluminophosphate molecular sieves must be modified by contact with steam to improve catalytic activity and selectivity when used as catalysts for chemical production.
- ultra-stabilized Y-type zeolite (USY) used for fluid catalytic cracking (FCC) is obtained by contacting with steam at 600 to 800 ° C.
- Patent Document 15 and Non-Patent Document 1 Barger et al.
- Barger et al. show that the treatment of crystalline silicoaluminophosphate molecular sieves at 700-900 ° C. in a steam atmosphere improves the selectivity of C2-C3 olefins and catalyst life in methanol conversion. Have been reported (see Patent Document 16).
- Patent Document 9 discloses that a crystalline aluminosilicate molecular sieve such as mordenite is brought into contact with water vapor in the range of 250 to 700 ° C. It describes that the amine selectivity is improved. However, although the selectivity is improved, the effect is not sufficient, and catalytic activity is sacrificed by contact with water vapor.
- Patent Document 17 discloses a method for improving the strength of a molded body containing crystalline aluminosilicate molecular sieve by treating at a temperature of 100 to 600 ° C. under the flow of a steam-containing gas.
- Patent Document 18 discloses a method of removing halogen in a catalyst by bringing crystalline silicoaluminophosphate molecular sieve formed using a halogen-containing binder into contact with water vapor at 400 ° C. to 1000 ° C. ing.
- these catalysts can also be used for methylamine synthesis reaction, effects on catalyst activity and selectivity are not described.
- An object of the present invention is to provide a method for producing a catalyst for producing methylamines comprising crystalline silicoaluminophosphate molecular sieve capable of maintaining high dimethylamine selectivity and continuously using the catalyst for a long period of time.
- the present invention provides a more efficient method for producing methylamines using the prepared catalyst.
- the present inventors adsorbed 5 to 30% by weight of water of the crystalline silicoaluminophosphate molecular sieve to the crystalline silicoaluminophosphate molecular sieve.
- heat treatment reforming at 130 ° C to 350 ° C for 5 to 40 hours under a pressure of 1 MPa or more, it is possible to maintain high dimethylamine selectivity and low trimethylamine selectivity while reducing the decrease in activity due to long-term use.
- the present inventors have found that a catalyst for producing methylamines composed of a refined crystalline silicoaluminophosphate molecular sieve can be obtained, and the present invention has been completed.
- the present invention includes the following aspects. ⁇ 1> a moisture conditioning step of adsorbing 5 to 30% by weight of the crystalline silicoaluminophosphate molecular sieve on the crystalline silicoaluminophosphate molecular sieve; and A step of heat-treating the crystalline silicoaluminophosphate molecular sieve adsorbed with moisture at a temperature of 130 to 350 ° C. for 5 to 40 hours under a pressure of 0.1 MPa or more (hereinafter referred to as “heat treatment reforming step”).
- a catalyst for producing methylamines comprising a modified crystalline silicoaluminophosphate molecular sieve.
- the crystalline silicoaluminophosphate molecular sieve is selected from SAPO-14, 17, 18, 21, 22, 25, 33, 34, 35, 39, 42, 43, 44, 47, 52 and 56
- the crystalline silicoaluminophosphate molecular sieve is Mg, Ca, Sr, Y, Ti, Zr, V, Nb, Cr, Mn, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt. , Cu, Zn, B, Ga, In, Ge and Sn.
- a humidity control step of adsorbing moisture on the crystalline silicoaluminophosphate molecular sieve fills the reactor with crystalline silicoaluminophosphate molecular sieve, and the gas containing moisture is converted into crystalline silicoaluminophosphate.
- ⁇ 5> The method for producing a catalyst for producing methylamines according to ⁇ 4>, wherein the gas containing water is a mixed gas of water vapor and at least one selected from an inert gas and air.
- ⁇ 6> A method for producing methylamines comprising reacting methanol and ammonia in the presence of a catalyst for producing methylamines comprising crystalline silicoaluminophosphate molecular sieves, The methylamines produced by the method for producing a catalyst for producing methylamines comprising the modified crystalline silicoaluminophosphate molecular sieve according to any one of ⁇ 1> to ⁇ 5>. It is a manufacturing method.
- methylamines that react with methanol and monomethylamine, or react with methanol, ammonia, and monomethylamine in the presence of a catalyst for producing methylamines composed of crystalline silicoaluminophosphate molecular sieves
- a method The methylamines produced by the method for producing a catalyst for producing methylamines comprising the modified crystalline silicoaluminophosphate molecular sieve according to any one of ⁇ 1> to ⁇ 5>. It is a manufacturing method.
- a method for producing methylamines in which a disproportionation reaction of monomethylamine is performed in the presence of a catalyst for producing methylamines composed of crystalline silicoaluminophosphate molecular sieves The methylamines produced by the method for producing a catalyst for producing methylamines comprising the modified crystalline silicoaluminophosphate molecular sieve according to any one of ⁇ 1> to ⁇ 5>. It is a manufacturing method.
- the crystalline silicoaluminophosphate molecular sieve catalyst which was difficult with the conventional reforming method using water vapor, can be uniformly reformed, so that the activity and selectivity are improved in the methylamine synthesis reaction. And maintaining long-term activity and selectivity. Further, by performing the reforming in two stages of the humidity control process and the heat treatment reforming process, the reforming can be performed under milder conditions than in the past.
- Crystalline silicoaluminophosphate molecular sieves are crystalline and microporous, as described in US Pat. No. 4,440,871, and are PO 2 + , AlO 2 ⁇ and SiO 2. It is a compound having a three-dimensional microporous crystal skeleton structure composed of two tetrahedral units, and is called SAPO.
- SAPO a compound having a three-dimensional microporous crystal skeleton structure composed of two tetrahedral units
- a compound containing a tetrahedral unit of a metal other than silicon, aluminum, and phosphorus in a three-dimensional microporous crystal skeleton structure is also disclosed in European Patent No. 159,624, etc., and is called ELAPSO molecular sieve. Yes.
- SAPO and ELAPSO As SAPO and ELAPSO, SAPO and ELAPSO having various structures having different pore sizes and pore connection modes are known depending on the arrangement of the tetrahedral units.
- SAPO used for the production of the catalyst for producing methylamines of the present invention includes ELAPSO.
- the effective pore diameter of SAPO is desirably in the range of 0.3 to 0.6 nanometer.
- Such pores inhibit the passage of trimethylamine molecules and allow the passage of smaller molecular sizes of monomethylamine and dimethylamine, so that ultimately the selectivity of the reaction is offset by monomethylamine and dimethylamine (D. R).
- D. R monomethylamine and dimethylamine
- the effective pore diameter corresponds to the pore diameter of 8 to 10 oxygen member rings of SAPO.
- SAPO having 8 oxygen member ring pores is suitable and preferable for lowering the selectivity of trimethylamine.
