JP2017197458A - Method for producing conjugated diene compound by dehydration of allyl-type unsaturated alcohol - Google Patents
Method for producing conjugated diene compound by dehydration of allyl-type unsaturated alcohol Download PDFInfo
- Publication number
- JP2017197458A JP2017197458A JP2016088589A JP2016088589A JP2017197458A JP 2017197458 A JP2017197458 A JP 2017197458A JP 2016088589 A JP2016088589 A JP 2016088589A JP 2016088589 A JP2016088589 A JP 2016088589A JP 2017197458 A JP2017197458 A JP 2017197458A
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- aluminum
- conjugated diene
- general formula
- diene compound
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000006297 dehydration reaction Methods 0.000 title claims abstract description 54
- -1 diene compound Chemical class 0.000 title claims abstract description 45
- 230000018044 dehydration Effects 0.000 title claims abstract description 32
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 28
- ACIAHEMYLLBZOI-ZZXKWVIFSA-N Unsaturated alcohol Chemical compound CC\C(CO)=C/C ACIAHEMYLLBZOI-ZZXKWVIFSA-N 0.000 title abstract description 22
- 239000003054 catalyst Substances 0.000 claims abstract description 162
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 66
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 61
- 238000000034 method Methods 0.000 claims abstract description 47
- 239000002994 raw material Substances 0.000 claims abstract description 26
- 239000002253 acid Substances 0.000 claims abstract description 25
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 17
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 17
- 239000010703 silicon Substances 0.000 claims abstract description 11
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 9
- 125000003118 aryl group Chemical group 0.000 claims abstract description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 56
- 239000002131 composite material Substances 0.000 claims description 32
- 239000000377 silicon dioxide Substances 0.000 claims description 25
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- 239000011148 porous material Substances 0.000 claims description 18
- 229910001873 dinitrogen Inorganic materials 0.000 claims description 14
- 235000012239 silicon dioxide Nutrition 0.000 claims description 13
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 11
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 9
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 9
- 238000001179 sorption measurement Methods 0.000 claims description 7
- 239000010419 fine particle Substances 0.000 claims description 3
- 239000006185 dispersion Substances 0.000 abstract description 7
- 238000006243 chemical reaction Methods 0.000 description 51
- 239000000126 substance Substances 0.000 description 40
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 31
- 239000000843 powder Substances 0.000 description 26
- 238000003756 stirring Methods 0.000 description 22
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical class CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 17
- 238000002360 preparation method Methods 0.000 description 17
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 16
- 238000005259 measurement Methods 0.000 description 15
- 238000004458 analytical method Methods 0.000 description 13
- 239000007789 gas Substances 0.000 description 12
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 12
- 125000000746 allylic group Chemical group 0.000 description 11
- 150000001993 dienes Chemical class 0.000 description 11
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 10
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 10
- 239000006227 byproduct Substances 0.000 description 10
- 239000004809 Teflon Substances 0.000 description 9
- 229920006362 Teflon® Polymers 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- 239000012153 distilled water Substances 0.000 description 9
- 239000007788 liquid Substances 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- 230000005499 meniscus Effects 0.000 description 8
- XNDZQQSKSQTQQD-UHFFFAOYSA-N 3-methylcyclohex-2-en-1-ol Chemical compound CC1=CC(O)CCC1 XNDZQQSKSQTQQD-UHFFFAOYSA-N 0.000 description 7
- 238000001035 drying Methods 0.000 description 7
- 239000011259 mixed solution Substances 0.000 description 7
- 239000000178 monomer Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 description 6
- 239000000571 coke Substances 0.000 description 6
- MKUWVMRNQOOSAT-UHFFFAOYSA-N methylvinylmethanol Natural products CC(O)C=C MKUWVMRNQOOSAT-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000002002 slurry Substances 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 5
- 238000011088 calibration curve Methods 0.000 description 5
- 238000004939 coking Methods 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 229910052814 silicon oxide Inorganic materials 0.000 description 5
- WCASXYBKJHWFMY-NSCUHMNNSA-N 2-Buten-1-ol Chemical compound C\C=C\CO WCASXYBKJHWFMY-NSCUHMNNSA-N 0.000 description 4
- 235000002597 Solanum melongena Nutrition 0.000 description 4
- 235000010724 Wisteria floribunda Nutrition 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000003795 desorption Methods 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 239000004570 mortar (masonry) Substances 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 229910004298 SiO 2 Inorganic materials 0.000 description 3
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical group [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 238000005470 impregnation Methods 0.000 description 3
- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 description 3
- 239000000314 lubricant Substances 0.000 description 3
- 238000000691 measurement method Methods 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 229920000915 polyvinyl chloride Polymers 0.000 description 3
- 239000004800 polyvinyl chloride Substances 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 230000008929 regeneration Effects 0.000 description 3
- 238000011069 regeneration method Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- 238000003980 solgel method Methods 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 239000006200 vaporizer Substances 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000002156 adsorbate Substances 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- FUSUHKVFWTUUBE-UHFFFAOYSA-N buten-2-one Chemical compound CC(=O)C=C FUSUHKVFWTUUBE-UHFFFAOYSA-N 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000009849 deactivation Effects 0.000 description 2
- 238000006356 dehydrogenation reaction Methods 0.000 description 2
- 239000003085 diluting agent Substances 0.000 description 2
- 150000002009 diols Chemical class 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000007493 shaping process Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000000638 solvent extraction Methods 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 description 1
- 239000005695 Ammonium acetate Substances 0.000 description 1
- 239000007848 Bronsted acid Substances 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 229940043376 ammonium acetate Drugs 0.000 description 1
- 235000019257 ammonium acetate Nutrition 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 239000008119 colloidal silica Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- MLUCVPSAIODCQM-NSCUHMNNSA-N crotonaldehyde Chemical compound C\C=C\C=O MLUCVPSAIODCQM-NSCUHMNNSA-N 0.000 description 1
- MLUCVPSAIODCQM-UHFFFAOYSA-N crotonaldehyde Natural products CC=CC=O MLUCVPSAIODCQM-UHFFFAOYSA-N 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- WCASXYBKJHWFMY-UHFFFAOYSA-N gamma-methylallyl alcohol Natural products CC=CCO WCASXYBKJHWFMY-UHFFFAOYSA-N 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- 229910052863 mullite Inorganic materials 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 238000005839 oxidative dehydrogenation reaction Methods 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920001983 poloxamer Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000011403 purification operation Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000010079 rubber tapping Methods 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000011734 sodium Substances 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
- 239000002904 solvent Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- ZSDSQXJSNMTJDA-UHFFFAOYSA-N trifluralin Chemical compound CCCN(CCC)C1=C([N+]([O-])=O)C=C(C(F)(F)F)C=C1[N+]([O-])=O ZSDSQXJSNMTJDA-UHFFFAOYSA-N 0.000 description 1
Images
Abstract
Description
本発明はアリル型不飽和アルコールを脱水し、効率的に共役ジエン化合物を製造することのできる触媒を用いた共役ジエン化合物の製造方法に関する。 The present invention relates to a method for producing a conjugated diene compound using a catalyst capable of dehydrating an allylic unsaturated alcohol and efficiently producing a conjugated diene compound.
1,3−ブタジエン、イソプレン等の共役ジエンモノマーは、合成ゴム、プラスチックなどの樹脂原料としての工業的価値が高く、その効率的な製造法が求められている。 Conjugated diene monomers such as 1,3-butadiene and isoprene have high industrial value as resin raw materials such as synthetic rubbers and plastics, and their efficient production methods are required.
従来、ジエンモノマーはナフサの熱分解炉(クラッカー)の熱分解物を蒸留分離し、その一留分として得られている。しかしながら、この留分精製による方法では、ジエンモノマーを選択的に得たい場合であっても他のモノマー留分(エチレン、プロピレンなど)を含めた採算性を考慮せねばならず、工業的な製造の自由度が低かった。 Conventionally, the diene monomer is obtained as a fraction by distilling and separating a thermal decomposition product of a naphtha pyrolysis furnace (cracker). However, in this method of fraction purification, even when it is desired to selectively obtain a diene monomer, the profitability including other monomer fractions (ethylene, propylene, etc.) must be taken into consideration, and industrial production. The degree of freedom was low.
そこで、入手の容易なエチレン等の低分子量の化合物を原料としたジエンモノマーの製造方法が検討されている。例えば低級オレフィンの二量化を行った後にMo−Bi−X系触媒の存在下で酸化脱水素処理を行うことによる製造法が特許文献1及び特許文献2に開示されている。しかしこの方法では、酸素を用いることによる爆発の危険性があるほか、未反応ブテンの分離等を行うなど付帯設備が必要となり、設備全体が大型化するという問題がある。特にブテンの副生量が多い場合、1,3−ブタジエン中からブテンを除去する工程が必要となるが、ブテンは蒸留操作では除去することが困難であるため、溶媒抽出法等の多大なコスト又は設備投資が必要な精製操作が必要となる。 Therefore, a method for producing a diene monomer using a low molecular weight compound such as ethylene, which is easily available, as a raw material has been studied. For example, Patent Document 1 and Patent Document 2 disclose a production method in which a lower olefin is dimerized and then subjected to oxidative dehydrogenation in the presence of a Mo-Bi-X catalyst. However, in this method, there is a risk of explosion due to the use of oxygen, and incidental equipment such as separation of unreacted butene is required, resulting in an increase in size of the entire equipment. In particular, when the amount of butene produced as a by-product is large, a process for removing butene from 1,3-butadiene is required. However, since it is difficult to remove butene by distillation operation, a large amount of cost such as solvent extraction is required. Alternatively, a refining operation that requires capital investment is required.
