WO2015156301A1 - メタクリル酸メチル製造用触媒成型体及びそれを用いたメタクリル酸メチルの製造方法 - Google Patents
メタクリル酸メチル製造用触媒成型体及びそれを用いたメタクリル酸メチルの製造方法 Download PDFInfo
- Publication number
- WO2015156301A1 WO2015156301A1 PCT/JP2015/060912 JP2015060912W WO2015156301A1 WO 2015156301 A1 WO2015156301 A1 WO 2015156301A1 JP 2015060912 W JP2015060912 W JP 2015060912W WO 2015156301 A1 WO2015156301 A1 WO 2015156301A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- methyl methacrylate
- silicate compound
- catalyst
- synthetic
- molded body
- Prior art date
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 108
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 36
- 238000000034 method Methods 0.000 title description 11
- -1 aluminum silicate compound Chemical class 0.000 claims abstract description 67
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 54
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 48
- 239000010457 zeolite Substances 0.000 claims abstract description 48
- 239000000391 magnesium silicate Substances 0.000 claims abstract description 31
- 229910052919 magnesium silicate Inorganic materials 0.000 claims abstract description 31
- 235000019792 magnesium silicate Nutrition 0.000 claims abstract description 31
- 238000006243 chemical reaction Methods 0.000 claims abstract description 29
- XYVQFUJDGOBPQI-UHFFFAOYSA-N Methyl-2-hydoxyisobutyric acid Chemical compound COC(=O)C(C)(C)O XYVQFUJDGOBPQI-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000012013 faujasite Substances 0.000 claims abstract description 23
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 72
- 239000002994 raw material Substances 0.000 claims description 26
- 239000011734 sodium Substances 0.000 claims description 17
- 150000001875 compounds Chemical class 0.000 claims description 12
- 239000004927 clay Substances 0.000 claims description 11
- 239000006185 dispersion Substances 0.000 claims description 11
- AZJYLVAUMGUUBL-UHFFFAOYSA-A u1qj22mc8e Chemical compound [F-].[F-].[F-].[F-].[F-].[F-].[F-].[F-].[F-].[F-].[F-].[F-].[F-].[F-].[F-].[F-].[F-].[F-].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].O=[Si]=O.O=[Si]=O.O=[Si]=O.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3 AZJYLVAUMGUUBL-UHFFFAOYSA-A 0.000 claims description 9
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 8
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 8
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 8
- 229910052708 sodium Inorganic materials 0.000 claims description 8
- 239000003085 diluting agent Substances 0.000 claims description 5
- VNSBYDPZHCQWNB-UHFFFAOYSA-N calcium;aluminum;dioxido(oxo)silane;sodium;hydrate Chemical compound O.[Na].[Al].[Ca+2].[O-][Si]([O-])=O VNSBYDPZHCQWNB-UHFFFAOYSA-N 0.000 claims description 3
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052622 kaolinite Inorganic materials 0.000 claims description 3
- 239000012808 vapor phase Substances 0.000 abstract description 2
- 239000007858 starting material Substances 0.000 abstract 1
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 22
- 239000006227 byproduct Substances 0.000 description 22
- 229910001415 sodium ion Inorganic materials 0.000 description 17
- 239000011230 binding agent Substances 0.000 description 12
- 239000007789 gas Substances 0.000 description 12
- 238000011056 performance test Methods 0.000 description 12
- 238000003786 synthesis reaction Methods 0.000 description 12
- XCOBTUNSZUJCDH-UHFFFAOYSA-B lithium magnesium sodium silicate Chemical compound [Li+].[Li+].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Na+].[Na+].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3 XCOBTUNSZUJCDH-UHFFFAOYSA-B 0.000 description 11
- 239000000203 mixture Substances 0.000 description 11
- 238000011084 recovery Methods 0.000 description 11
- 239000012071 phase Substances 0.000 description 10
- 229940094522 laponite Drugs 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 238000004458 analytical method Methods 0.000 description 8
- 238000000465 moulding Methods 0.000 description 8
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 7
- 239000007795 chemical reaction product Substances 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 6
- 239000003513 alkali Substances 0.000 description 6
- 229910000323 aluminium silicate Inorganic materials 0.000 description 6
- 238000009835 boiling Methods 0.000 description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 5
- 239000000440 bentonite Substances 0.000 description 5
- 229910000278 bentonite Inorganic materials 0.000 description 5
- 238000006555 catalytic reaction Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000006297 dehydration reaction Methods 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 150000001768 cations Chemical class 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- QSJXEFYPDANLFS-UHFFFAOYSA-N Diacetyl Chemical group CC(=O)C(C)=O QSJXEFYPDANLFS-UHFFFAOYSA-N 0.000 description 3
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
- 239000011229 interlayer Substances 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- DRYMMXUBDRJPDS-UHFFFAOYSA-N 2-hydroxy-2-methylpropanamide Chemical compound CC(C)(O)C(N)=O DRYMMXUBDRJPDS-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 241000871495 Heeria argentea Species 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000004480 active ingredient Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 150000001733 carboxylic acid esters Chemical class 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 238000001132 ultrasonic dispersion Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- MWFMGBPGAXYFAR-UHFFFAOYSA-N 2-hydroxy-2-methylpropanenitrile Chemical compound CC(C)(O)C#N MWFMGBPGAXYFAR-UHFFFAOYSA-N 0.000 description 1
- JIRULJUIQOAJPM-UHFFFAOYSA-N 3-methoxy-2-methylpropanoic acid Chemical compound COCC(C)C(O)=O JIRULJUIQOAJPM-UHFFFAOYSA-N 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