- SAPO having eight oxygen member ring pores examples include SAPO-14, 17, 18, 21, 22, 25, 33, 34, 35, 39, 42, 43, 44, 47, 52, and 56. .
- SAPO IUPAC structure codes correspond to AFN, ERI, AEI, AWO, AWW, ATV, ATT, CHA, LEV, ATN, LTA, GIS, CHA, CHA, AFT, and AFX, respectively.
- SAPO-17, 18, 34, 35, 44, 47 and 56 are more preferable, and SAPO-34 having a CHA type structure is particularly preferable.
- the SAPO used in the present invention is Mg, Ca, Sr, Y, Ti, Zr, V, Nb, Cr, Mn, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Zn, B, Ga. And at least one element selected from In, Ge, and Sn.
- a case where an element selected from Mg, Y, Ti, Zr, Mn, Fe, Co, and Sn is more preferable is included, and Ti and Zr are particularly preferable because they have an effect of improving catalyst activity and life performance.
- These element components may exist outside the three-dimensional microporous crystal skeleton structure and / or the skeleton structure.
- SAPO-34 having a CHA type structure can be synthesized by hydrothermal treatment of a mixture of a silicon compound, an aluminum compound, a phosphorus compound, and water using tetraethylammonium hydroxide as a template agent.
- SAPO containing metals other than silicon, aluminum, and phosphorus includes templating agents, silicon compounds, aluminum compounds, phosphorus compounds, water, and nitrates, sulfates, and chlorides of metal elements other than silicon, aluminum, and phosphorus.
- Oxide sol, oxide powder, alkoxide and / or complex mixture can be synthesized by hydrothermal treatment.
- SAPO used in the present invention may have an amorphous oxide layer composed of an oxide containing silicon, aluminum, and phosphorus. Further, SAPO modified with an oxide or SAPO modified with silica using an organosilicon compound may be used.
- the form of SAPO used in the present invention is not particularly limited, and may be a powder form or a granule form, or may be a molded body formed by a method such as extrusion or tableting.
- the SAPO used in the production of the catalyst for producing methylamines of the present invention is a humidity control step for uniformly adsorbing an appropriate amount of moisture to the SAPO, and a heat treatment reforming step for heat treatment for a predetermined time at an appropriate temperature and pressure. It is a modified SAPO.
- the amount of moisture adsorbed on SAPO is preferably 5 to 30% by weight, particularly preferably 10 to 25% by weight, based on the dry weight of SAPO. This is because, when the amount of humidity control is less than 5% by weight, the selectivity of trimethylamine in the methylamine synthesis reaction using methanol and ammonia is high, so that the selectivity of monomethylamine and dimethylamine is low. On the other hand, when the amount of humidity control exceeds 30% by weight, the methanol conversion rate in the methylamine synthesis reaction becomes low.
- the dry weight of SAPO is the weight when dried in a dryer at 110 ° C. until there is no change in weight.
- the method of adsorbing moisture on SAPO is not particularly limited, but it is preferably performed by contacting SAPO with a gas containing moisture.
- a humidity control method for example, the SAPO is placed in a sealed container such as a steam furnace or an autoclave so that a predetermined amount of water is not in direct contact, and is left to stand until all the water is adsorbed by the SAPO.
- a closed container containing SAPO and a predetermined amount of water may be heated at a temperature of 50 ° C. to 120 ° C. in order to promote moisture adsorption on SAPO.
- the method of mixing and contacting SAPO with liquid water may cause rapid heat of adsorption, which may cause damage to the molded body and deterioration of reaction active points, and the amount of water in SAPO will be uneven. Because it is easy, it is better not to do as much as possible.
- a practical and particularly preferred humidity control method is a method in which a reactor for performing a methylamine synthesis reaction is filled with SAPO, and a gas containing moisture is continuously circulated through and contacted with the SAPO packed bed. By performing the contact with the containing gas at a temperature exceeding the dew point, moisture can be adsorbed up to the saturated adsorption moisture amount of SAPO determined by the temperature and the water vapor partial pressure.
- the reactor is filled with SAPO, and at a pressure of atmospheric pressure to 0.5 MPa, more preferably at atmospheric pressure, 80 to 130 ° C., more preferably 100 to 120 ° C., and a water concentration of 3 to 100 vol. %, More preferably 10 to 80 vol% of an inert gas and / or a mixed gas of air and water vapor is continuously passed through the SAPO packed bed.
- the type of the reactor is not particularly limited, and may be any of a heat insulation type, a tubular type, and a multi-tube type.
- the kind of inert gas is not specifically limited, For example, nitrogen, helium, and argon can be used.
- the method of continuously adjusting the humidity by continuously supplying a gas containing moisture to the SAPO packed bed utilizes the isothermal adsorption property of SAPO, so the temperature in the SAPO packed bed during the humidity control process should be controlled uniformly.
- the temperature difference in the SAPO filled layer at the end of humidity control is preferably 5 ° C. or less, more preferably 2 ° C. or less. At that time, there is almost no difference in moisture concentration between the reactor inlet and outlet.
- heat generation of the SAPO filled layer due to moisture adsorption may increase depending on the moisture content of SAPO and the moisture concentration of the gas brought into contact with the SAPO filled layer. Since rapid heat generation in the SAPO packed layer may cause damage to the molded body or deterioration of the reaction active point, it is preferable to suppress the temperature rise due to heat of adsorption to less than 20 ° C. from the temperature at which humidity is controlled. It is preferable that the moisture concentration in the gas is lower than the concentration in the above range, the moisture concentration is gradually increased according to the calorific value of the SAPO filled layer, and the humidity is finally adjusted at the moisture concentration in the above range.
- the SAPO that has been conditioned in the humidity adjusting step described above so as to have a uniform amount of water is heat-treated at an appropriate temperature and pressure for a predetermined time to modify the SAPO.
- a preferred heat treatment temperature is 130 to 350 ° C.
- a more preferred heat treatment temperature is 150 to 200 ° C. This is because the modification is slow at a heat treatment temperature of less than 130 ° C., so that the trimethylamine selectivity in the methylamine synthesis reaction using methanol and ammonia is increased.
- the heat treatment temperature exceeds 350 ° C., reforming occurs excessively, resulting in a low methanol conversion rate in the methylamine synthesis reaction or a high trimethylamine selectivity.
- the pressure at the time of the heat treatment should be 0.1 MPa or more as long as it can limit the evaporation of the moisture adsorbed on the SAPO by the humidity control treatment.
- the upper limit of the pressure is not particularly limited, but less than 5 MPa is economical from an industrial viewpoint, and more preferably 0.1 to 2 MPa.
- the method for controlling the pressure during the heat treatment is not particularly limited. For example, an increase in the internal pressure of the apparatus due to heating to the heat treatment temperature may be used, and an inert gas such as nitrogen, helium, or argon, or air may be used. You may control by pressing. At that time, there is no problem even if the pressure is controlled to an appropriate pressure using a pressure regulating valve.