別の方法として、不飽和アルコールの脱水反応による製造法があげられる。このような不飽和アルコールは、例えば特許文献3及び特許文献4に示すようなジオールの1分子脱水反応により得ることができる。しかし、ジエン生成物である1,3−ブタジエンの選択率が不十分であり、特にブテンの副生成量が多く、ブテンの分離のためには上述のような設備上の問題点を有している。 As another method, a production method by dehydration reaction of unsaturated alcohol can be mentioned. Such an unsaturated alcohol can be obtained, for example, by a one-molecule dehydration reaction of a diol as shown in Patent Document 3 and Patent Document 4. However, the selectivity of 1,3-butadiene, which is a diene product, is insufficient. Particularly, the amount of by-product of butene is large, and the above-mentioned equipment problems are necessary for the separation of butene. Yes.
別の方法として、特許文献5に記載されるようなアリル型不飽和アルコールの脱水反応による製造法があげられる。特許文献5では特定のケイバン比のシリカアルミナ触媒を用いてα,β−脂肪族不飽和アルコールを脱水して、共役ジエンを生成させている。実施例ではクロチアルコールの脱水反応により1,3−ブタジエンを製造しているが、その選択率は94〜96%にとどまっている。副生物のブテンについての記述はないほか、複数種のα,β−不飽和アルコールを同時に脱水して共役ジエン化合物を得る可能性の記載もない。また、明細書中でブレンステッド酸点とルイス酸点の比率や弱酸と強酸の比率についても記述があるが、酸量及び酸量をアルミニウム量で割った値であるアルミニウム分散度についての記載はない。
As another method, there is a production method by dehydration reaction of allyl unsaturated alcohol as described in
本反応の原料であるアリル型不飽和アルコール及び生成物である共役ジエンモノマーは重合性化合物である。また、副生物であるブテン等も重合性を示すほか、クロトンアルデヒドやメチルビニルケトンに代表される脱水素副生物は特に高い重合性を有する。そのため、本脱水反応は本質的にコークの生成が起こりやすい反応であり、触媒にコークが付着することが触媒失活の主要因となる。多量のコークの付着に起因して触媒寿命(連続使用時間)が短いこと、及び共役ジエンモノマーの消費による選択率低下が起こることが本脱水反応の大きな問題点として挙げられる。 The allylic unsaturated alcohol that is the raw material of this reaction and the conjugated diene monomer that is the product are polymerizable compounds. In addition, butene as a by-product exhibits polymerizability, and dehydrogenation by-products represented by crotonaldehyde and methyl vinyl ketone have particularly high polymerizability. For this reason, this dehydration reaction is essentially a reaction in which coke formation is likely to occur, and adhesion of coke to the catalyst is the main factor of catalyst deactivation. A major problem of this dehydration reaction is that the catalyst life (continuous use time) is short due to the adhesion of a large amount of coke and the selectivity is lowered due to consumption of the conjugated diene monomer.
このようなコークの付着により失活した触媒は、例えば空気を含むガスの流通下に触媒を高温で処理するなど、適切な再生処理を行うことにより、その性能を回復させることができるが、その為には余分な設備、工程、費用などが必要となる。したがって、共役ジエン選択率が高く、ブテンなどの副生物が少なく、触媒寿命の長い触媒が強く望まれている。 Such a deactivated catalyst due to the adhesion of coke can be recovered in its performance by performing an appropriate regeneration treatment, for example, by treating the catalyst at a high temperature under the flow of a gas containing air. To do this, extra equipment, processes and costs are required. Therefore, a catalyst having a high conjugated diene selectivity, few by-products such as butene, and a long catalyst life is strongly desired.
本発明の課題は、選択率が高く、触媒寿命の長い、アリル型不飽和アルコール原料から対応する共役ジエン化合物を効率よく製造する方法を提供することである。 An object of the present invention is to provide a method for efficiently producing a corresponding conjugated diene compound from an allylic unsaturated alcohol raw material having a high selectivity and a long catalyst life.
本発明者らはさらなる鋭意検討を行った結果、アリル型不飽和アルコールに対し、アルミニウムの酸化物及びケイ素の酸化物を含み、NH3−TPD法により測定された酸量(mol/g)をアルミニウム含有量(mol/g)で割った値で定義されるアルミニウム分散度が特定の範囲内にある脱水触媒を作用させることにより、効率的に対応する共役ジエン化合物を製造できることを見いだし、本発明を完成させるに至った。 As a result of further intensive studies, the inventors of the present invention calculated the amount of acid (mol / g) measured by the NH 3 -TPD method, including an oxide of aluminum and an oxide of silicon, with respect to the allylic unsaturated alcohol. It has been found that the corresponding conjugated diene compound can be efficiently produced by acting a dehydration catalyst whose aluminum dispersity defined by the value divided by the aluminum content (mol / g) is within a specific range. It came to complete.
すなわち本発明は以下の項目[1]〜[7]に関する。
[1]
脱水触媒の存在下、一般式(1)又は一般式(2)で示されるアリル型不飽和アルコールの少なくとも一種を原料とし、脱水反応によって一般式(3)で示される共役ジエン化合物を製造する方法であって、前記脱水触媒がケイ素の酸化物とアルミニウムの酸化物とが原子レベル又は微粒子レベルで混ざり合った複合型触媒であり、NH3−TPD法により測定された酸量(mol/g)をアルミニウムの含有量(mol/g)で割った値で定義されるアルミニウム分散度が0.10〜0.30であることを特徴とする共役ジエン化合物の製造方法。
脱水触媒の存在下、一般式(1)又は一般式(2)で示されるアリル型不飽和アルコールの少なくとも一種を原料とし、脱水反応によって一般式(3)で示される共役ジエン化合物を製造する方法であって、前記脱水触媒が二酸化ケイ素担体上にアルミニウムの酸化物が担持された担持型触媒であり、NH3−TPD法により測定された酸量(mol/g)をアルミニウムの含有量(mol/g)で割った値で定義されるアルミニウム分散度が0.20〜0.45であることを特徴とする共役ジエン化合物の製造方法。
前記脱水触媒のアルミニウムとケイ素の原子比(Al/Si)が0.03〜0.13である[1]に記載の共役ジエン化合物の製造方法。
[4]
前記脱水触媒のアルミニウムとケイ素の原子比(Al/Si)が0.005〜0.025である[2]に記載の共役ジエン化合物の製造方法。
[5]
前記脱水触媒がシリカアルミナである[1]又は[3]のいずれかに記載の共役ジエン化合物の製造方法。
[6]
前記脱水触媒の窒素ガス吸着法により測定された平均細孔径が6.0〜70.0nmである[1]〜[5]のいずれかに記載の共役ジエン化合物の製造方法。
[7]
一般式(1)及び一般式(2)のR1〜R6がすべて水素原子である[1]〜[6]のいずれかに記載の共役ジエン化合物の製造方法。
That is, the present invention relates to the following items [1] to [7].
[1]
A method for producing a conjugated diene compound represented by general formula (3) by dehydration reaction using at least one of allyl unsaturated alcohol represented by general formula (1) or general formula (2) as a raw material in the presence of a dehydration catalyst The dehydration catalyst is a composite catalyst in which an oxide of silicon and an oxide of aluminum are mixed at the atomic level or fine particle level, and the acid amount (mol / g) measured by the NH 3 -TPD method A method for producing a conjugated diene compound, wherein the aluminum dispersity defined by a value obtained by dividing the content by the aluminum content (mol / g) is 0.10 to 0.30.
A method for producing a conjugated diene compound represented by general formula (3) by dehydration reaction using at least one of allyl unsaturated alcohol represented by general formula (1) or general formula (2) as a raw material in the presence of a dehydration catalyst The dehydration catalyst is a supported catalyst in which an oxide of aluminum is supported on a silicon dioxide support, and the acid amount (mol / g) measured by the NH 3 -TPD method is calculated based on the aluminum content (mol / G) The aluminum dispersity defined by the value divided by 0.2 g is 0.20 to 0.45. A method for producing a conjugated diene compound.
The method for producing a conjugated diene compound according to [1], wherein the dehydration catalyst has an aluminum to silicon atomic ratio (Al / Si) of 0.03 to 0.13.
[4]
The method for producing a conjugated diene compound according to [2], wherein the dehydration catalyst has an aluminum to silicon atomic ratio (Al / Si) of 0.005 to 0.025.
[5]
The method for producing a conjugated diene compound according to any one of [1] or [3], wherein the dehydration catalyst is silica alumina.
[6]
The method for producing a conjugated diene compound according to any one of [1] to [5], wherein an average pore diameter measured by a nitrogen gas adsorption method of the dehydration catalyst is 6.0 to 70.0 nm.
[7]
Production method of general formula (1) and R 1 to R 6 are all hydrogen atoms of the general formula (2) [1] conjugated diene compound according to any one of to [6].
本発明の触媒を用いると、アリル型不飽和アルコールの脱水による共役ジエンの製造をより高い選択率かつより長い触媒寿命で行うことができ、副生物の生成量をより減らすことができる。よって、一般的な蒸留操作のみで工業的に価値のある共役ジエンを得ることができ、溶媒抽出法等の多大なコストや設備投資が必要な精製操作を経る必要がない。また、触媒再生頻度を抑えることで再生操作にかかる設備、工程、及び費用を大きく抑えることができる。 When the catalyst of the present invention is used, production of a conjugated diene by dehydration of an allylic unsaturated alcohol can be performed with a higher selectivity and a longer catalyst life, and the amount of by-products generated can be further reduced. Therefore, industrially valuable conjugated dienes can be obtained only by a general distillation operation, and it is not necessary to go through a purification operation such as a solvent extraction method that requires a large cost and equipment investment. Further, by reducing the frequency of catalyst regeneration, it is possible to greatly reduce the equipment, processes, and costs involved in the regeneration operation.