- NGEWQZIDQIYUNV-UHFFFAOYSA-N L-valinic acid Natural products CC(C)C(O)C(O)=O NGEWQZIDQIYUNV-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical class [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 1
- RJDOZRNNYVAULJ-UHFFFAOYSA-L [O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[F-].[F-].[Mg++].[Mg++].[Mg++].[Al+3].[Si+4].[Si+4].[Si+4].[K+] Chemical compound [O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[F-].[F-].[Mg++].[Mg++].[Mg++].[Al+3].[Si+4].[Si+4].[Si+4].[K+] RJDOZRNNYVAULJ-UHFFFAOYSA-L 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- KWLMIXQRALPRBC-UHFFFAOYSA-L hectorite Chemical class [Li+].[OH-].[OH-].[Na+].[Mg+2].O1[Si]2([O-])O[Si]1([O-])O[Si]([O-])(O1)O[Si]1([O-])O2 KWLMIXQRALPRBC-UHFFFAOYSA-L 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical class [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 159000000003 magnesium salts Chemical class 0.000 description 1
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 1
- 238000006140 methanolysis reaction Methods 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000012264 purified product Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910021647 smectite Inorganic materials 0.000 description 1
- 229910001388 sodium aluminate Inorganic materials 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 239000004071 soot Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 239000004094 surface-active agent Substances 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/19—Catalysts containing parts with different compositions
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/317—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by splitting-off hydrogen or functional groups; by hydrogenolysis of functional groups
- C07C67/327—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by splitting-off hydrogen or functional groups; by hydrogenolysis of functional groups by elimination of functional groups containing oxygen only in singly bound form
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/16—Clays or other mineral silicates
-
- 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
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B61/00—Other general methods
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/52—Esters of acyclic unsaturated carboxylic acids having the esterified carboxyl group bound to an acyclic carbon atom
- C07C69/533—Monocarboxylic acid esters having only one carbon-to-carbon double bond
- C07C69/54—Acrylic acid esters; Methacrylic acid esters
Definitions
- the present invention relates to a method for producing methyl methacrylate by vapor phase contact reaction using methyl ⁇ -hydroxyisobutyrate as a raw material and a molded catalyst for producing methyl methacrylate used therefor.
- Methyl methacrylate has industrially important uses such as a raw material for polymethyl methacrylate excellent in weather resistance and transparency and a raw material for various methacrylic acid esters.
- Patent Document 1 discloses ⁇ -hydroxycarboxylic acid ester, ⁇ -alkoxycarboxylic acid ester and ⁇ -alkoxy.
- a method for producing an ⁇ , ⁇ -unsaturated carboxylic ester by using a single or mixture of carboxylic esters as a raw material and subjecting the crystalline aluminosilicate to a dehydration or dealcoholization reaction using a catalyst.
- crystalline aluminosilicate used in the production method it is described that X-type or Y-type zeolite exhibits particularly excellent catalytic activity.
- Patent Document 2 Patent Document 3 and Patent Document 4, crystalline aluminosilicate modified with alkali metal and / or platinum group element, particularly X-type or Y-type zeolite is effective as a catalyst for the production method. It is disclosed.
- Patent Document 5 uses a transition-type synthetic faujasite-type zeolite having a lattice constant in the boundary region between X-type and Y-type with a prescribed Na content, thereby diacetyl which is a coloring substance. It is disclosed that by-production of high boiling point by-products can be reduced and catalytic activity can be maintained for a long time. At that time, it is described that a clay having an Al content of less than 5% by weight, particularly a silica magnesia clay, is suitable as a binder for suppressing diacetyl by-product.
- Patent Document 6 discloses that a catalyst comprising a synthetic faujasite type zeolite having a free alkali amount of 0.1 meq / g or less as an active ingredient, or a pH when the synthetic faujasite type zeolite is dispersed in water is 9. It is disclosed that by using a catalyst made of a molded body using less than clay, by-product of a high-boiling by-product that causes temporary deterioration of the catalyst is suppressed, and the life of the catalyst is further increased.
- the object of the present invention is to use methyl ⁇ -hydroxyisobutyrate as a raw material in a method for producing methyl methacrylate by gas phase catalytic reaction, which has a higher methanol recovery rate and longer catalyst life than conventional methods.
- the object is to provide a molded catalyst for production and a method for producing methyl methacrylate using the molded catalyst for production of methyl methacrylate.
- the present inventors molded a synthetic faujasite-type zeolite and a binder component obtained by mixing a layered aluminum silicate compound and a synthetic layered magnesium silicate compound at a specific ratio.
- a molded catalyst obtained as a catalyst for the production of methyl methacrylate we found that by-product amount of DME was suppressed compared to the conventional method, and while maintaining a high methanol recovery rate, the catalyst life was also extended.
- the present invention has been completed.