- the heat treatment time is preferably 5 to 40 hours, more preferably 10 to 30 hours. This is because the modification is insufficient in the treatment time of less than 5 hours, and the trimethylamine selectivity in the methylamine synthesis reaction using methanol and ammonia becomes high. On the other hand, when the treatment time exceeds 40 hours, the reforming proceeds excessively, and the methanol conversion rate in the methylamine synthesis reaction becomes low.
- the apparatus used for the heat treatment reforming may be any apparatus that can be controlled to the temperature and pressure during the heat treatment.
- a closed vessel such as a steam furnace or an autoclave, or a reactor equipped with a pressure regulating valve may be used. it can.
- the heat treatment reforming may be carried out using the steam furnace or autoclave sealed vessel used in the humidity control described above, or the reactor used for the methylamine synthesis reaction as it is, or the moisture-treated SAPO. May be transferred to another device.
- the moisture-treated SAPO is transferred to another apparatus for heat treatment reforming, it can be modified without problems if it is handled so that the moisture content of SAPO does not change.
- SAPO can be uniformly modified, the activity and selectivity can be improved in the methylamine synthesis reaction, and the activity and selectivity can be maintained for a long time.
- the reforming can be performed under milder conditions than before by performing the reforming in two stages of the humidity control process and the heat treatment reforming process.
- the heat-treated SAPO can be used for the methylamine synthesis reaction as it is, but it is more preferable to use it for the reaction after drying or removing part or all of the water adsorbed on the SAPO.
- heat treatment reforming is performed using a methylamine synthesis reactor
- the moisture adsorbed on the SAPO is released by releasing the pressure after the heat treatment reforming and circulating a dry gas such as inert gas or air through the SAPO packed bed. Can be removed.
- the SAPO modified by the method of the present invention can be used as a catalyst for the production of methylamines that undergo a reaction such as a reaction between methanol and ammonia, a reaction between methanol and monomethylamine, and a disproportionation reaction of monomethylamine.
- the form of reaction may be either a fixed bed system or a fluidized bed system.
- the reaction temperature is preferably 200 to 400 ° C, particularly preferably 250 to 350 ° C.
- the reaction pressure is not particularly limited, but it is usually preferable to carry out at a pressure of 0.1 to 5 MPa.
- Humidity adjustment method (standing): A predetermined amount of SAPO that has been dried with a dryer at 110 ° C in advance until there is no change in weight and water corresponding to the target humidity control amount are weighed in separate magnetic dishes, and these dishes are placed in a desiccator and sealed. did. The desiccator was heated in a dryer at 110 ° C., taken out of the dryer after 2 hours, and cooled to room temperature.
- the calculation method of the amount of humidity control is as follows.
- Humidity adjustment method continuous: A pressure gauge, a nitrogen supply valve, a steam supply valve were attached to the upper part of a reaction tube having an inner diameter of 13 mm ⁇ and a length of 30 cm, and the gas closing valve was attached to the lower part. 10 g of dried SAPO was placed in the reaction tube, and the reaction tube was heated with an aluminum block heater. A predetermined amount of water vapor and nitrogen were supplied from the top of the reactor, and the conditions of temperature, pressure, and moisture concentration were maintained until the adsorption and desorption of moisture reached equilibrium and the temperature distribution of the SAPO layer became constant.
- the humidity control amount was obtained by measuring the weight of the reaction tube after the humidity control operation and calculating from the moisture adsorption amount to SAPO.
- (3) Heat treatment method An SUS tube having an inner diameter of 10 mm and a length of 30 cm was used. The pipe part was heated with a mantle heater, a pressure gauge, a nitrogen pressurizing valve and a pressure regulating valve were attached to the upper part, and the lower part was closed with a plug. After about 4 g (about 7 ml) of SAPO was added, the entire SUS tube was heated with a mantle heater. After a predetermined time, the pressure in the SUS tube was reduced and the SAPO was taken out. SAPO was dried again at 110 ° C. before using the methylamine synthesis reaction.
- Methylamine synthesis reaction A reaction tube having an inner diameter of 13 mm ⁇ and a length of 30 cm was filled with 2.5 g (3.5 ml) of dried SAPO after conditioning and heat treatment, the pressure was increased to 2 MPa, the temperature was increased to 305 ° C., and the weight ratio of methanol to ammonia was 1. The mixed raw material was supplied at a rate of 8.62 g / hour and a space velocity (GHSV) of 2500 h ⁇ 1 .
- Analysis method of reaction product The reaction solution was collected as an aqueous solution, and then analyzed by GC-FID manufactured by Shimadzu using a capillary column CP-Volamine.
- Example 1 4.00 g of dry SAPO-34 was conditioned with 0.62 g of water by the above-described humidity control method (standing). The weight of SAPO taken out after cooling was 4.62 g, and the humidity control amount was 15.5 wt%. Subsequently, the SAPO was filled in a SUS tube for heat treatment, and heat treatment was performed at 170 ° C. for 20 hours. The internal pressure at that time was 0.3 MPa. After the heat treatment was completed, the pressure was reduced and the mixture was dried at 110 ° C. for 2 hours and used for the methylamine synthesis reaction.
- the reaction results 24 hours after the start of the reaction were a methanol conversion rate of 92 wt%, a monomethylamine selectivity of 35 wt%, a dimethylamine selectivity of 60 wt%, and a trimethylamine selectivity of 5 wt%.
- the reaction results after 240 hours were a methanol conversion rate of 90 wt%, a monomethylamine selectivity of 38 wt%, a dimethylamine selectivity of 59 wt%, and a trimethylamine selectivity of 3 wt%.
- Example 2 SAPO-34 adjusted to 10.2 wt% by the above-described humidity control method (standing) was filled in a SUS tube, pressurized to 1 MPa with nitrogen, and heat-treated at 250 ° C. for 15 hours. After the heat treatment, the catalyst was extracted, dried at 110 ° C., and used for methylamine synthesis reaction. The reaction results are shown in Table 2.
- Example 3 SAPO-34 which had been conditioned to 25.4 wt% by the above humidity control method (standing), was filled into a SUS tube, pressurized to 2 MPa with nitrogen, and then heat treated at 140 ° C. for 20 hours. After the heat treatment, the catalyst was extracted, dried at 110 ° C., and used for methylamine synthesis reaction. The reaction results are shown in Table 2.
- Example 4 SAPO-34 adjusted to 15.3% by the above humidity control method (standing) was filled in a SUS tube, pressurized to 2 MPa with nitrogen, and heat-treated at 320 ° C. for 15 hours. After the heat treatment, the catalyst was extracted, dried at 110 ° C., and used for methylamine synthesis reaction. The reaction results are shown in Table 2.