本発明では、一般式(1)又は一般式(2)で示されるアリル型不飽和アルコールの少なくとも一種を原料とし、脱水反応によって一般式(3)で示される共役ジエン化合物を製造するにあたり、アルミニウムの酸化物及びケイ素の酸化物を含み、下記数式であらわされるアルミニウム分散度が特定の範囲内にある脱水触媒を使用する。本明細書において、「アルミニウムの酸化物及びケイ素の酸化物を含む触媒」は、後述する担持型(本明細書において「表面型」ともいう。)触媒と複合型(本明細書において「バルク型」ともいう。)触媒の両方を包含する。
一般式(1)、(2)及び(3)においてR1〜R6はそれぞれ独立に水素原子、炭素数1〜5のアルキル基、又は炭素数6〜12のアリール基を示す。炭素数1〜5のアルキル基としてはメチル基、エチル基、プロピル基、イソプロピル基、ペンチル基などが挙げられる。炭素数6〜12のアリール基としてはフェニル基、トリル基、ナフチル基などが挙げられる。R1〜R6はそれぞれ独立に、水素原子、又は炭素数1〜5のアルキル基であることが好ましく、得られる共役ジエン化合物の有用性から水素原子であることがより好ましい。R1〜R6は互いに同じであっても、異なっていてもよいが、すべて水素原子であることが最も好ましい。このとき、一般式(1)の化合物は2−ブテン−1−オール(クロチルアルコール)、一般式(2)の化合物は3−ブテン−2−オールとなり、生成物である一般式(3)の化合物は1,3−ブタジエンとなる。 In the general formulas (1), (2) and (3), R 1 to R 6 each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or an aryl group having 6 to 12 carbon atoms. Examples of the alkyl group having 1 to 5 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, and a pentyl group. Examples of the aryl group having 6 to 12 carbon atoms include a phenyl group, a tolyl group, and a naphthyl group. R 1 to R 6 are each independently preferably a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and more preferably a hydrogen atom in view of the usefulness of the resulting conjugated diene compound. R 1 to R 6 may be the same as or different from each other, but are all preferably hydrogen atoms. At this time, the compound of the general formula (1) is 2-buten-1-ol (crotyl alcohol), the compound of the general formula (2) is 3-buten-2-ol, and the product of the general formula (3) This compound is 1,3-butadiene.
本脱水反応では、一般式(1)で示されるアリル型不飽和アルコール及び一般式(2)で示されるアリル型不飽和アルコールの両方を原料とし、同時に脱水反応に供することが有利である。これにより、例えばジオールの一分子脱水反応によって得ることができる、一般式(1)で示されるアリル型不飽和アルコール及び一般式(2)で示されるアリル型不飽和アルコールの両方を含有する生成物を、これらのアリル型不飽和アルコールを互いに分離することなく脱水反応に使用することができる。脱水反応の前に上記生成物に対して必要に応じて他の成分の分離及び精製を行ってもよい。 In this dehydration reaction, it is advantageous to use both an allylic unsaturated alcohol represented by the general formula (1) and an allylic unsaturated alcohol represented by the general formula (2) as raw materials and simultaneously subject to the dehydrating reaction. Thereby, for example, a product containing both an allylic unsaturated alcohol represented by the general formula (1) and an allylic unsaturated alcohol represented by the general formula (2), which can be obtained by a monomolecular dehydration reaction of a diol. Can be used in the dehydration reaction without separating these allyl unsaturated alcohols from each other. Prior to the dehydration reaction, other components may be separated and purified as necessary.
本脱水反応においては、一般式(1)又は一般式(2)で示されるアリル型不飽和アルコール以外の不飽和アルコールが併存していてもよい。 In the dehydration reaction, an unsaturated alcohol other than the allyl unsaturated alcohol represented by the general formula (1) or the general formula (2) may coexist.
本発明の脱水触媒は、アルミニウムの酸化物及びケイ素の酸化物を含み、NH3−TPD(Temperature−Programmed Desorption)法により測定された酸量(mol/g)をアルミニウム含有量(mol/g)で割った値で定義されるアルミニウム分散度が、下記特定の範囲内にある触媒である。
(1)前記脱水触媒がケイ素の酸化物とアルミニウムの酸化物とが原子レベル又は微粒子レベルで混ざり合った複合型触媒である場合:
アルミニウム分散度 0.10〜0.30
(2)前記脱水触媒が二酸化ケイ素担体上にアルミニウムの酸化物が担持された担持型触媒である場合:
アルミニウム分散度 0.20〜0.45
The dehydration catalyst of the present invention contains an oxide of aluminum and an oxide of silicon, and an acid amount (mol / g) measured by NH 3 -TPD (Temperature-Programmed Desorption) method is used as an aluminum content (mol / g). A catalyst whose aluminum dispersity defined by the value divided by is within the following specific range.
(1) When the dehydration catalyst is a composite catalyst in which silicon oxide and aluminum oxide are mixed at the atomic level or fine particle level:
Aluminum dispersity 0.10-0.30
(2) When the dehydration catalyst is a supported catalyst in which an aluminum oxide is supported on a silicon dioxide support:
Aluminum dispersity 0.20 to 0.45
脱水触媒のNH3−TPD法による酸量(mol/g)は、自動昇温脱離装置を用いて以下の手順で決定することができる。粉砕した触媒100mgに対してHeガスを50sccmで流通させながら、400℃で2時間前処理を行う。100℃まで冷却したら、NH3を100Torrの定圧で吸着させる。続いて、50sccmのHeガス流通下、100℃、160Torrの減圧条件で50分間処理を行う。その後、160〜200Torrの間の減圧条件で、700℃まで10℃/分の速度で昇温し、700℃で50分間保持する。分析終了後、0.193体積%のNH3ガス(Heバランス)と0.97体積%のNH3ガス(Heバランス)を用いて検量線を作成する。各温度で脱離するNH3と水の合計量と検量線作成時のNH3の量を質量分析計(Mass=16)で測定し、脱離するNH3と水の合計量を算出する。続いて、100℃、100TorrでのNH3定圧吸着を行わない他は同一の条件でブランク測定を行い、触媒から脱離する水由来の測定値を算出する。本測定の測定値からブランク測定の測定値を減算し、脱離NH3量とする。脱離NH3量(mol数)が触媒の酸点のmol数と等しいとして、触媒1g当たりの酸量(mol/g)を計算することができる。 Acid amount of NH 3 -TPD method dehydration catalyst (mol / g), using an automatic temperature-programmed desorption apparatus can be determined by the following procedure. Pretreatment is performed at 400 ° C. for 2 hours while flowing He gas at 50 sccm with respect to 100 mg of the pulverized catalyst. After cooling to 100 ° C., NH 3 is adsorbed at a constant pressure of 100 Torr. Subsequently, treatment is performed for 50 minutes under a reduced pressure condition of 100 ° C. and 160 Torr under a flow of He gas of 50 sccm. Thereafter, the temperature is raised to 700 ° C. at a rate of 10 ° C./min under reduced pressure conditions of 160 to 200 Torr, and held at 700 ° C. for 50 minutes. After the analysis is completed, a calibration curve is created using 0.193% by volume of NH 3 gas (He balance) and 0.97% by volume of NH 3 gas (He balance). The total amount of NH 3 and water desorbed at each temperature and the amount of NH 3 at the time of preparing the calibration curve are measured with a mass spectrometer (Mass = 16), and the total amount of NH 3 and water desorbed is calculated. Subsequently, blank measurement is performed under the same conditions except that NH 3 constant pressure adsorption is not performed at 100 ° C. and 100 Torr, and a measurement value derived from water desorbed from the catalyst is calculated. The measurement value of the blank measurement is subtracted from the measurement value of the main measurement to obtain the amount of desorbed NH 3 . The amount of acid (mol / g) per gram of catalyst can be calculated assuming that the amount of desorbed NH 3 (number of moles) is equal to the number of moles of acid points of the catalyst.
脱水触媒のアルミニウム含有量(mol/g)は、複合型触媒に関しては走査型蛍光X線分析装置を用いたXRF分析により、担持型触媒に関してはICP−MSにより、それぞれ決定することができる。測定方法の詳細は実施例の項に記載する。 The aluminum content (mol / g) of the dehydration catalyst can be determined by XRF analysis using a scanning fluorescent X-ray analyzer for the composite catalyst and ICP-MS for the supported catalyst, respectively. Details of the measurement method are described in the Examples section.
アルミニウムの酸化物及びケイ素の酸化物を含む触媒は、調製法により一般に複合型(バルク型)触媒と担持型(表面型)触媒の2種類に分類することができる。触媒の調製方法としては種々の方法を用いることが可能であり、例えば含浸法、イオン交換法、CVD法、混練法、共沈法、ゾルゲル法等があげられる。 Catalysts containing an aluminum oxide and a silicon oxide can be generally classified into two types, a composite type (bulk type) catalyst and a supported type (surface type) catalyst, depending on the preparation method. Various methods can be used as a method for preparing the catalyst, and examples thereof include an impregnation method, an ion exchange method, a CVD method, a kneading method, a coprecipitation method, and a sol-gel method.