- the present invention is as follows. ⁇ 1> A catalyst molded body for producing methyl methacrylate, wherein methyl methacrylate is produced by gas phase contact reaction using methyl ⁇ -hydroxyisobutyrate as a raw material, the catalyst molded body comprising synthetic faujasite type zeolite and layered silica A methacrylic acid comprising an aluminum silicate compound and a synthetic layered magnesium silicate compound, wherein a weight ratio of the layered aluminum silicate compound to the synthetic layered magnesium silicate compound is 1: 5 to 6: 1 This is a molded catalyst for methyl production.
- ⁇ 2> The catalyst molded body for producing methyl methacrylate according to the above ⁇ 1>, wherein the pH value of the aqueous dispersion containing the catalyst molded body component at a ratio of 2% by weight is 10.2 to 10.8.
- ⁇ 3> The catalyst molded body for producing methyl methacrylate according to the above ⁇ 1> or ⁇ 2>, wherein the amount of free sodium in the catalyst molded body is 0.03 meq / g or less.
- the ratio of the total amount of the layered aluminum silicate compound and the synthetic layered magnesium silicate compound to the total amount of the synthetic faujasite type zeolite, the layered aluminum silicate compound, and the synthetic layered magnesium silicate compound is 3 to 30
- ⁇ 6> The catalyst molded body for producing methyl methacrylate according to any one of ⁇ 1> to ⁇ 5>, wherein the layered aluminum silicate compound is a clay compound containing montmorillonite as a main component.
- ⁇ 7> The catalyst molded body for producing methyl methacrylate according to any one of ⁇ 1> to ⁇ 6>, wherein the synthetic layered magnesium silicate compound is a synthetic hectorite.
- ⁇ 8> Producing methyl methacrylate by gas phase contact reaction using methyl ⁇ -hydroxyisobutyrate as a raw material in the presence of the catalyst molded product for producing methyl methacrylate according to any one of ⁇ 1> to ⁇ 7> above. It is a manufacturing method of methyl methacrylate.
- ⁇ 9> The method for producing methyl methacrylate according to ⁇ 8>, wherein methanol is used in a range of 0.1 to 3.0 times by weight of methanol relative to methyl ⁇ -hydroxyisobutyrate as a diluent.
- the catalyst molded body for producing methyl methacrylate according to the present invention is obtained by molding a synthetic faujasite type zeolite, a layered aluminum silicate compound, and a synthetic layered magnesium silicate compound.
- the synthetic faujasite-type zeolite that can be used in the present invention is a three-letter code representing the crystal structure of a crystalline molecular sieve defined by the International Zeolite Society (IZA). It has an aluminosilicate.
- IZA International Zeolite Society
- types of synthetic faujasite-type zeolite X-type and Y-type having the same crystal structure but different chemical composition, that is, different Si / Al atomic ratio are generally known, and any of them can be suitably used.
- the transition type synthetic faujasite type zeolite is a zeolite whose lattice constant measured by X-ray diffraction is in the range of 24.80 to 24.94 ⁇ .
- the cation type of the synthetic faujasite type zeolite used in the present invention is not particularly limited, but the sodium ion type is preferable, and the atomic ratio of Na to Al (Na / Al atomic ratio) in the zeolite is in the range of 0.90 to 1.02. Is particularly preferred.
- synthetic faujasite-type zeolite is produced by filtering, washing and drying crystals obtained by hydrothermal synthesis under alkaline conditions. At that time, if the washing is insufficient, the alkali component remains in the crystal, and the zeolite has a large amount of free alkali as defined below.
- the amount of free alkali is a numerical value measured and calculated by titrating a 4% by weight aqueous dispersion of zeolite with 0.01N hydrochloric acid.
- the amount of free alkali of the synthetic faujasite type zeolite used in the present invention is preferably 0.1 meq or less per gram of zeolite.
- the synthetic faujasite type zeolite is produced in the form of fine powder unless it is produced as a binderless zeolite molding. Therefore, when industrially used as a fixed bed catalyst, it is difficult to use the fine powder as it is. For this reason, it is generally used as a molded body having an appropriate shape such as a spherical shape or a columnar shape. However, since the zeolite fine powder itself has no mutual bonding property, a binder is used to impart appropriate plasticity and strength.
- the catalyst molded body of the present invention contains a layered aluminum silicate compound and a layered magnesium silicate compound in a specific ratio as a binder component.
- the reason for this is that the methanol recovery rate and catalyst life in the reaction of synthesizing methyl methacrylate by dehydration of methyl ⁇ -hydroxyisobutyrate are appropriate for the amount of sodium ion in the synthetic faujasite type zeolite that is the active component of the reaction.
- the amount of sodium in the synthetic faujasite-type zeolite in the form of a molded catalyst can be improved by using a mixture of a layered aluminum silicate compound and a synthetic layered magnesium silicate compound as a binder. This is because the amount of ions can be adjusted to an appropriate amount.
- DME by-product and catalyst life As the amount of sodium ions in the synthetic faujasite-type zeolite, which is the active ingredient, increases, the amount of DME by-product decreases, and as the amount of sodium ions increases, the catalyst life becomes shorter. In the region, it was found that both the amount of DME by-product and the catalyst life were good.
- the synthetic faujasite type zeolite powder is not moldable by itself, so when considering it as a molded catalyst, it is necessary to control the amount of sodium ions to an appropriate amount including not only the zeolite but also the binder component. There is. Therefore, the present inventors have also studied in detail the behavior of a solution in which the binder component is dispersed in water. As a result, layered aluminum silicate compounds such as bentonite have the property of easily adsorbing sodium ions in the aqueous solution, and synthetic layered magnesium silicate compounds such as synthetic hectorite have the property of easily supplying sodium ions into the aqueous solution. I found out.