- Example 5 SAPO-34 adjusted to 16.0 wt% by the above humidity control method (standing) was filled in a SUS tube, pressurized to 1.5 MPa with nitrogen, and heat-treated at 170 ° C. for 20 hours. After the heat treatment, the catalyst was extracted, dried at 110 ° C., and used for methylamine synthesis reaction. The reaction results are shown in Table 2.
- Example 6 SAPO-34 which was conditioned to 15.4% by the above-described humidity control method (standing), was filled in a SUS tube and heat-treated at 170 ° C. for 10 hours. The internal pressure at that time was 0.3 MPa. After the heat treatment, the catalyst was extracted, dried at 110 ° C., and used for methylamine synthesis reaction. The reaction results are shown in Table 2.
- Example 7 SAPO-34 which was conditioned to 15.3% by the above humidity control method (standing), was filled in a SUS tube and heat-treated at 170 ° C. for 35 hours. The internal pressure at that time was 0.3 MPa. After the heat treatment, the catalyst was extracted, dried at 110 ° C., and used for methylamine synthesis reaction. The reaction results are shown in Table 2.
- Example 8 Humidity control was performed by the above-described humidity control method (continuous). 10 g of dried SAPO-34 was placed in the reaction tube, the SAPO layer temperature was 112 ° C., the nitrogen flow rate was 60 ml / min, the water vapor flow rate was 2.02 g / h, and the mixed gas was supplied until the SAPO layer temperature was constant. The SAPO humidity control amount calculated from the weight increase was 15.4 wt%. After completion of humidity control, the steam supply valve, nitrogen supply valve, and lower gas shut-off valve at the upper part of the reaction tube were closed and heated to 170 ° C. and heat-treated for 15 hours. The internal pressure during the heat treatment was 0.3 MPa. After heat treatment, SAPO was dried at 110 ° C. and then used for methylamine synthesis reaction. The reaction results are shown in Table 2.
- Example 9 Humidity adjustment and heat treatment were performed in the same manner as in Example 1 except that Ti-containing SAPO-34 was used instead of SAPO-34, and used for methylamine synthesis reaction. The reaction results are shown in Table 2.
- Comparative Example 1 The dried SAPO-34 was used for the methylamine synthesis reaction without humidity conditioning and heat treatment. The reaction results are shown in Table 2.
- Comparative Example 2 SAPO-34 which was conditioned to 16.2 wt% by the above humidity control method (standing), was filled into a SUS tube and heat-treated at 170 ° C. for 1 h. The internal pressure at that time was 0.3 MPa. After the heat treatment, the catalyst was extracted, dried at 110 ° C., and used for methylamine synthesis reaction. The reaction results are shown in Table 2.
- Comparative Example 3 SAPO-34 which was conditioned to 16.9 wt% by the above-described humidity control method (standing), was filled in a SUS tube and heat-treated at 170 ° C. for 60 hours. The internal pressure at that time was 0.3 MPa. After the heat treatment, the catalyst was extracted, dried at 110 ° C., and used for methylamine synthesis reaction. The reaction results are shown in Table 2.
- Comparative Example 4 SAPO-34, which was conditioned to 3.1 wt% by the above-described humidity control method (standing), was filled in a SUS tube, pressurized to 2 MPa with nitrogen, and then heat treated at 100 ° C. for 20 hours. After the heat treatment, the catalyst was extracted, dried at 110 ° C., and used for methylamine synthesis reaction. The reaction results are shown in Table 2.
- Comparative Example 5 SAPO-34 adjusted to 25.5 wt% by the above-mentioned humidity control method (standing) was filled in a SUS tube, pressurized to 7 MPa with nitrogen, and heat-treated at 400 ° C. for 15 hours. After the heat treatment, the catalyst was taken out and dried at 110 ° C. and used for methylamine reaction. The reaction results are shown in Table 2.
- Example 10 Using SAPO-34 which was conditioned and heat-treated as in Example 1, a methylamine synthesis reaction using methanol, monomethylamine and ammonia was carried out.
- the reaction temperature was 300 ° C.
- methanol, monomethylamine, and ammonia were fed at 1.60 g / h, 1.37 g / h, 2.39 g / h, and space velocity (GHSV) 1500 h ⁇ 1 , respectively.
- the reaction results after 24 h and after 240 h were as shown in Table 3, respectively.
- Example 11 A monomethylamine disproportionation reaction was carried out using SAPO-34 which was conditioned and heat-treated in the same manner as in Example 1.
- the reaction temperature was 300 ° C.
- the supply amount of monomethylamine was GHSV 3000 h ⁇ 1
- the reaction results after 6 h and 240 h were as shown in Table 4, respectively.
- Example 12 A methylamine synthesis reaction using methanol and monomethylamine was carried out using SAPO-34 which had been conditioned and heat-treated as in Example 1.
- the reaction temperature was 320 ° C.
- methanol and monomethylamine were fed at 1.17 g / h, 4.69 g / h, and space velocity (GHSV) 1200 h ⁇ 1 , respectively.
- the reaction results after 24 h and after 240 h were as shown in Table 5, respectively.
- Comparative Example 8 Using SAPO-34 of Comparative Example 1, methylamine synthesis reaction was performed under the same conditions as in Example 12. The reaction results were as shown in Table 5.
- the method for producing methylamines according to the present invention maintains high dimethylamine selectivity and low trimethylamine selectivity, and further reduces the decrease in activity due to long-term use.
- Target value is extremely high.