複合型(バルク型)触媒は、二酸化ケイ素前駆体及び二酸化ケイ素から選ばれる第1触媒原料と、アルミニウム酸化物前駆体及びアルミニウム酸化物から選ばれる第2触媒原料との組み合わせを用いて、混練法、共沈法、ゾルゲル法などによって調製される。複合型(バルク型)触媒は、各成分が原子レベルで結合した複合酸化物であり、表面だけでなく固体内部にもアルミニウム原子が多く存在している。ゾルゲル法としては、ケイ素アルコキシド及びアルミニウムアルコキシドのアルコール溶液に、水を添加してゲルを調製した後、乾燥及び焼成する方法が挙げられる。この際、触媒として酸又は塩基を加えてもよいし、無触媒で触媒調製を行ってもよい。複合酸化物の例としてはシリカアルミナ等が挙げられる。 The composite type (bulk type) catalyst is a kneading method using a combination of a first catalyst raw material selected from a silicon dioxide precursor and silicon dioxide and a second catalyst raw material selected from an aluminum oxide precursor and aluminum oxide. It is prepared by a coprecipitation method, a sol-gel method or the like. A composite type (bulk type) catalyst is a composite oxide in which each component is bonded at an atomic level, and many aluminum atoms exist not only on the surface but also inside the solid. Examples of the sol-gel method include a method in which water is added to an alcohol solution of silicon alkoxide and aluminum alkoxide to prepare a gel, followed by drying and baking. At this time, an acid or a base may be added as a catalyst, or the catalyst may be prepared without a catalyst. Examples of the composite oxide include silica alumina.
担持型(表面型)触媒は、二酸化ケイ素(SiO2)担体に含浸法、イオン交換法、CVD法などによってアルミニウム酸化物前駆体を付着又は堆積させて調製される触媒であり、二酸化ケイ素(SiO2)担体上にアルミニウム酸化物が担持されている。この型の場合、焼結時に一部のアルミニウム酸化物と二酸化ケイ素は混じり合い複合酸化物を形成することがあるが、アルミニウム原子の多くが触媒表面に存在している。二酸化ケイ素(SiO2)は市販の物をそのまま、あるいは粉砕処理、強熱処理、酸処理等の前処理を行ってから使用することができる。含浸法としては、アルミニウムの硝酸塩水溶液又はアルミニウムアルコキシドのアルコール溶液を二酸化ケイ素担体に加えた後、乾燥及び焼成する方法が挙げられる。加える溶液の量は二酸化ケイ素担体の細孔容積相当でもよいし、細孔容積以上の量を加えて溶液を濃縮し得られた含浸担体を濾別してもよい。アルミニウムの硝酸塩水溶液に二酸化ケイ素担体を加えた後、pHを調整するなどしてアルミニウムを水酸化物にして沈降させ担体上に担持させる等の方法をとることもできる。 The supported type (surface type) catalyst is a catalyst prepared by adhering or depositing an aluminum oxide precursor on a silicon dioxide (SiO 2 ) support by an impregnation method, an ion exchange method, a CVD method, or the like. 2 ) Aluminum oxide is supported on the carrier. In this type, a part of aluminum oxide and silicon dioxide may be mixed during sintering to form a composite oxide, but many aluminum atoms are present on the catalyst surface. As silicon dioxide (SiO 2 ), a commercially available product can be used as it is or after pretreatment such as pulverization, strong heat treatment, and acid treatment. Examples of the impregnation method include a method of adding an aqueous nitrate solution of aluminum or an alcohol solution of aluminum alkoxide to a silicon dioxide support, followed by drying and firing. The amount of the solution to be added may be equivalent to the pore volume of the silicon dioxide support, or the impregnated support obtained by adding the amount larger than the pore volume to concentrate the solution may be filtered off. After adding a silicon dioxide support to an aqueous nitrate solution of aluminum, a method such as adjusting the pH to precipitate aluminum as a hydroxide to be supported on the support can be used.
本発明の触媒には、アルミニウムとは異なる金属酸化物又は金属が含まれていてもよい。そのような金属酸化物又は金属の例としては、酸化マグネシウム、酸化ランタン、酸化モリブデンなどがあげられる。 The catalyst of the present invention may contain a metal oxide or metal different from aluminum. Examples of such metal oxides or metals include magnesium oxide, lanthanum oxide, molybdenum oxide, and the like.
本発明の触媒のアルミニウム分散度は複合型(バルク型)触媒においては、0.10〜0.30、好ましくは、0.10〜0.15である。担持型(表面型)触媒においては0.20〜0.45、好ましくは0.30〜0.40である。 The aluminum dispersity of the catalyst of the present invention is 0.10 to 0.30, preferably 0.10 to 0.15 in a composite (bulk) catalyst. In the supported type (surface type) catalyst, it is 0.20 to 0.45, preferably 0.30 to 0.40.
本発明の反応では、コーキングにより触媒の反応点である酸点が覆われ、失活が進行する。そのため酸量が多いと、コーキングにより酸点がある程度減少しても原料の転化率が維持される。すなわち、触媒寿命が長くなる。一般にアルミニウム含有量がシリカ含有量より少ない場合は、アルミニウム含有量を増やすと酸量は増える。しかし、単にアルミニウム含有量を増やすとアルミナクラスターがより多く生成してしまう。アルミナ触媒は、本反応の発明においては脱水素副反応又はコーキングを起こしやすく、選択率も触媒寿命も短い。反応成績低下の原因となるアルミナクラスターを減らすためには、シリカとアルミナの混合具合が良いこと、つまりアルミニウムの分散性が高いことが好ましい。すなわち、アルミニウム分散度が高い触媒は、反応点である酸点を増やしつつも、アルミナクラスターに代表される好ましくない反応点が少ない触媒であることを意味し、選択率が高く、触媒寿命が長い。一方で、反応点である酸点が多すぎると、反応点の密度が高く、活性化された基質又は生成物が互いに近傍に位置しやすいために反応生成物などの重合反応が進行しやすく、コーキングが生じてしまう。よって、アルミニウム分散度の高すぎる触媒は、反応の選択率又は触媒寿命が低下してしまう。また、複合型触媒と担持型触媒では反応点となる表面に存在するアルミニウムの比率が異なるため、最適なアルミニウム分散度の範囲が異なる。 In the reaction of the present invention, acid points that are reaction points of the catalyst are covered by coking, and deactivation proceeds. Therefore, when the acid amount is large, the conversion rate of the raw material is maintained even if the acid point is reduced to some extent by coking. That is, the catalyst life is increased. In general, when the aluminum content is less than the silica content, increasing the aluminum content increases the acid amount. However, simply increasing the aluminum content results in more alumina clusters. In the invention of this reaction, the alumina catalyst is liable to cause a dehydrogenation side reaction or coking, and has a short selectivity and catalyst life. In order to reduce the number of alumina clusters that cause a reduction in reaction results, it is preferable that the silica and alumina are mixed well, that is, the dispersibility of aluminum is high. That is, a catalyst having a high degree of aluminum dispersion means that the acid point, which is a reaction point, is increased, but there are few undesirable reaction points represented by alumina clusters, and the selectivity is high and the catalyst life is long. . On the other hand, if there are too many acid points as reaction points, the density of the reaction points is high, and the activated substrate or product is likely to be located in the vicinity of each other, so that a polymerization reaction such as a reaction product easily proceeds, Caulking occurs. Therefore, a catalyst having an aluminum dispersion degree that is too high results in a decrease in reaction selectivity or catalyst life. In addition, since the ratio of aluminum existing on the surface serving as a reaction point is different between the composite catalyst and the supported catalyst, the optimum range of aluminum dispersion is different.
本発明の脱水触媒のアルミニウムとケイ素の原子比(Al/Si)は0.001〜0.13であることが好ましい。複合型の脱水触媒では0.03〜0.13であることがより好ましく、0.08〜0.12が最も好ましい。担持型の脱水触媒では0.005〜0.025であることがより好ましく、0.006〜0.012が最も好ましい。原子比がこの範囲内であると、副生物の低減又はコーキングの抑制の面で好ましく、また、細孔構造及び成形性を含めた触媒調製の自由度を高くできる。複合型触媒の原子比(Al/Si)は、リガク製の走査型蛍光X線分析装置ZSX PrimusIIを用いて、XRF分析にて決定される。担持型(表面型)触媒の原子比(Al/Si)は仕込み比から計算することもできるが、ICP−MSによりアルミニウム量を求め、触媒の乾燥質量からアルミニウム酸化物の質量を差し引いた質量を二酸化ケイ素の質量とし、Al/Siが計算される。測定方法の詳細は実施例の項に記載する。 The atomic ratio (Al / Si) of aluminum and silicon of the dehydration catalyst of the present invention is preferably 0.001 to 0.13. In the composite type dehydration catalyst, 0.03 to 0.13 is more preferable, and 0.08 to 0.12 is most preferable. The supported dehydration catalyst is more preferably 0.005 to 0.025, and most preferably 0.006 to 0.012. When the atomic ratio is within this range, it is preferable in terms of reduction of by-products or suppression of coking, and the degree of freedom of catalyst preparation including pore structure and moldability can be increased. The atomic ratio (Al / Si) of the composite catalyst is determined by XRF analysis using a scanning fluorescent X-ray analyzer ZSX Primus II manufactured by Rigaku. The atomic ratio (Al / Si) of the supported type (surface type) catalyst can be calculated from the charge ratio, but the amount of aluminum is obtained by ICP-MS, and the mass obtained by subtracting the mass of the aluminum oxide from the dry mass of the catalyst is obtained. Al / Si is calculated as the mass of silicon dioxide. Details of the measurement method are described in the Examples section.