- the amount of sodium ions in the synthetic faujasite-type zeolite is appropriately adjusted even in the form of a molded catalyst.
- the amount of DME by-product can be suppressed, and the catalyst can be made into a catalyst having a good methanol recovery rate and a long catalyst life.
- a catalyst molded using only a layered aluminum silicate compound tends to reduce the amount of sodium ions in the synthetic faujasite-type zeolite, resulting in a large amount of by-product DME, and conversely, a synthetic layered magnesium silicate compound.
- the amount of sodium ions in the synthetic faujasite-type zeolite tends to increase, and in many cases, the catalyst life is short.
- the layered aluminum silicate compound in the present invention is a compound having a layered crystalline structure composed of at least elements of silicon, aluminum, and oxygen.
- examples of such compounds include natural clay compounds mainly composed of at least one selected from montmorillonite, beidellite, and kaolinite, and purified products thereof.
- Specific examples of the purified bentonite include, for example, Wengel, Wenger HV, Wenger HVP, Wenger FW, Wenger Bright 11, Wenger Bright 23, Wenger Bright 25 and Wenger A manufactured by Nippon Organoclay Co., Ltd.
- the kind of interlayer cation of the layered aluminum silicate compound of the present invention is not particularly limited, a sodium ion type or a mixed type of sodium ions and calcium ions is particularly preferable.
- the synthetic layered magnesium silicate compound in the present invention is a compound having a layered crystalline structure composed of at least silicon, magnesium, and oxygen elements, and chemically synthesized and modified natural clay compounds.
- such compounds include synthetic hectorite and synthetic mica chemically synthesized from sodium, lithium and magnesium salts and sodium silicate, and modified hectorite and modified mica obtained by modifying natural clay compounds. It is done.
- synthetic hectorite obtained by chemical synthesis is particularly preferable.
- Specific examples of the synthetic hectorite include Laponite RD, Laponite RDS, Laponite OG manufactured by Rockwood Additives, and Lucentite SWN and Lucentite SWF manufactured by Corp Chemical Co., Ltd.
- Synthetic hectorite is a trioctahedral layered silicate having a smectite structure, and various synthetic methods are known, but the synthetic method of synthetic hectorite that can be used in the present invention is particularly limited.
- the method for producing a synthetic swellable silicate described in JP-A-6-345419, the method for producing a hectorite-like silicate described in JP-A-9-249412, Known methods such as a method for producing synthetic magnesium silicate described in JP-A-71108 can be used.
- the kind of interlayer cation of the synthetic layered magnesium silicate compound of the present invention is not particularly limited, a sodium ion type is preferable.
- the amount of sodium ion adsorbed varies depending on the type of layered aluminum silicate compound, and the amount of sodium ion released varies depending on the type of synthetic layered magnesium silicate compound. Therefore, the layered aluminum silicate compound and the synthetic layered magnesium silicate compound in the present invention
- the optimum mixing ratio depends on the combination of the layered aluminum silicate compound and the synthetic layered magnesium silicate compound used.
- the mixing ratio of the layered aluminum silicate compound and the synthetic layered magnesium silicate compound is preferably 1: 5 to 6: 1 in terms of weight ratio, more preferably 1: 5 to 4: 1. 1: 5 to 7: 2 is more preferable, and 1: 5 to 3: 1 is most preferable.
- the catalyst life tends to be reduced.
- the cause is considered to be an increase in the amount of free sodium in the molded catalyst.
- the proportion of the layered aluminum silicate compound is larger than the above range, the amount of DME by-product tends to increase. As described above, this is presumably because the amount of sodium ions in the synthetic faujasite type zeolite in the molded catalyst body after molding is less than the appropriate range.
- Total amount of layered aluminum silicate compound and synthetic layered magnesium silicate compound relative to the total amount of synthetic faujasite type zeolite, layered aluminum silicate compound and synthetic layered magnesium silicate compound in the catalyst molded body of the present invention The ratio is preferably in the range of 3 to 30% by weight in consideration of ease of molding and mechanical strength of the molded body. A range of 5 to 20% by weight is particularly preferable.
- the molded catalyst of the present invention can also be added with molding aids and lubricants to improve moldability.
- molding aids and lubricants for example, carboxymethyl cellulose, stearic acid, alcohols, surfactants, fibers and the like are used. Can do.
- the molding method of the catalyst molded body of the present invention is not particularly limited, and can be molded by various methods such as an extrusion molding method, a rolling granulation method, and a tableting molding method according to the shape of the molded body.
- the shape of the molded body is not particularly limited, and for example, it can be used in a spherical shape, a cylindrical shape, a ring shape, a petal shape or the like.
- the pH value of the aqueous dispersion obtained by dispersing the molded catalyst of the present invention in water at a ratio of 2% by weight is preferably 10.2 to 10.8.
- the pH value of the aqueous dispersion is lower than 10.2, the amount of DME by-product tends to increase. This is considered to be because the amount of sodium ions in the synthetic faujasite type zeolite in the molded catalyst body after molding is less than the appropriate range.