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Abstract
Description
<1> 結晶質シリコアルミノリン酸塩モレキュラーシーブに該結晶質シリコアルミノリン酸塩モレキュラーシーブの5~30重量%の水分を吸着させる調湿工程、及び、
前記水分を吸着させた結晶質シリコアルミノリン酸塩モレキュラーシーブを、0.1MPa以上の圧力下、130~350℃の温度で5~40時間熱処理する工程(以下、「熱処理改質工程」と呼ぶことがある)を含む、改質した結晶質シリコアルミノリン酸塩モレキュラーシーブからなるメチルアミン類製造用触媒の製造方法である。
<2> 前記結晶質シリコアルミノリン酸塩モレキュラーシーブが、SAPO-14、17、18、21、22、25、33、34、35、39、42、43、44、47、52及び56から選ばれる少なくとも一種である上記<1>に記載のメチルアミン類製造用触媒の製造方法である。
<3> 前記結晶質シリコアルミノリン酸塩モレキュラーシーブが、Mg、Ca、Sr、Y、Ti、Zr、V、Nb、Cr、Mn、Fe、Ru、Co、Rh、Ir、Ni、Pd、Pt、Cu、Zn、B、Ga、In、Ge及びSnの中から選択される少なくとも一種の元素を含有する上記<1>または<2>に記載のメチルアミン類製造用触媒の製造方法である。
<4> 前記結晶質シリコアルミノリン酸塩モレキュラーシーブに水分を吸着させる調湿工程が、反応器に結晶質シリコアルミノリン酸塩モレキュラーシーブを充填し、水分を含むガスを結晶質シリコアルミノリン酸塩モレキュラーシーブ充填層に連続流通して接触させることを含み、その際、結晶質シリコアルミノリン酸塩モレキュラーシーブと水分を含むガスとの接触をその露点を超える温度で行う上記<1>~<3>のいずれかに記載のメチルアミン類製造用触媒の製造方法である。
<5> 前記水分を含むガスが、水蒸気と、不活性ガスおよび空気から選ばれる少なくとも1種との混合ガスである上記<4>に記載のメチルアミン類製造用触媒の製造方法である。
<6> 結晶質シリコアルミノリン酸塩モレキュラーシーブからなるメチルアミン類製造用触媒の存在下、メタノールとアンモニアとの反応を行うメチルアミン類の製造方法であって、
前記触媒が、上記<1>から<5>のいずれかに記載の改質した結晶質シリコアルミノリン酸塩モレキュラーシーブからなるメチルアミン類製造用触媒の製造方法によって製造される、前記メチルアミン類の製造方法である。
<7> 結晶質シリコアルミノリン酸塩モレキュラーシーブからなるメチルアミン類製造用触媒の存在下、メタノールとモノメチルアミンとの反応、あるいは、メタノールとアンモニアとモノメチルアミンとの反応を行うメチルアミン類の製造方法であって、
前記触媒が、上記<1>から<5>のいずれかに記載の改質した結晶質シリコアルミノリン酸塩モレキュラーシーブからなるメチルアミン類製造用触媒の製造方法によって製造される、前記メチルアミン類の製造方法である。
<8> 結晶質シリコアルミノリン酸塩モレキュラーシーブからなるメチルアミン類製造用触媒の存在下、モノメチルアミンの不均化反応を行うメチルアミン類の製造方法であって、
前記触媒が、上記<1>から<5>のいずれかに記載の改質した結晶質シリコアルミノリン酸塩モレキュラーシーブからなるメチルアミン類製造用触媒の製造方法によって製造される、前記メチルアミン類の製造方法である。
結晶質シリコアルミノリン酸塩モレキュラーシーブとは、米国特許第4,440,871号明細書に記載されているように、結晶質であるとともに微孔質でありPO2 +、AlO2 -及びSiO2四面体単位からなる三次元微孔質結晶骨格構造を有する化合物のことであり、SAPOと呼ばれる。また、ケイ素、アルミニウム、リン以外の金属の四面体単位を三次元微孔質結晶骨格構造に含む化合物も欧州特許第159,624号明細書などに開示されており、ELAPSOモレキュラーシーブと呼ばれている。SAPO及びELAPSOは、前記四面体単位の配列により、細孔径や細孔の連結様式が異なる種々の構造のSAPO、ELAPSOが知られている。本発明のメチルアミン類製造用触媒の製造に用いられるSAPOはELAPSOも含む。
なお、実施例及び比較例で用いたSAPO及び金属含有SAPOは、特許文献14記載の実施例1(SAPO-34合成)及び実施例6(Ti含有SAPO-34合成)に従って合成したものを1~2mmに整粒し使用した。また調湿方法(静置、連続)、熱処理方法、メチルアミン合成反応及び反応生成物の分析方法は以下の通りである。
(1)調湿方法(静置):
あらかじめ110℃の乾燥器で重量変化がなくなるまで乾燥させたSAPOの所定量と目標調湿量に対応する水とを別々の磁性皿にはかりとり、これらの皿をデシケーター内に設置して、密閉した。このデシケーターを110℃の乾燥器内で加熱し、2h後に乾燥器から取り出して、室温まで冷却した。調湿量の計算方法は、以下の通りである。
SAPO調湿量(重量%)=(調湿後のSAPO重量-調湿前の乾燥SAPO重量)/調湿前の乾燥SAPO重量×100
(2)調湿方法(連続):
あらかじめ重量を測定した内径13mmφ、長さ30cmの反応管の上部に圧力ゲージ、窒素供給バルブ、蒸気供給バルブ、下部にガス閉止用バルブを取り付けて行った。反応管に乾燥させたSAPOを10g入れ、反応管をアルミブロックヒーターで加熱した。所定量の水蒸気及び窒素を反応器上部から供給し、水分の吸着と脱離が平衡に達してSAPO層の温度分布が一定になるまで、温度、圧力、水分濃度の条件を維持した。調湿量は調湿操作終了後に反応管の重量を測定し、SAPOへの水分吸着量から計算して求めた。
(3)熱処理方法:
内径10mm、長さ30cmのSUS管を使用した。管部分はマントルヒーターで加熱し、上部に圧力ゲージ、窒素加圧用のバルブ、調圧弁を取り付け、下部はプラグで閉止した。SAPO約4g(約7ml)を入れた後、マントルヒーターでSUS管全体を加熱し、所定時間終了後、SUS管内を落圧し、SAPOを取り出した。なおSAPOはメチルアミン合成反応の使用前に110℃で再度乾燥した。
(4)メチルアミン合成反応:
内径13mmφ、長さ30cmの反応管に、調湿・熱処理後の乾燥SAPO2.5g(3.5ml)を充填し、2MPaに昇圧後、305℃に昇温し、その後メタノールとアンモニア重量比1の混合原料を毎時8.62g、空間速度(GHSV)2500h-1で供給して行った。
(5)反応生成物の分析方法:
反応液を水溶液として捕集した後、キャピラリーカラムCP-Volamineを使用し、島津製GC-FIDにて分析した。
4.00gの乾燥SAPO-34を、0.62gの水を用いて、上記の調湿方法(静置)で調湿した。冷却後に取り出したSAPOの重量は4.62gであり、調湿量は15.5wt%であった。続いて該SAPOを熱処理用のSUS管に充填し、170℃で20h熱処理を行った。その際の内圧は0.3MPaであった。熱処理終了後、落圧して110℃で2h乾燥し、メチルアミン合成反応に使用した。反応開始後24h後の反応成績はメタノール転化率92wt%、モノメチルアミン選択率35wt%、ジメチルアミン選択率60wt%、トリメチルアミン選択率5wt%であった。また240h後の反応成績はメタノール転化率90wt%、モノメチルアミン選択率38wt%、ジメチルアミン選択率59wt%、トリメチルアミン選択率3wt%であった。
上記の調湿方法(静置)で10.2wt%に調湿したSAPO-34をSUS管に充填し、窒素で1MPaに加圧後、250℃で15h熱処理した。熱処理後、触媒を抜き出して、110℃で乾燥後、メチルアミン合成反応に使用した。反応結果を表2に示した。
上記の調湿方法(静置)で25.4wt%に調湿したSAPO-34をSUS管に充填し、窒素で2MPaに加圧後、140℃で20h熱処理した。熱処理後、触媒を抜き出して、110℃で乾燥後、メチルアミン合成反応に使用した。反応結果を表2に示した。
上記の調湿方法(静置)で15.3%に調湿したSAPO-34をSUS管に充填し、窒素で2MPaに加圧後、320℃で15h熱処理した。熱処理後、触媒を抜き出して、110℃で乾燥後、メチルアミン合成反応に使用した。反応結果を表2に示した。
上記の調湿方法(静置)で16.0wt%に調湿したSAPO-34をSUS管に充填し、窒素で1.5MPaに加圧後、170℃で20h熱処理した。熱処理後、触媒を抜き出して、110℃で乾燥後、メチルアミン合成反応に使用した。反応結果を表2に示した。