本発明の触媒は、窒素ガス吸着法により測定された平均細孔径が6.0〜70.0nmであるメソ孔を有することが好ましい。平均細孔径はより好ましくは9.0〜55.0nm、特に好ましくは12.0〜40.0nmである。測定方法の詳細は実施例の項に記載する。平均細孔径が6.0nm以上であると、コーキングの進行が遅く、触媒寿命が長くなる。また、副反応が少ないため共役ジエン化合物の選択率も向上する。平均細孔径が70.0nm以下である触媒は表面積及び反応点の数が適切であり、生産性(STY)の低下が小さい。 The catalyst of the present invention preferably has mesopores having an average pore diameter measured by a nitrogen gas adsorption method of 6.0 to 70.0 nm. The average pore diameter is more preferably 9.0 to 55.0 nm, and particularly preferably 12.0 to 40.0 nm. Details of the measurement method are described in the Examples section. When the average pore diameter is 6.0 nm or more, the progress of coking is slow and the catalyst life is prolonged. Moreover, since there are few side reactions, the selectivity of a conjugated diene compound is also improved. A catalyst having an average pore diameter of 70.0 nm or less has an appropriate surface area and the number of reaction points, and a decrease in productivity (STY) is small.
触媒成形体は、成形体に触媒成分を担持して得ることもできるし、粉末触媒を種々の方法で成形して得ることもできる。成形方法に特に制限はなく、例えば打錠成形、押出成形、転動造粒等から選択される。 The catalyst molded body can be obtained by supporting a catalyst component on the molded body, or can be obtained by molding a powder catalyst by various methods. There is no restriction | limiting in particular in a shaping | molding method, For example, it selects from tableting shaping | molding, extrusion molding, rolling granulation, etc.
触媒成形体の粒径及び形状は、反応方式、反応器の形状などに応じて適宜選択できる。 The particle size and shape of the catalyst molded body can be appropriately selected depending on the reaction method, the shape of the reactor, and the like.
触媒の成形に用いるバインダー、滑剤等の添加剤は、特に制限されない。なお、これらの添加剤の添加による平均細孔径への影響は本発明において考慮しない。すなわち、バインダー、滑剤等の添加剤を加えて調製した触媒について測定して得られた平均細孔径が、バインダー、滑剤等の添加剤を添加せずに類似の方法で調製した触媒について測定して得られた平均細孔径と異なる場合、後者を本発明における平均細孔径とみなす。 Additives such as a binder and a lubricant used for forming the catalyst are not particularly limited. In addition, the influence on the average pore diameter due to the addition of these additives is not considered in the present invention. That is, the average pore diameter obtained by measuring a catalyst prepared by adding an additive such as a binder and a lubricant was measured for a catalyst prepared by a similar method without adding an additive such as a binder and a lubricant. When the average pore diameter is different from the obtained average pore diameter, the latter is regarded as the average pore diameter in the present invention.
本発明の脱水反応で使用する反応装置として連続式の気相流通反応装置が好適である。触媒は固定床又は流動床のいずれの方式でもよく、特にメンテナンスの面などから固定床が望ましい。 A continuous gas-phase flow reaction apparatus is suitable as the reaction apparatus used in the dehydration reaction of the present invention. The catalyst may be either a fixed bed or a fluidized bed, and a fixed bed is desirable from the standpoint of maintenance.
反応装置の一例として、上部に反応原料であるアリル型不飽和アルコールの気化器を備えた直管型反応器が挙げられる。反応器に触媒を充填し、原料を気化器で蒸発させて生じた原料ストリームを反応器に導入する。反応器下部の熱交換器で反応生成物を冷却して水等を分離し、生成物を回収する。気化した原料のアリル型不飽和アルコールを窒素ガス、水蒸気などの不活性ガスで希釈して反応に供してもよい。 As an example of the reaction apparatus, a straight pipe type reactor having a vaporizer for an allyl unsaturated alcohol as a reaction raw material at the upper part can be mentioned. The reactor is filled with the catalyst, and the raw material stream generated by evaporating the raw material in the vaporizer is introduced into the reactor. The reaction product is cooled by a heat exchanger at the bottom of the reactor to separate water and the like, and the product is recovered. The vaporized raw material allyl unsaturated alcohol may be diluted with an inert gas such as nitrogen gas or water vapor and used for the reaction.
反応温度は200〜450℃の範囲であることが適しており、250〜350℃であることがより好ましい。200℃以上であると反応が速やかに進む。また、450℃以下とすると副反応による選択率低下の影響が小さくなる。反応圧力は加圧、常圧、又は減圧のいずれでもよい。 The reaction temperature is suitably in the range of 200 to 450 ° C, more preferably 250 to 350 ° C. If it is 200 ° C. or higher, the reaction proceeds rapidly. Moreover, if it is 450 degrees C or less, the influence of the selectivity fall by a side reaction will become small. The reaction pressure may be pressurized, normal pressure, or reduced pressure.
触媒充填容積あたりの不飽和アルコールの導入量は0.05〜20kg/(h・L−cat)の範囲とすることができ、好ましくは0.1〜10kg/(h・L−cat)であり、最も好ましくは0.2〜5kg/(h・L−cat)である。導入量が少ない場合は十分な生産量を得ることができないことがある。多い場合には未反応の原料が増加し、分離及び精製に余分な労力が必要となる。 The amount of unsaturated alcohol introduced per catalyst packing volume can be in the range of 0.05 to 20 kg / (h · L-cat), preferably 0.1 to 10 kg / (h · L-cat). Most preferably, it is 0.2 to 5 kg / (h · L-cat). When the introduction amount is small, a sufficient production amount may not be obtained. In many cases, unreacted raw materials increase, and extra labor is required for separation and purification.
アリル型不飽和アルコールを含む原料ストリームの触媒充填容積に対する空間速度[SV]は100〜40000[/h]の範囲とすることができ、特に400〜10000[/h]であることが好適である。空間速度が低すぎる場合は接触時間の増加により、不飽和アルコール原料及び生成したジエン化合物から副生成物が生じる可能性がある。空間速度が高すぎる場合には転化率が低下し、収率が低下することがある。触媒の空時収率STYは、反応圧力を上げる、原料ガス中の不飽和アルコール濃度を高める、SVを上げることにより大きくすることができる。 The space velocity [SV] with respect to the catalyst filling volume of the raw material stream containing the allylic unsaturated alcohol can be in the range of 100 to 40000 [/ h], particularly preferably 400 to 10,000 [/ h]. . When the space velocity is too low, by-products may be generated from the unsaturated alcohol raw material and the produced diene compound due to an increase in contact time. If the space velocity is too high, the conversion rate may decrease and the yield may decrease. The space-time yield STY of the catalyst can be increased by increasing the reaction pressure, increasing the unsaturated alcohol concentration in the raw material gas, and increasing the SV.
得られた共役ジエン化合物に対し、さらに蒸留等による精製操作を行うことで、純度を高めたジエン化合物を入手することができる。 By further purifying the resulting conjugated diene compound by distillation or the like, a diene compound with increased purity can be obtained.
上記に述べた方法は、本発明の実施形態の一つであり、実施に当たってはその神髄に照らして、別の実施形態をとることもできるが、それらは全て本発明の範疇に含まれる。 The method described above is one of the embodiments of the present invention, and in the light of its essence, other embodiments can be taken. However, they are all included in the scope of the present invention.
以下、実施例により本発明の効果を具体的に説明するが、本発明はこれらの実施例により限定されるものではない。 Examples The effects of the present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.
[測定方法]
酸量はNH3−TPD法により測定する。具体的には、日本ベル株式会社製自動昇温脱離装置TPD−1−ATを用いて以下の手順で測定する。乳鉢で粉砕した触媒100mgを測定用セルに充填する。Heガスを50sccmで流通させながら、400℃で2時間触媒の前処理を行う。100℃まで冷却したら、NH3を100Torrの定圧で吸着させる。続いて、50sccmのHeガス流通下、100℃、160Torrの減圧条件で50分間処理を行う。その後、160〜200Torrの間の減圧条件で、700℃まで10℃/分の速度で昇温し、700℃で50分間保持する。分析終了後、0.193体積%のNH3ガス(Heバランス)と0.97体積%のNH3ガス(Heバランス)を用いて検量線を作成する。各温度で脱離するNH3と水の合計量と検量線作成時のNH3の量を質量分析計(Mass=16)で測定し、脱離するNH3と水の合計量を算出する。続いて、100℃、100TorrでのNH3定圧吸着を行わない他は同一の条件でブランク測定を行い、触媒から脱離する水由来の測定値を算出する。本測定の測定値からブランク測定の測定値を減算し、脱離NH3量とする。脱離NH3量(mol数)が触媒の酸点のmol数と等しいとして、触媒1g当たりの酸量(mol/g)を計算する。
[Measuring method]
Acid amount is measured by NH 3 -TPD method. Specifically, the measurement is performed by the following procedure using an automatic temperature-programmed desorption device TPD-1-AT manufactured by Nippon Bell Co., Ltd. The measurement cell is filled with 100 mg of the catalyst pulverized in a mortar. The catalyst is pretreated at 400 ° C. for 2 hours while flowing He gas at 50 sccm. After cooling to 100 ° C., NH 3 is adsorbed at a constant pressure of 100 Torr. Subsequently, treatment is performed for 50 minutes under a reduced pressure condition of 100 ° C. and 160 Torr under a flow of He gas of 50 sccm. Thereafter, the temperature is raised to 700 ° C. at a rate of 10 ° C./min under reduced pressure conditions of 160 to 200 Torr, and held at 700 ° C. for 50 minutes. After the analysis is completed, a calibration curve is created using 0.193% by volume of NH 3 gas (He balance) and 0.97% by volume of NH 3 gas (He balance). The total amount of NH 3 and water desorbed at each temperature and the amount of NH 3 at the time of preparing the calibration curve are measured with a mass spectrometer (Mass = 16), and the total amount of NH 3 and water desorbed is calculated. Subsequently, blank measurement is performed under the same conditions except that NH 3 constant pressure adsorption is not performed at 100 ° C. and 100 Torr, and a measurement value derived from water desorbed from the catalyst is calculated. The measurement value of the blank measurement is subtracted from the measurement value of the main measurement to obtain the amount of desorbed NH 3 . The amount of acid (mol / g) per gram of catalyst is calculated on the assumption that the amount of desorbed NH 3 (number of mol) is equal to the number of moles of the acid point of the catalyst.