- the pH value of the aqueous dispersion exceeds 10.8, the amount of by-produced DME can be suppressed, but the catalyst life tends to be reduced.
- the amount of free sodium in the catalyst molded body of the present invention is preferably 0.03 meq / g or less.
- the amount of free sodium in the molded catalyst exceeds the above, the amount of by-product DME is small, but the catalyst life tends to be reduced.
- the production method of the raw material ⁇ -hydroxyisobutyric acid methyl is not particularly limited, and ⁇ -hydroxyisobutyric acid amide and methyl formate disclosed in Japanese Patent Publication No. 2-2874 and methanolysis of ⁇ -hydroxyisobutyric acid amide Those prepared by amide-ester exchange can be used.
- Methyl ⁇ -hydroxyisobutyrate can also be obtained from high-boiling by-products of the ACH method for producing methyl methacrylate from acetone cyanohydrin and sulfuric acid and the C4 soot oxidation method using isobutylene as a raw material.
- the methyl ⁇ -hydroxyisobutyrate recovered from such high-boiling by-products generally contains methyl ⁇ or ⁇ -methoxyisobutyrate, but the catalyst of the present invention is also effective for the demethanol reaction of such homologues. And both can be recovered as methyl methacrylate.
- the reaction of the present invention can be carried out in a fixed bed gas phase flow type, and a reactor such as an adiabatic type or a multi-tube heat exchange type can be used.
- Raw material methyl ⁇ -hydroxyisobutyrate is preheated and vaporized and supplied to the reactor.
- the vaporized raw material can be introduced as it is, or it can be diluted with an inert gas such as nitrogen, argon or helium.
- an inert gas such as nitrogen, argon or helium.
- methanol is used as a diluent. More preferably it is used.
- the proportion of methanol in the diluent is preferably in the range of 0.1 to 3.0 times by weight, more preferably in the range of 0.2 to 2.0 times by weight with respect to methyl ⁇ -hydroxyisobutyrate.
- the feed rate of the raw material is preferably in the range of 0.1 to 5.0 hr ⁇ 1 in terms of the total weight of the raw material methyl ⁇ -hydroxyisobutyrate and diluent methanol per unit catalyst weight, that is, the weight space velocity (WHSV).
- the reaction temperature is preferably in the range of 230 to 300 ° C., and may be maintained at a constant temperature. However, in order to suppress various by-products and maintain the catalytic activity, the reaction rate of methyl ⁇ -hydroxyisobutyrate is reduced. A method in which the temperature is gradually raised in a specific temperature range as the reaction time elapses is more preferable so as to maintain the range of 98.0 to 99.9%.
- the reaction start temperature is 230 to 270 ° C., more preferably 240 to 260 ° C.
- the reaction end temperature is 250 to 300 ° C., more preferably 260 to 290 ° C.
- reaction temperature is necessary to compensate for the fact that high-boiling by-products and the like adhere to the catalyst and the active sites decrease over time.
- the reaction of methyl ⁇ -hydroxyisobutyrate within the above reaction temperature range is necessary.
- the rate cannot be maintained in the range of 98.0-99.9%, the raw material supply is temporarily stopped, and air firing is performed at a temperature at which the FAU type structure of the catalyst is not destroyed, preferably at a temperature not exceeding 550 ° C.
- the catalytic activity can be almost completely recovered.
- the catalyst of the present invention can be easily regenerated and used repeatedly.
- the reaction pressure is not particularly limited, but the reaction can be performed under normal pressure or slight pressure.
- the reaction product liquid obtained by the method of the present invention contains by-products such as unreacted raw materials, methacrylic acid, acetone, and polymethylbenzenes in addition to the target product, methyl methacrylate.
- by-products can be easily separated by applying a normal purification method such as distillation or extraction.
- ⁇ Analysis of molded catalyst> ⁇ PH analysis of molded catalyst>
- a catalyst molded body component pulverized with agate and the like was mixed with water and a catalyst molded body component was mixed at a ratio of 2% by weight. Thereafter, the mixture was subjected to ultrasonic dispersion treatment, and was further allowed to stand overnight to obtain an aqueous dispersion that was completely dispersed.
- the pH of the aqueous dispersion was measured using a pH meter D54 manufactured by Horiba, Ltd.
- the electrical conductivity of the catalyst molded body was obtained by mixing the catalyst molded body component pulverized with agate and the like into a powder form and mixing water to prepare a mixed solution containing the catalyst molded body component at a ratio of 2% by weight. . Thereafter, the mixture was subjected to ultrasonic dispersion treatment, and was further allowed to stand overnight to obtain an aqueous dispersion that was completely dispersed. The electrical conductivity of the aqueous dispersion was measured using a pH meter D54 manufactured by Horiba, Ltd.
- the amount of free Na in the catalyst molded body was obtained from the calculated value by preparing a 4 wt% aqueous dispersion of the catalyst molded body and allowing it to stand overnight, and titrating the supernatant with 0.01 N hydrochloric acid.
- ⁇ Performance test of methyl methacrylate synthesis reaction The performance test of methyl methacrylate synthesis reaction is fixed with a raw material tank, raw material supply pump, raw material gas introduction device, reaction tube (made of SUS316, inner diameter 18mm ⁇ , length 300mm), cooling device, reaction product liquid collecting device, etc. This was carried out using a bed gas phase flow reactor. In the performance test, 7 g of a molded product sized to 10-20 mesh was filled in the center of the reaction tube, and a 55 wt% methanol solution of methyl ⁇ -hydroxyisobutyrate was supplied at 9 g / hr. I went there.