上記の調湿方法(静置)で15.4%に調湿したSAPO-34をSUS管に充填し、170℃で10h熱処理した。その際の内圧は0.3MPaであった。熱処理後、触媒を抜き出して、110℃で乾燥後、メチルアミン合成反応に使用した。反応結果を表2に示した。
上記の調湿方法(静置)で15.3%に調湿したSAPO-34をSUS管に充填し、170℃で35h熱処理した。その際の内圧は0.3MPaであった。熱処理後、触媒を抜き出して、110℃で乾燥後、メチルアミン合成反応に使用した。反応結果を表2に示した。
上記の調湿方法(連続)で調湿を行った。反応管に乾燥したSAPO-34を10g入れ、SAPO層温度を112℃とし、窒素流量60ml/min、水蒸気流量2.02g/hで、SAPO層温度が一定となるまで混合ガスを供給した。重量増加から計算したSAPO調湿量は15.4wt%であった。調湿終了後、反応管上部の蒸気供給バルブ、窒素供給バルブ、下部ガス閉止バルブを閉とし、そのままの状態で170℃まで加熱、15h熱処理した。なお熱処理時の内圧は0.3MPaであった。熱処理後、110℃でSAPOを乾燥後、メチルアミン合成反応に使用した。反応結果を表2に示した。
SAPO-34の代わりにTi含有SAPO-34を使用した以外は実施例1と同様の方法で調湿と熱処理を行い、メチルアミン合成反応に使用した。反応結果を表2に示した。
乾燥したSAPO-34を、調湿と熱処理を行わないでメチルアミン合成反応に使用した。反応結果を表2に示した。
上記の調湿方法(静置)で16.2wt%に調湿したSAPO-34をSUS管に充填し、170℃で1h熱処理した。その際の内圧は0.3MPaであった。熱処理後、触媒を抜き出して、110℃で乾燥後、メチルアミン合成反応に使用した。反応結果を表2に示した。
上記の調湿方法(静置)で16.9wt%に調湿したSAPO-34をSUS管に充填し、170℃で60h熱処理した。その際の内圧は0.3MPaであった。熱処理後、触媒を抜き出して、110℃で乾燥後、メチルアミン合成反応に使用した。反応結果を表2に示した。
上記の調湿方法(静置)で3.1wt%に調湿したSAPO-34をSUS管に充填し、窒素で2MPaに加圧後、100℃で20h熱処理した。熱処理後、触媒を抜き出して、110℃で乾燥後、メチルアミン合成反応に使用した。反応結果を表2に示した。
上記の調湿方法(静置)で25.5wt%に調湿したSAPO-34をSUS管に充填し、窒素で7MPaに加圧後、400℃で15h熱処理した。熱処理後、触媒を抜き出し、110℃で乾燥後にメチルアミン反応に使用した。反応結果を表2に示す。
実施例1と同様に調湿と熱処理したSAPO-34を用いて、メタノールとモノメチルアミン、アンモニアを使用するメチルアミン合成反応を行った。反応温度は300℃、メタノール、モノメチルアミン、アンモニアはそれぞれ1.60g/h、1.37g/h、2.39g/h、空間速度(GHSV)1500h-1で供給した。24h後、240h後の反応成績はそれぞれ表3に示す通りであった。
比較例1のSAPO-34を用いて、実施例10と同じ条件でメチルアミン合成反応を行った。反応結果は表3に示す通りであった。
実施例1と同様に調湿と熱処理したSAPO-34を用いて、モノメチルアミンの不均化反応を行った。反応温度は300℃、モノメチルアミンの供給量はGHSV3000h-1とし、6h後、240h後の反応成績は、それぞれ表4に示す通りであった。
比較例1のSAPO-34を用いて、実施例11と同じ条件でモノメチルアミンの不均化反応を行った。反応結果を表4に示す。
実施例1と同様に調湿と熱処理したSAPO-34を用いて、メタノールとモノメチルアミンを使用するメチルアミン合成反応を行った。反応温度は320℃、メタノール、モノメチルアミンはそれぞれ1.17g/h、4.69g/h、空間速度(GHSV)1200h-1で供給した。24h後、240h後の反応成績はそれぞれ表5に示す通りであった。
比較例1のSAPO-34を用いて、実施例12と同じ条件でメチルアミン合成反応を行った。反応結果は表5に示す通りであった。
Claims (8)
- 結晶質シリコアルミノリン酸塩モレキュラーシーブに該結晶質シリコアルミノリン酸塩モレキュラーシーブの5~30重量%の水分を吸着させる調湿工程、及び、
前記水分を吸着させた結晶質シリコアルミノリン酸塩モレキュラーシーブを、0.1MPa以上の圧力下、130~350℃の温度で5~40時間熱処理する工程を含む、改質した結晶質シリコアルミノリン酸塩モレキュラーシーブからなるメチルアミン類製造用触媒の製造方法。 - 前記結晶質シリコアルミノリン酸塩モレキュラーシーブが、SAPO-14、17、18、21、22、25、33、34、35、39、42、43、44、47、52及び56から選ばれる少なくとも一種である請求項1に記載のメチルアミン類製造用触媒の製造方法。
- 前記結晶質シリコアルミノリン酸塩モレキュラーシーブが、Mg、Ca、Sr、Y、Ti、Zr、V、Nb、Cr、Mn、Fe、Ru、Co、Rh、Ir、Ni、Pd、Pt、Cu、Zn、B、Ga、In、Ge及びSnの中から選択される少なくとも一種の元素を含有する請求項1または2に記載のメチルアミン類製造用触媒の製造方法。
- 前記結晶質シリコアルミノリン酸塩モレキュラーシーブに水分を吸着させる調湿工程が、反応器に結晶質シリコアルミノリン酸塩モレキュラーシーブを充填し、水分を含むガスを結晶質シリコアルミノリン酸塩モレキュラーシーブ充填層に連続流通して接触させることを含み、その際、結晶質シリコアルミノリン酸塩モレキュラーシーブと水分を含むガスとの接触をその露点を超える温度で行う請求項1~3のいずれかに記載のメチルアミン類製造用触媒の製造方法。
- 前記水分を含むガスが、水蒸気と、不活性ガスおよび空気から選ばれる少なくとも1種との混合ガスである請求項4に記載のメチルアミン類製造用触媒の製造方法。
- 結晶質シリコアルミノリン酸塩モレキュラーシーブからなるメチルアミン類製造用触媒の存在下、メタノールとアンモニアとの反応を行うメチルアミン類の製造方法であって、
前記触媒が、請求項1から5のいずれかに記載の改質した結晶質シリコアルミノリン酸塩モレキュラーシーブからなるメチルアミン類製造用触媒の製造方法によって製造される、前記メチルアミン類の製造方法。 - 結晶質シリコアルミノリン酸塩モレキュラーシーブからなるメチルアミン類製造用触媒の存在下、メタノールとモノメチルアミンとの反応、あるいは、メタノールとアンモニアとモノメチルアミンとの反応を行うメチルアミン類の製造方法であって、
前記触媒が、請求項1から5のいずれかに記載の改質した結晶質シリコアルミノリン酸塩モレキュラーシーブからなるメチルアミン類製造用触媒の製造方法によって製造される、前記メチルアミン類の製造方法。 - 結晶質シリコアルミノリン酸塩モレキュラーシーブからなるメチルアミン類製造用触媒の存在下、モノメチルアミンの不均化反応を行うメチルアミン類の製造方法であって、
前記触媒が、請求項1から5のいずれかに記載の改質した結晶質シリコアルミノリン酸塩モレキュラーシーブからなるメチルアミン類製造用触媒の製造方法によって製造される、前記メチルアミン類の製造方法。
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Citations (23)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4082805A (en) | 1974-11-01 | 1978-04-04 | Mobil Oil Corporation | Production of aliphatic amines utilizing a crystalline aluminosilicate catalyst of zsm-5, zsm-11 or zsm-21 |
JPS54148708A (en) | 1978-04-21 | 1979-11-21 | Ici Ltd | Manufacture of amine |
JPS5646846A (en) | 1979-09-11 | 1981-04-28 | Du Pont | Improved manufacture of dimethylamine |
JPS56113747A (en) | 1979-09-11 | 1981-09-07 | Du Pont | Manufacture of monomethylamine |