複合型触媒のアルミニウム酸化物量とケイ素酸化物量は、リガク製の走査型蛍光X線分析装置ZSX PrimusIIを用いて、XRF分析にて行う。乳鉢で粉砕した触媒粉を、外径18mm、内径13mm、高さ5mmのポリ塩化ビニル製のセルにつめて35kNで15秒間加圧して、測定試料を調製する。標準試料を外標準としてEZスキャンモードにて分析する。アルミニウム酸化物量とケイ素酸化物量の測定値から、Al/Si比及びアルミニウム含有量を求める。アルミニウム含有量は触媒1gあたりのアルミニウム元素のmol数とする。 The amount of aluminum oxide and silicon oxide in the composite catalyst is determined by XRF analysis using a scanning fluorescent X-ray analyzer ZSX Primus II manufactured by Rigaku. A catalyst sample pulverized in a mortar is packed in a polyvinyl chloride cell having an outer diameter of 18 mm, an inner diameter of 13 mm, and a height of 5 mm, and pressurized at 35 kN for 15 seconds to prepare a measurement sample. The standard sample is analyzed as an external standard in the EZ scan mode. From the measured values of the amount of aluminum oxide and the amount of silicon oxide, the Al / Si ratio and the aluminum content are determined. The aluminum content is the number of moles of aluminum element per gram of catalyst.
担持型触媒のアルミニウム含有量はICP−MSにより求め、乾燥減量を考慮したうえで算出することができる。具体的には、以下の手順で求める。乳鉢で粉砕した試料にフッ酸2mL及び純水10mLを添加し試料を溶解させる。その後50mLに定容してICP発光分析によりアルミニウム元素を定量する。TG−DTAを用いて、乳鉢で粉砕した試料を窒素ガス気流下300℃で1時間処理し、その質量変化から乾燥質量を算出する。乾燥触媒1g中のアルミニウム元素のmol数をアルミニウム含有量とする。乾燥質量からアルミニウムの酸化物の質量を差し引いた質量を二酸化ケイ素の質量とし、Al/Si比を計算する。簡便のため、仕込み比から算出することも可能であり、本実施例ではこの簡便法によった。 The aluminum content of the supported catalyst can be calculated by ICP-MS and can be calculated in consideration of loss on drying. Specifically, the following procedure is used. 2 mL of hydrofluoric acid and 10 mL of pure water are added to the sample ground in the mortar to dissolve the sample. Thereafter, the volume is adjusted to 50 mL, and the aluminum element is quantified by ICP emission analysis. Using TG-DTA, a sample pulverized in a mortar is treated at 300 ° C. for 1 hour in a nitrogen gas stream, and the dry mass is calculated from the mass change. The number of moles of aluminum element in 1 g of the dry catalyst is defined as the aluminum content. The mass obtained by subtracting the mass of the oxide of aluminum from the dry mass is defined as the mass of silicon dioxide, and the Al / Si ratio is calculated. For simplicity, it is also possible to calculate from the charging ratio. In this example, this simple method was used.
アルミニウム分散度は、下記数式より算出する。アルミニウム分散度は触媒に含有されるアルミニウム原子のうち酸として寄与しているものの比率を表す値である。
触媒成形体の窒素ガス吸着法による平均細孔径とBET比表面積は、以下のように測定する。150℃、40mTorrで3時間前処理したサンプルについて、Micromeritics社製の自動比表面積/細孔分布測定装置(TristarII 3020)を用い、液体窒素温度で、相対圧(P/P0、P0:飽和蒸気圧)が0.14〜0.992の範囲で窒素脱着等温線を測定する。窒素ガスを吸着質として用い、吸着質断面積は0.162nm2として計算する。BET多点法を用いてBET比表面積を算出する。平均細孔径及び細孔容積はBJH法を用い、吸着膜の厚みをHarkins−Juraの式でt=[13.99/0.034―log(P/P0)]^0.5として算出する。 The average pore diameter and the BET specific surface area of the catalyst molded body by the nitrogen gas adsorption method are measured as follows. For a sample pretreated at 150 ° C. and 40 mTorr for 3 hours, using an automatic specific surface area / pore distribution measuring device (Tristar II 3020) manufactured by Micromeritics, at a liquid nitrogen temperature, relative pressure (P / P 0 , P 0 : saturation) The nitrogen desorption isotherm is measured in the range of (vapor pressure) in the range of 0.14 to 0.992. Nitrogen gas is used as the adsorbate, and the adsorbate cross section is calculated as 0.162 nm 2 . The BET specific surface area is calculated using the BET multipoint method. The average pore diameter and pore volume are calculated using the BJH method, and the thickness of the adsorption film is calculated as Harkins-Jura as t = [13.9 / 0.034−log (P / P 0 )] ^ 0.5. .
触媒成形体の嵩密度は以下のように決定する。10mLメスシリンダーに約5mLの触媒を測りとる。その際、数回タッピングを行い、触媒をならし、その体積と重量を測定する。測定重量を測定体積で除算し、嵩密度を計算する。 The bulk density of the catalyst molded body is determined as follows. Weigh about 5 mL of catalyst into a 10 mL graduated cylinder. At that time, tapping is performed several times, the catalyst is smoothed, and its volume and weight are measured. Divide the measured weight by the measured volume to calculate the bulk density.
[反応装置]
以下の実施例及び比較例の脱水反応には、固定床の常圧気相流通反応装置を使用した。反応管(ステンレス製)は内径13mm、全長300mmで、上部に原料を蒸発させるための気化器、及び希釈剤(窒素ガス)の導入口が接続され、下部には冷却器、及び気液分離器が設置されている。反応によって生じたガス及び液はそれぞれ別々に回収し、ガスクロマトグラフィー装置にて測定し、検量線補正後、目的物の収量及び原料残量を求め、これらより転化率及び選択率を求めた。
[Reactor]
For the dehydration reactions of the following Examples and Comparative Examples, a fixed bed atmospheric pressure gas flow reactor was used. The reaction tube (made of stainless steel) has an inner diameter of 13 mm and an overall length of 300 mm. The vaporizer for evaporating the raw material and the diluent (nitrogen gas) inlet are connected to the upper part, and the lower part is a cooler and a gas-liquid separator. Is installed. The gas and liquid produced by the reaction were collected separately, measured with a gas chromatography apparatus, and after correcting the calibration curve, the yield of the target product and the remaining amount of the raw material were determined, and the conversion and selectivity were determined from these.
脱水反応における、転化率及び選択率の計算には以下の式を用いた。選択率は、転化率が98.5%を下回るまでの結果から計算した。
代表的な副生成物であるブテンの選択率計算には、以下の式を用いた。選択率は、転化率が98.5%を下回るまでの結果から計算した。
[触媒調製]
以下、脱水触媒の調製に関する実施例及び比較例を示す。
[Catalyst preparation]
Examples and comparative examples relating to the preparation of the dehydration catalyst are shown below.