- the reaction temperature was gradually increased so that the reaction rate of methyl ⁇ -hydroxyisobutyrate was in the range of 99.5 to 99.9%, and the number of days until reaching 280 ° C. was defined as the catalyst life.
- the reaction results were obtained by introducing the reaction product liquid into a gas chromatograph and quantitatively analyzing it.
- MeOH recovery rate (molar number of methanol in reaction product) / (molar number of methanol in raw material) ⁇ 100
- DME production rate (%) (number of moles of dimethyl ether in reaction product solution ⁇ 2) / (number of moles of methanol in raw material) ⁇ 100
- MMA + MAA yield (%) (number of moles of methyl methacrylate in reaction product liquid + number of moles of methacrylic acid in reaction product liquid) / (number of moles of methyl ⁇ -hydroxyisobutyrate in raw material) ⁇ 100
- Example 1 75.9 g of NaOH was dissolved in 462.9 g of ion-exchanged water, and 27.7 g of sodium aluminate (Al 2 O 3 51.0 wt% , Na 2 O 36.0 wt%) was added and dissolved. Further, a mixed solution of 333.0 g of silica sol (SiO 2 20 wt%) and 200.0 g of ion-exchanged water was added and stirred until a uniform slurry mixture was obtained. The above mixture was placed in an autoclave and crystallized at 100 ° C. for 48 hours.
- 34 g of the synthetic faujasite zeolite powder is a layered aluminum silicate compound, and montmorillonite content is 75 to 95% Bengelbright 11 (purified bentonite manufactured by Nippon Organic Clay Co., Ltd. A certain type) 1.2g and Laponite RD (Lot No. 10-4550, registered trademark of Laponite), a synthetic hectorite commercially available from Rockwood Additives, are mixed, and kneaded well while gradually adding ion-exchanged water. Then, it was molded, dried at 150 ° C., and calcined at 350 ° C. to obtain a molded catalyst.
- the mixture ratio of the synthetic faujasite type zeolite / Bengelbright 11 (layered aluminum silicate compound) / Laponite RD (synthetic layered magnesium silicate compound) of this catalyst molded body was 85/3/12 by weight.
- Table 1 shows the analysis results of the molded catalyst, and Table 2 shows the performance test results of the methyl methacrylate synthesis reaction.
- the pH was 10.55, the electric conductivity was 217 ⁇ S / cm, and the amount of free Na was 0.023 meq / g.
- Example 2 Synthetic faujasite-type zeolite / bengel (layered) using Bengel (purified bentonite made by Nippon Organic Clay Co., Ltd., whose interlayer cation is Na) with a montmorillonite content of 85-99% instead of Bengelbright 11.
- Bengel purified bentonite made by Nippon Organic Clay Co., Ltd., whose interlayer cation is Na
- a catalyst was prepared in the same manner as in Example 1 except that the mixing ratio of aluminum silicate compound) / Laponite RD (synthetic layered magnesium silicate compound) was 90/7/3 by weight.
- the performance test of methyl methacrylate synthesis reaction was conducted. Table 1 shows the analysis results of the molded catalyst, and Table 2 shows the performance test results of the methyl methacrylate synthesis reaction.
- Comparative Example 1 The mixing ratio of synthetic faujasite type zeolite / Wengerbright 11 (layered aluminum silicate compound) / laponite RD (synthetic layered magnesium silicate compound) was 85/15/0 by weight, and laponite RD was not used as a binder.
- a catalyst was prepared in the same manner as in Example 1, and a performance test of methyl methacrylate synthesis reaction of the obtained catalyst molded body was performed. Table 1 shows the analysis results of the molded catalyst, and Table 2 shows the performance test results of the methyl methacrylate synthesis reaction.
- Comparative Example 2 Synthetic faujasite-type zeolite / Bengelsbrite 11 (layered aluminum silicate compound) / Laponite RD (synthetic layered magnesium silicate compound) in a weight ratio of 85/0/15, and Wengerbright 11 is not used as a binder
- a catalyst was prepared in the same manner as in Example 1, and a performance test of methyl methacrylate synthesis reaction of the obtained molded catalyst was performed.
- Table 1 shows the analysis results of the molded catalyst
- Table 2 shows the performance test results of the methyl methacrylate synthesis reaction.
- the example catalyst formed into a molded body using a mixture of a layered aluminum silicate compound and a synthetic layered magnesium silicate compound as a binder was a comparative example catalyst. It can be seen that this is superior in terms of lifetime and methanol recovery.