JPS5849340A (ja) | 1981-09-19 | 1983-03-23 | Toyo Soda Mfg Co Ltd | ジメチルアミンの選択的製造方法 |
JPS5869846A (ja) | 1981-09-18 | 1983-04-26 | インペリアル・ケミカル・インダストリ−ズ・ピ−エルシ− | メチルアミンの製法 |
US4440871A (en) | 1982-07-26 | 1984-04-03 | Union Carbide Corporation | Crystalline silicoaluminophosphates |
US4477336A (en) | 1982-03-02 | 1984-10-16 | Harshaw/Filtrol Partnership | Acid dealuminated Y-zeolite and cracking process employing the same |
JPS59210050A (ja) | 1983-05-13 | 1984-11-28 | Nitto Chem Ind Co Ltd | ジメチルアミンの製造法 |
JPS59227841A (ja) | 1983-06-08 | 1984-12-21 | Nitto Chem Ind Co Ltd | ジメチルアミンの選択的製造法 |
EP0159624A2 (en) | 1984-04-13 | 1985-10-30 | Uop | Molecular sieve compositions |
JPS61254256A (ja) | 1985-04-30 | 1986-11-12 | イ−・アイ・デユポン・ドウ・ヌム−ル・アンド・カンパニ− | メタノ−ル及びアンモニアをジメチルアミンに転換する触媒としての8−環ゼオライト |
JPH01239729A (ja) | 1988-03-18 | 1989-09-25 | Hitachi Ltd | カラーブラウン管の製造方法 |
JPH02734A (ja) | 1987-12-23 | 1990-01-05 | Uop Inc | アルキルアミンの製造方法 |
US5248647A (en) | 1991-02-28 | 1993-09-28 | Uop | Sapo catalysts and use thereof in methanol conversion processes |
JPH1135527A (ja) | 1997-07-23 | 1999-02-09 | Mitsubishi Gas Chem Co Inc | メチルアミン類の製造法 |
JP2000005604A (ja) | 1998-06-26 | 2000-01-11 | Mitsubishi Gas Chem Co Inc | メチルアミン製造用触媒及び該触媒を用いたメチルアミン類の製造方法 |
JP2002210374A (ja) * | 2001-01-18 | 2002-07-30 | Mitsubishi Gas Chem Co Inc | モレキュラーシーブ打錠成型体 |
JP2004049987A (ja) * | 2002-07-17 | 2004-02-19 | Mitsubishi Gas Chem Co Inc | シャバサイト型結晶質シリコアルミノリン酸塩モレキュラーシーブの圧縮打錠成型体及び成型方法 |
JP2005518930A (ja) * | 2002-02-28 | 2005-06-30 | エクソンモービル・ケミカル・パテンツ・インク | 分子篩組成物、それらの触媒、それらの製造、及び変換法における使用 |
JP2006527150A (ja) | 2003-06-06 | 2006-11-30 | ビーエーエスエフ アクチェンゲゼルシャフト | 成形体の切削硬さを上昇させる方法 |
JP4362363B2 (ja) | 2001-06-25 | 2009-11-11 | エクソンモービル・ケミカル・パテンツ・インク | 非ゼオライト系分子篩触媒を用いる炭化水素変換方法 |
JP4596116B2 (ja) | 2002-05-24 | 2010-12-08 | 三菱瓦斯化学株式会社 | 8酸素員環細孔を持つ結晶質シリコアルミノリン酸塩モレキュラーシーブ及びその製造方法、並びにそれを触媒とするメチルアミン類の製造方法 |
Family Cites Families (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4313003A (en) | 1979-09-11 | 1982-01-26 | E. I. Du Pont De Nemours And Company | Preparation of dimethylamine |
TWI234556B (en) * | 1997-07-23 | 2005-06-21 | Mitsubishi Gas Chemical Co | Catalysts for methanol conversion reactions |
JP4174634B2 (ja) | 1997-12-26 | 2008-11-05 | 三菱瓦斯化学株式会社 | シリカ変性シリコアルミノホスフェート触媒、その製造方法及びそれを用いるメチルアミン類等の製造方法 |
US6906232B2 (en) | 2002-08-09 | 2005-06-14 | Exxonmobil Chemical Patents Inc. | Molecular sieve compositions, catalysts thereof, their making and use in conversion processes |
US6844291B2 (en) | 2002-02-28 | 2005-01-18 | Exxonmobil Chemical Patents Inc. | Molecular sieve compositions, catalyst thereof, their making and use in conversion processes |
US7319178B2 (en) | 2002-02-28 | 2008-01-15 | Exxonmobil Chemical Patents Inc. | Molecular sieve compositions, catalysts thereof, their making and use in conversion processes |
US6995111B2 (en) | 2002-02-28 | 2006-02-07 | Exxonmobil Chemical Patents Inc. | Molecular sieve compositions, catalysts thereof, their making and use in conversion processes |
US7208442B2 (en) | 2002-02-28 | 2007-04-24 | Exxonmobil Chemical Patents Inc. | Molecular sieve compositions, catalyst thereof, their making and use in conversion processes |
US7307196B2 (en) | 2002-02-28 | 2007-12-11 | Exxonmobil Chemical Patents Inc. | Molecular sieve compositions, catalyst thereof, their making and use in conversion processes |
KR100987726B1 (ko) | 2002-05-24 | 2010-10-13 | 미츠비시 가스 가가쿠 가부시키가이샤 | 8산소원환 미세공을 갖는 결정질 실리코알루미노포스페이트 분자체, 그 제조방법 및 촉매로서 상기분자체를 사용한 메틸아민류의 제조방법 |
DE10313853A1 (de) * | 2003-03-27 | 2004-10-07 | Basf Ag | Verfahren zur Herstellung von Alkylaminen und zur Erhöhung der Hydroaminierungsaktivität von calcinierten zeolithischen Katalysatoren |