(実施例1:複合型触媒Aの調製)
500mLの3口フラスコに、メカニカルスターラーに接続したテフロン(登録商標)半月板撹拌翼、滴下ロート、及びジムロート冷却管を装着した。このフラスコに、窒素ガス雰囲気中で、テトラエチルオルトシリケート(シグマアルドリッチ社製、>99%)60.0g、アルミニウムイソプロポキシド(東京化成工業株式会社製)2.9g、超脱水イソプロパノール(和光純薬工業株式会社製)173gを加え、液温が79〜80℃になるように油浴中、250rpmで撹拌した。滴下ロートにイソプロパノール(特級、和光純薬工業株式会社製)9gと蒸留水(和光純薬工業株式会社製)10.9gの混合溶液を入れ、上記フラスコに30分間かけて滴下した。滴下終了後も撹拌を続け、合計9時間、79〜80℃で反応させた。得られた白色粉末を濾過後、イソプロパノールで洗浄した。70℃のオーブンで12時間乾燥したのち、マッフル炉(ADVANTEC製KM−280)で500℃、5時間焼成した。得られた粉末を、ポリ塩化ビニル製のセル(30mmφ)に入れ、80MPaの圧力で1分間プレスした。得られたディスク状のセル(厚さ5mm)を破砕し、1.4〜2.8mmのふるい間に残るものを回収した。得られた成形体を、同じマッフル炉で500℃、2時間焼成し、複合型触媒Aを得た。XRF分析で測定されたAlとSiの原子比(Al/Si)は0.09(mol/mol)であった。
(Example 1: Preparation of composite catalyst A)
A 500 mL three-necked flask was equipped with a Teflon (registered trademark) meniscus stirring blade connected to a mechanical stirrer, a dropping funnel, and a Dimroth condenser. In a nitrogen gas atmosphere, 60.0 g of tetraethylorthosilicate (Sigma Aldrich,> 99%), 2.9 g of aluminum isopropoxide (Tokyo Chemical Industry Co., Ltd.), ultra-dehydrated isopropanol (Wako Pure Chemical) 173 g (manufactured by Kogyo Co., Ltd.) was added, and the mixture was stirred at 250 rpm in an oil bath so that the liquid temperature became 79 to 80 ° C. A mixed solution of 9 g of isopropanol (special grade, manufactured by Wako Pure Chemical Industries, Ltd.) and 10.9 g of distilled water (manufactured by Wako Pure Chemical Industries, Ltd.) was placed in the dropping funnel and dropped into the flask over 30 minutes. Stirring was continued after completion of the dropwise addition, and the reaction was carried out at 79-80 ° C. for a total of 9 hours. The resulting white powder was filtered and washed with isopropanol. After drying in an oven at 70 ° C. for 12 hours, it was baked at 500 ° C. for 5 hours in a muffle furnace (KM-280 manufactured by ADVANTEC). The obtained powder was put into a cell (30 mmφ) made of polyvinyl chloride and pressed at a pressure of 80 MPa for 1 minute. The obtained disk-shaped cell (
(実施例2:複合型触媒Bの調製)
1Lの3口フラスコに、メカニカルスターラーに接続したテフロン(登録商標)半月板撹拌翼、滴下ロート、及びジムロート冷却管を装着した。このフラスコに、窒素ガス雰囲気中で、テトラエチルオルトシリケート(シグマアルドリッチ社製、>99%)120.0g、アルミニウムイソプロポキシド(東京化成工業株式会社製)5.9g、超脱水イソプロパノール(和光純薬工業株式会社製)320gを加え、液温が69〜70℃になるように油浴中、250rpmで撹拌した。滴下ロートにイソプロパノール(特級、和光純薬工業株式会社製)44gと蒸留水(和光純薬工業株式会社製)21.8gの混合溶液を入れ、上記フラスコに30分間かけて滴下した。滴下終了後も撹拌を続け、合計24時間、69〜70℃で反応させた。得られた白色粉末を濾過後、イソプロパノールで洗浄した。70℃のオーブンで12時間乾燥したのち、マッフル炉(ADVANTEC製KM−280)で500℃、5時間焼成した。得られた粉末を実施例1と同様の方法で成形及び焼成し、複合型触媒Bを得た。XRF分析で測定されたAlとSiの原子比(Al/Si)は0.10(mol/mol)であった。
(Example 2: Preparation of composite catalyst B)
A 1 L three-necked flask was equipped with a Teflon (registered trademark) meniscus stirring blade connected to a mechanical stirrer, a dropping funnel, and a Dimroth condenser. In a nitrogen gas atmosphere, 120.0 g of tetraethylorthosilicate (Sigma Aldrich,> 99%), 5.9 g of aluminum isopropoxide (Tokyo Chemical Industry Co., Ltd.), ultra-dehydrated isopropanol (Wako Pure Chemical) 320 g of Kogyo Co., Ltd. was added, and the mixture was stirred at 250 rpm in an oil bath so that the liquid temperature was 69 to 70 ° C. A mixed solution of 44 g of isopropanol (special grade, manufactured by Wako Pure Chemical Industries, Ltd.) and 21.8 g of distilled water (manufactured by Wako Pure Chemical Industries, Ltd.) was placed in the dropping funnel and dropped into the flask over 30 minutes. Stirring was continued after completion of the dropwise addition, and the reaction was performed at 69 to 70 ° C. for a total of 24 hours. The resulting white powder was filtered and washed with isopropanol. After drying in an oven at 70 ° C. for 12 hours, it was baked at 500 ° C. for 5 hours in a muffle furnace (KM-280 manufactured by ADVANTEC). The obtained powder was molded and fired in the same manner as in Example 1 to obtain a composite catalyst B. The atomic ratio (Al / Si) of Al and Si measured by XRF analysis was 0.10 (mol / mol).
(比較例1:複合型触媒Cの調製)
500mLの3口フラスコに、メカニカルスターラーに接続したテフロン(登録商標)半月板撹拌翼、滴下ロート、及びジムロート冷却管を装着した。このフラスコに、窒素ガス雰囲気中で、テトラエチルオルトシリケート(シグマアルドリッチ社製、>99%)90.0g、アルミニウムイソプロポキシド(東京化成工業株式会社製)4.4g、超脱水イソプロパノール(和光純薬工業株式会社製)260gを加え、液温が71〜72℃になるように油浴中、100rpmで撹拌した。滴下ロートにイソプロパノール(特級、和光純薬工業株式会社製)13gと蒸留水(和光純薬工業株式会社製)16.3gの混合溶液を入れ、上記フラスコに30分間かけて滴下した。滴下終了後も撹拌を続け、合計24時間、71〜72℃で反応させた。得られた白色粉末を濾過後、イソプロパノールで洗浄した。70℃のオーブンで12時間乾燥したのち、マッフル炉(ADVANTEC製KM−280)で500℃、5時間焼成した。得られた粉末を実施例1と同様の方法で成形及び焼成し、複合型触媒Cを得た。XRF分析で測定されたAlとSiの原子比(Al/Si)は0.10(mol/mol)であった。
(Comparative Example 1: Preparation of composite catalyst C)
A 500 mL three-necked flask was equipped with a Teflon (registered trademark) meniscus stirring blade connected to a mechanical stirrer, a dropping funnel, and a Dimroth condenser. In a nitrogen gas atmosphere, 90.0 g of tetraethylorthosilicate (Sigma Aldrich,> 99%), 4.4 g of aluminum isopropoxide (Tokyo Chemical Industry Co., Ltd.), ultra-dehydrated isopropanol (Wako Pure Chemical) 260 g) (manufactured by Kogyo Co., Ltd.) was added, and the mixture was stirred at 100 rpm in an oil bath so that the liquid temperature became 71 to 72 ° C. A mixed solution of 13 g of isopropanol (special grade, manufactured by Wako Pure Chemical Industries, Ltd.) and 16.3 g of distilled water (manufactured by Wako Pure Chemical Industries, Ltd.) was placed in the dropping funnel and dropped into the flask over 30 minutes. Stirring was continued after completion of the dropwise addition, and the reaction was carried out at 71 to 72 ° C. for a total of 24 hours. The resulting white powder was filtered and washed with isopropanol. After drying in an oven at 70 ° C. for 12 hours, it was baked at 500 ° C. for 5 hours in a muffle furnace (KM-280 manufactured by ADVANTEC). The obtained powder was molded and fired in the same manner as in Example 1 to obtain a composite catalyst C. The atomic ratio (Al / Si) of Al and Si measured by XRF analysis was 0.10 (mol / mol).
(実施例3:複合型触媒Dの調製)
500mLの3口フラスコに、メカニカルスターラーに接続したテフロン(登録商標)半月板撹拌翼、滴下ロート、及びジムロート冷却管を装着した。このフラスコに、窒素ガス雰囲気中で、アセチルアセトン(特級、和光純薬工業株式会社製)2.2gと超脱水イソプロパノール(和光純薬工業株式会社製)100gを入れたのち、アルミニウムイソプロポキシド(東京化成工業株式会社製)4.4g、テトラエチルオルトシリケート(シグマアルドリッチ社製、>99%)60.0g、超脱水イソプロパノール(和光純薬工業株式会社製)60gの順に加え、液温が69〜70℃になるように油浴中、250rpmで撹拌した。滴下ロートに25質量%のアンモニア水2.0gと蒸留水(和光純薬工業株式会社製)23.2gの混合溶液を入れ、上記フラスコに30分間かけて滴下した。滴下終了後も撹拌を続け、合計24時間、69〜70℃で反応させた。得られたゲルを70℃のオーブンで12時間乾燥したのち、1Mアンモニア水で10質量%のスラリーとして50℃で24時間熟成させた。得られた白色粉末を濾過及び水洗後、70℃のオーブンで12時間乾燥し、次いでマッフル炉(ADVANTEC製KM−280)で500℃、5時間焼成した。得られた粉末を実施例1と同様の方法で成形及び焼成し、複合型触媒Dを得た。XRF分析で測定されたAlとSiの原子比(Al/Si)は0.08(mol/mol)であった。
(Example 3: Preparation of composite catalyst D)
A 500 mL three-necked flask was equipped with a Teflon (registered trademark) meniscus stirring blade connected to a mechanical stirrer, a dropping funnel, and a Dimroth condenser. In a nitrogen gas atmosphere, 2.2 g of acetylacetone (special grade, manufactured by Wako Pure Chemical Industries, Ltd.) and 100 g of ultra-dehydrated isopropanol (made by Wako Pure Chemical Industries, Ltd.) were placed in the flask, and then aluminum isopropoxide (Tokyo, Japan). (Chemical Industry Co., Ltd.) 4.4 g, Tetraethylorthosilicate (Sigma Aldrich Co.,> 99%) 60.0 g, Super Dehydrated Isopropanol (Wako Pure Chemical Industries Co., Ltd.) 60 g are added in this order, and the liquid temperature is 69-70. The mixture was stirred at 250 rpm in an oil bath so that the temperature became 0 ° C. A mixed solution of 2.0 g of 25 mass% ammonia water and 23.2 g of distilled water (manufactured by Wako Pure Chemical Industries, Ltd.) was placed in the dropping funnel and dropped into the flask over 30 minutes. Stirring was continued after completion of the dropwise addition, and the reaction was performed at 69 to 70 ° C. for a total of 24 hours. The obtained gel was dried in an oven at 70 ° C. for 12 hours, and then aged as a 10 mass% slurry with 1M ammonia water at 50 ° C. for 24 hours. The obtained white powder was filtered and washed with water, dried in an oven at 70 ° C. for 12 hours, and then baked in a muffle furnace (KM-280 manufactured by ADVANTEC) at 500 ° C. for 5 hours. The obtained powder was molded and fired in the same manner as in Example 1 to obtain a composite catalyst D. The atomic ratio of Al to Si (Al / Si) measured by XRF analysis was 0.08 (mol / mol).