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Abstract
Description
<1> α-ヒドロキシイソ酪酸メチルを原料として気相接触反応によりメタクリル酸メチルを製造するメタクリル酸メチル製造用触媒成型体であって、前記触媒成型体が、合成フォージャサイト型ゼオライトと層状ケイ酸アルミニウム化合物と合成層状ケイ酸マグネシウム化合物とを含み、前記層状ケイ酸アルミニウム化合物と前記合成層状ケイ酸マグネシウム化合物との重量比が1:5~6:1であることを特徴とする、メタクリル酸メチル製造用触媒成型体である。
<2> 前記触媒成型体成分を2重量%の割合で含む水分散液のpH値が10.2~10.8である、上記<1>に記載のメタクリル酸メチル製造用触媒成型体である。
<3> 前記触媒成型体中の遊離ナトリウム量が0.03ミリ当量/g以下である、上記<1>または<2>に記載のメタクリル酸メチル製造用触媒成型体である。
<4> 合成フォージャサイト型ゼオライトと層状ケイ酸アルミニウム化合物と合成層状ケイ酸マグネシウム化合物との合計量に対する、層状ケイ酸アルミニウム化合物と合成層状ケイ酸マグネシウム化合物との合計量の割合が3~30重量%である、上記<1>から<3>のいずれかに記載のメタクリル酸メチル製造用触媒成型体である。
<5> 前記層状ケイ酸アルミニウム化合物が、モンモリロナイト、バイデライト、及びカオリナイトから選ばれる少なくとも一種類を主成分とする粘土化合物である、上記<1>から<4>のいずれかに記載のメタクリル酸メチル製造用触媒成型体である。
<6> 前記層状ケイ酸アルミニウム化合物が、モンモリロナイトを主成分とする粘土化合物である、上記<1>から<5>のいずれかに記載のメタクリル酸メチル製造用触媒成型体である。
<7> 前記合成層状ケイ酸マグネシウム化合物が、合成ヘクトライトである、上記<1>から<6>のいずれかに記載のメタクリル酸メチル製造用触媒成型体である。
<8> 上記<1>から<7>のいずれかに記載のメタクリル酸メチル製造用触媒成型体の存在下、α-ヒドロキシイソ酪酸メチルを原料として気相接触反応によりメタクリル酸メチルを製造する、メタクリル酸メチルの製造方法である。
<9> 希釈剤としてα-ヒドロキシイソ酪酸メチルに対して0.1~3.0 重量倍の範囲のメタノールを用いる、上記<8>に記載のメタクリル酸メチルの製造方法である。
本発明に用いられる合成フォージャサイト型ゼオライトの遊離アルカリ量は、ゼオライト1g当たり0.1ミリ当量以下であるのが好ましい。
合成ヘクトライトは、スメクタイト構造を持つトリオクタヘドラル型層状ケイ酸塩であり、種々の合成方法が知られているが、本発明で使用することができる合成ヘクトライトの化学合成方法は特に限定されず、特開平6-345419号公報に記載されている合成膨潤性ケイ酸塩の製造方法、特開平9-249412号公報に記載されているヘクトライト様ケイ酸塩の製造方法、特開平11-71108号公報に記載されている合成ケイ酸マグネシウムの製造方法などの公知の方法が使用できる。本発明の合成層状ケイ酸マグネシウム化合物の層間カチオンの種類は特に限定されないが、ナトリウムイオン型が好ましい。
層状ケイ酸アルミニウム化合物の割合が上記の範囲より小さい場合、触媒寿命が低下する傾向がある。触媒成型体中の遊離ナトリウム量が増加することが原因と考えられる。層状ケイ酸アルミニウム化合物の割合が上記の範囲より大きい場合、DMEの副生量が多くなる傾向がある。これは前述したように、成型後の触媒成型体における、合成フォージャサイト型ゼオライト中のナトリウムイオン量が適正範囲よりも少なくなることが原因と考えられる。
<触媒成型体のpH分析>
触媒成型体のpHは、触媒成型体をメノウなどで粉砕して粉末状とした触媒成型体成分と水を混合し、触媒成型体成分を2重量%の割合で含む混合液を調製した。その後、混合液を超音波分散処理をし、さらに一晩放置して完全に分散させた水分散液を得た。水分散液のpHは、株式会社堀場製作所製のpHメータD54を使用して測定した。
触媒成型体の電気伝導度は、触媒成型体をメノウなどで粉砕して粉末状とした触媒成型体成分と水を混合し、触媒成型体成分を2重量%の割合で含む混合液を調製した。その後、混合液を超音波分散処理をし、さらに一晩放置して完全に分散させた水分散液を得た。水分散液の電気伝導度は、株式会社堀場製作所製のpHメータD54を使用して測定した。
触媒成型体の遊離Na量は、触媒成型体の4重量%水分散液を調製したあと一晩放置し、その上澄み液について0.01N塩酸で滴定することにより計算値から求めた。
メタクリル酸メチル合成反応の性能試験は、原料タンク、原料供給ポンプ、原料ガス導入装置、反応管(SUS316製、内径18mmφ、長さ300mm)、冷却装置、反応生成液捕集装置などを備えた固定床気相流通式反応装置を用いて行った。性能試験は、10-20メッシュのサイズに整粒した成型体7gを反応管の中央に充填し、55重量%のα-ヒドロキシイソ酪酸メチルのメタノール溶液を9g/hrで供給し、大気圧下で行った。反応温度は、α-ヒドロキシイソ酪酸メチルの反応率が99.5~99.9%の範囲となるように徐々に上げ、280℃に到達するまでの日数を触媒寿命とした。反応成績は、反応生成液をガスクロマトグラフに導入して、定量分析して求めた。