US7015174B2 (en) * | 2003-06-20 | 2006-03-21 | Exxonmobil Chemical Patents Inc. | Maintaining molecular sieve catalytic activity under water vapor conditions |
-
2013
- 2013-10-11 US US14/433,500 patent/US9180444B2/en active Active
- 2013-10-11 WO PCT/JP2013/077706 patent/WO2014061569A1/ja active Application Filing
- 2013-10-11 JP JP2014542096A patent/JP6065014B2/ja active Active
- 2013-10-11 EP EP13847944.9A patent/EP2907571B1/en active Active
- 2013-10-11 CN CN201380052998.3A patent/CN104718025B/zh active Active
Patent Citations (23)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4082805A (en) | 1974-11-01 | 1978-04-04 | Mobil Oil Corporation | Production of aliphatic amines utilizing a crystalline aluminosilicate catalyst of zsm-5, zsm-11 or zsm-21 |
JPS54148708A (en) | 1978-04-21 | 1979-11-21 | Ici Ltd | Manufacture of amine |
JPS5646846A (en) | 1979-09-11 | 1981-04-28 | Du Pont | Improved manufacture of dimethylamine |
JPS56113747A (en) | 1979-09-11 | 1981-09-07 | Du Pont | Manufacture of monomethylamine |
JPS5869846A (ja) | 1981-09-18 | 1983-04-26 | インペリアル・ケミカル・インダストリ−ズ・ピ−エルシ− | メチルアミンの製法 |
JPS5849340A (ja) | 1981-09-19 | 1983-03-23 | Toyo Soda Mfg Co Ltd | ジメチルアミンの選択的製造方法 |
US4477336A (en) | 1982-03-02 | 1984-10-16 | Harshaw/Filtrol Partnership | Acid dealuminated Y-zeolite and cracking process employing the same |
US4440871A (en) | 1982-07-26 | 1984-04-03 | Union Carbide Corporation | Crystalline silicoaluminophosphates |
JPS59210050A (ja) | 1983-05-13 | 1984-11-28 | Nitto Chem Ind Co Ltd | ジメチルアミンの製造法 |
JPS59227841A (ja) | 1983-06-08 | 1984-12-21 | Nitto Chem Ind Co Ltd | ジメチルアミンの選択的製造法 |
EP0159624A2 (en) | 1984-04-13 | 1985-10-30 | Uop | Molecular sieve compositions |
JPS61254256A (ja) | 1985-04-30 | 1986-11-12 | イ−・アイ・デユポン・ドウ・ヌム−ル・アンド・カンパニ− | メタノ−ル及びアンモニアをジメチルアミンに転換する触媒としての8−環ゼオライト |
JPH02734A (ja) | 1987-12-23 | 1990-01-05 | Uop Inc | アルキルアミンの製造方法 |
JPH01239729A (ja) | 1988-03-18 | 1989-09-25 | Hitachi Ltd | カラーブラウン管の製造方法 |
US5248647A (en) | 1991-02-28 | 1993-09-28 | Uop | Sapo catalysts and use thereof in methanol conversion processes |
JPH1135527A (ja) | 1997-07-23 | 1999-02-09 | Mitsubishi Gas Chem Co Inc | メチルアミン類の製造法 |
JP2000005604A (ja) | 1998-06-26 | 2000-01-11 | Mitsubishi Gas Chem Co Inc | メチルアミン製造用触媒及び該触媒を用いたメチルアミン類の製造方法 |
JP2002210374A (ja) * | 2001-01-18 | 2002-07-30 | Mitsubishi Gas Chem Co Inc | モレキュラーシーブ打錠成型体 |
JP4362363B2 (ja) | 2001-06-25 | 2009-11-11 | エクソンモービル・ケミカル・パテンツ・インク | 非ゼオライト系分子篩触媒を用いる炭化水素変換方法 |
JP2005518930A (ja) * | 2002-02-28 | 2005-06-30 | エクソンモービル・ケミカル・パテンツ・インク | 分子篩組成物、それらの触媒、それらの製造、及び変換法における使用 |
JP4596116B2 (ja) | 2002-05-24 | 2010-12-08 | 三菱瓦斯化学株式会社 | 8酸素員環細孔を持つ結晶質シリコアルミノリン酸塩モレキュラーシーブ及びその製造方法、並びにそれを触媒とするメチルアミン類の製造方法 |
JP2004049987A (ja) * | 2002-07-17 | 2004-02-19 | Mitsubishi Gas Chem Co Inc | シャバサイト型結晶質シリコアルミノリン酸塩モレキュラーシーブの圧縮打錠成型体及び成型方法 |
JP2006527150A (ja) | 2003-06-06 | 2006-11-30 | ビーエーエスエフ アクチェンゲゼルシャフト | 成形体の切削硬さを上昇させる方法 |
Non-Patent Citations (4)
Title |
---|
D. R. CORBIN; S. SCHWARZ; G. C. SONNICHSEN, CATALYSIS TODAY, vol. 37, 1997, pages 71 - 102 |
See also references of EP2907571A4 |
SYNTHESIS AND APPLICATION OF FUNCTIONAL ZEOLITE, pages 83 - 92 |
THE STRUCTURE COMMISSION OF THE INTERNATIONAL ZEOLITE ASSOCIATION: "Atlas of Zeolite Framework Types", ELSEVIER |
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EP2907571A1 (en) | 2015-08-19 |
CN104718025B (zh) | 2017-05-10 |
CN104718025A (zh) | 2015-06-17 |
US20150258538A1 (en) | 2015-09-17 |
US9180444B2 (en) | 2015-11-10 |
JPWO2014061569A1 (ja) | 2016-09-05 |
EP2907571A4 (en) | 2016-06-15 |
EP2907571B1 (en) | 2017-12-13 |
JP6065014B2 (ja) | 2017-01-25 |
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