(1)MeOH回収率(%)=(反応生成液中のメタノールのモル数)/(原料中のメタノールのモル数)×100
(2)DME生成率(%)=(反応生成液中のジメチルエーテルのモル数×2)/(原料中のメタノールのモル数)×100
(3)MMA+MAA収率(%)=(反応生成液中のメタクリル酸メチルのモル数+反応生成液中のメタクリル酸のモル数)/(原料中のα-ヒドロキシイソ酪酸メチルのモル数)×100
NaOH 75.9gをイオン交換水 462.9g に溶解し、アルミン酸ソーダ(Al2O3 51.0wt% , Na2O 36.0wt%) 27.7g を添加、溶解した。さらにシリカゾル(SiO2 20wt%) 333.0g とイオン交換水 200.0g との混合液を加え、均一なスラリー混合物になるまで撹拌した。上記混合物をオートクレーブに入れ、100 ℃で48時間結晶化を行った。その後室温に戻して濾過し、ろ液の遊離アルカリ量が0.01ミリ当量/gになるまで水洗後、150℃で乾燥して白色のゼオライト粉末 51.6 gを得た。このゼオライトはX線回折と化学組成分析の結果、格子定数24.86 Å,Na/Al = 0.96の合成フォージャサイト型ゼオライトであった。
ベンゲルブライト11の代わりにモンモリロナイトの含有量が85~99%であるベンゲル(日本有機粘土株式会社製の精製ベントナイト、層間カチオンがNaであるタイプ)を用い、合成フォージャサイト型ゼオライト/ベンゲル(層状ケイ酸アルミニウム化合物)/ラポナイトRD(合成層状ケイ酸マグネシウム化合物)の混合比を重量比で90/7/3としたほかは、実施例1と同様に触媒調製し、得られた触媒成型体のメタクリル酸メチル合成反応の性能試験を行った。触媒成型体の分析結果を表1に、またメタクリル酸メチル合成反応の性能試験結果を表2に示す。
合成フォージャサイト型ゼオライト/ベンゲルブライト11(層状ケイ酸アルミニウム化合物)/ラポナイトRD(合成層状ケイ酸マグネシウム化合物)の混合比を重量比で85/15/0とし、ラポナイトRDをバインダーに用いなかったほかは、実施例1と同様に触媒調製し、得られた触媒成型体のメタクリル酸メチル合成反応の性能試験を行った。触媒成型体の分析結果を表1に、またメタクリル酸メチル合成反応の性能試験結果を表2に示す。
合成フォージャサイト型ゼオライト/ベンゲルブライト11(層状ケイ酸アルミニウム化合物)/ラポナイトRD(合成層状ケイ酸マグネシウム化合物)の混合比を重量比で85/0/15とし、ベンゲルブライト11をバインダーに用いなかったほかは、実施例1と同様に触媒調製し、得られた触媒成型体のメタクリル酸メチル合成反応の性能試験を行った。触媒成型体の分析結果を表1に、またメタクリル酸メチル合成反応の性能試験結果を表2に示す。
Claims (9)
- α-ヒドロキシイソ酪酸メチルを原料として気相接触反応によりメタクリル酸メチルを製造するメタクリル酸メチル製造用触媒成型体であって、前記触媒成型体が、合成フォージャサイト型ゼオライトと層状ケイ酸アルミニウム化合物と合成層状ケイ酸マグネシウム化合物とを含み、前記層状ケイ酸アルミニウム化合物と前記合成層状ケイ酸マグネシウム化合物との重量比が1:5~6:1であることを特徴とする、メタクリル酸メチル製造用触媒成型体。
- 前記触媒成型体成分を2重量%の割合で含む水分散液のpH値が10.2~10.8である、請求項1に記載のメタクリル酸メチル製造用触媒成型体。
- 前記触媒成型体中の遊離ナトリウム量が0.03ミリ当量/g以下である、請求項1または2に記載のメタクリル酸メチル製造用触媒成型体。
- 合成フォージャサイト型ゼオライトと層状ケイ酸アルミニウム化合物と合成層状ケイ酸マグネシウム化合物の合計量に対する、層状ケイ酸アルミニウム化合物と合成層状ケイ酸マグネシウム化合物の合計量の割合が3~30重量%である、請求項1から3のいずれかに記載のメタクリル酸メチル製造用触媒成型体。
- 前記層状ケイ酸アルミニウム化合物が、モンモリロナイト、バイデライト、及びカオリナイトから選ばれる少なくとも一種類を主成分とする粘土化合物である、請求項1から4のいずれかに記載のメタクリル酸メチル製造用触媒成型体。
- 前記層状ケイ酸アルミニウム化合物が、モンモリロナイトを主成分とする粘土化合物である、請求項1から5のいずれかに記載のメタクリル酸メチル製造用触媒成型体。
- 前記合成層状ケイ酸マグネシウム化合物が、合成ヘクトライトである、請求項1から6のいずれかに記載のメタクリル酸メチル製造用触媒成型体。
- 請求項1から7のいずれかに記載のメタクリル酸メチル製造用触媒成型体の存在下、α-ヒドロキシイソ酪酸メチルを原料として気相接触反応によりメタクリル酸メチルを製造する、メタクリル酸メチルの製造方法。
- 希釈剤としてα-ヒドロキシイソ酪酸メチルに対して0.1~3.0 重量倍の範囲のメタノールを用いる、請求項8に記載のメタクリル酸メチルの製造方法。
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