(実施例4:複合型触媒Eの調製)
500mLナスフラスコに硝酸アルミニウム・九水和物(和光純薬工業株式会社製、特級)16.2g、エタノール(特級、和光純薬工業株式会社製)34mL、蒸留水(和光純薬工業株式会社製)66mLを加え、メカニカルスターラーに接続したテフロン(登録商標)半月板撹拌翼で撹拌した。テトラエチルオルトシリケート(シグマアルドリッチ社製、>99%)91.0g、エタノール100mLの混合溶液を上記フラスコに加え入れた。室温で3時間撹拌を継続した後、25%アンモニア水91.0gを投入した。内容物をナスフラスコに移し、ロータリーエバポレーターを用いて60℃の湯浴中で4時間かけて溶媒を留去し、粉末を得た。得られた粉末は120℃のオーブンで12時間乾燥し、次いでマッフル炉(ADVANTEC製KM−280)で500℃、4時間焼成した。得られた粉末を実施例1と同様の方法で成形及び焼成し、複合型触媒Eを得た。XRF分析で測定されたAlとSiの原子比(Al/Si)は0.11(mol/mol)であった。
(Example 4: Preparation of composite catalyst E)
In a 500 mL eggplant flask, 16.2 g of aluminum nitrate nonahydrate (special grade, manufactured by Wako Pure Chemical Industries, Ltd.), 34 mL of ethanol (special grade, manufactured by Wako Pure Chemical Industries, Ltd.), distilled water (manufactured by Wako Pure Chemical Industries, Ltd.) ) 66 mL was added and stirred with a Teflon (registered trademark) meniscus stirring blade connected to a mechanical stirrer. A mixed solution of 91.0 g of tetraethyl orthosilicate (Sigma Aldrich,> 99%) and 100 mL of ethanol was added to the flask. After stirring at room temperature for 3 hours, 91.0 g of 25% aqueous ammonia was added. The contents were transferred to an eggplant flask and the solvent was distilled off over 4 hours in a 60 ° C. hot water bath using a rotary evaporator to obtain a powder. The obtained powder was dried in an oven at 120 ° C. for 12 hours, and then baked in a muffle furnace (KM-280 manufactured by ADVANTEC) at 500 ° C. for 4 hours. The obtained powder was molded and fired in the same manner as in Example 1 to obtain a composite catalyst E. The atomic ratio (Al / Si) of Al and Si measured by XRF analysis was 0.11 (mol / mol).
(実施例5:複合型触媒Fの調製)
硝酸アルミニウム・九水和物(和光純薬工業株式会社製、特級)20.3gと硝酸(和光純薬工業株式会社製、特級、60%)51.3gと酢酸(和光純薬工業株式会社製、特級)3.3gとポリビニルアルコール(和光純薬工業株式会社製、完全鹸化型、平均重合度400〜600)16.0gと蒸留水(和光純薬工業株式会社製)326mLの混合液をメカニカルスターラーに接続したテフロン(登録商標)製撹拌翼で撹拌した。ケイ酸ナトリウム溶液(和光純薬工業株式会社製、濃度55質量%、SiO2/Na2O=2.2)93.1gと蒸留水(和光純薬工業株式会社製)334mLの混合溶液を、上記硝酸アルミニウム水溶液に滴下した。30分間熟成したのち、アンモニア水溶液でpHを8にして沈殿を析出させ、さらに3時間撹拌を継続した。析出物に対し、ろ過、水洗浄、1%酢酸アンモニウム(和光純薬工業株式会社製)水溶液洗浄、水洗浄の順に処置を行った後、得られた析出物を50℃に加温したpH9のアンモニア水溶液中で48時間熟成させた。イオン交換水で2回洗浄後、70℃で12時間乾燥したのち、マッフル炉(ADVANTEC製KM−280)で500℃、2時間焼成した。得られた粉末を実施例1と同様の方法で成形及び焼成し、複合型触媒Fを得た。XRF分析で測定されたAlとSiの原子比(Al/Si)は0.11(mol/mol)であった。
(Example 5: Preparation of composite catalyst F)
Aluminum nitrate nonahydrate (made by Wako Pure Chemical Industries, special grade) 20.3g, nitric acid (made by Wako Pure Chemical Industries, special grade, 60%) 51.3g and acetic acid (made by Wako Pure Chemical Industries, Ltd.) , Special grade) 3.3g and polyvinyl alcohol (Wako Pure Chemical Industries, complete saponification type, average polymerization degree 400-600) 16.0g and distilled water (Wako Pure Chemical Industries, Ltd.) 326mL mixed liquid The mixture was stirred with a Teflon (registered trademark) stirring blade connected to a stirrer. A mixed solution of 93.1 g of sodium silicate solution (manufactured by Wako Pure Chemical Industries, Ltd., concentration 55 mass%, SiO 2 / Na 2 O = 2.2) and 334 mL of distilled water (manufactured by Wako Pure Chemical Industries, Ltd.) It was dripped at the said aluminum nitrate aqueous solution. After aging for 30 minutes, the pH was adjusted to 8 with an aqueous ammonia solution to precipitate, and stirring was further continued for 3 hours. The precipitate was treated in the order of filtration, water washing, 1% ammonium acetate (manufactured by Wako Pure Chemical Industries, Ltd.) aqueous solution, water washing, and the obtained precipitate was heated to 50 ° C. It was aged in an aqueous ammonia solution for 48 hours. After washing twice with ion-exchanged water, drying was performed at 70 ° C. for 12 hours, and then baking was performed at 500 ° C. for 2 hours in a muffle furnace (KM-280 manufactured by ADVANTEC). The obtained powder was molded and fired in the same manner as in Example 1 to obtain a composite catalyst F. The atomic ratio (Al / Si) of Al and Si measured by XRF analysis was 0.11 (mol / mol).
(比較例2:複合型触媒Gの調製)
Pluronic123(シグマアルドリッチ社製)8.0gを蒸留水(和光純薬工業株式会社製)72gに溶解させた。この溶液にコロイダルシリカ(スノーテックス(登録商標)O、シリカ20.4質量%、日産化学工業化学株式会社)47.4g、ムライトゾル(AS−L10、固形分10質量%、多木化学製)11.8g、蒸留水(和光純薬工業株式会社製)49.3gを加えた。得られた白濁液を磁製皿に薄く広げて130℃のオーブンで乾燥させ、さらにマッフル炉(ADVANTEC製KM−280)で500℃、5時間焼成した。得られた粉末を実施例1と同様の方法で成形及び焼成し、複合型触媒Gを得た。XRF分析で測定されたAlとSiの原子比(Al/Si)は0.15(mol/mol)であった。
(Comparative Example 2: Preparation of composite catalyst G)
Pluronic 123 (manufactured by Sigma Aldrich) 8.0 g was dissolved in 72 g of distilled water (manufactured by Wako Pure Chemical Industries, Ltd.). Colloidal silica (Snowtex (registered trademark) O, silica 20.4% by mass, Nissan Chemical Industries, Ltd.) 47.4 g, mullite sol (AS-L10,
(実施例6:担持型触媒Aの調製)
1Lビーカーに硝酸アルミニウム・九水和物(和光純薬工業株式会社製、特級)0.88gとイオン交換水300gを入れ、メカニカルスターラーに接続したテフロン(登録商標)半月板撹拌翼で撹拌して硝酸アルミニウムを溶解させた。このビーカーにシリカ粉であるキャリアクト(登録商標)G−10(粒径5μm、富士シリシア化学株式会社)13.2gを加え、20分間撹拌を継続した。この時点でのスラリー液のpHは約3であった。続いて1Mアンモニア水28gを30分かけて滴下した。この時点でのスラリー液のpHは約9であった。さらに24時間室温で撹拌を継続したのち、ろ過及び水洗を3回繰り返した。最後にろ過した粉末を80℃のオーブン中で12時間風乾した。得られた粉末を、ポリ塩化ビニル製のセル(30mmφ)に入れ、80MPaの圧力で1分間プレスした。得られたディスク状のセル(厚さ5mm)を破砕し、1.4〜2.8mmのふるい間に残るものを回収し、その後、マッフル炉(ADVANTEC製KM−280)で600℃、5時間焼成し、担持型触媒Aを得た。
(Example 6: Preparation of supported catalyst A)
Place 0.88 g of aluminum nitrate nonahydrate (special grade, manufactured by Wako Pure Chemical Industries, Ltd.) and 300 g of ion-exchanged water in a 1 L beaker, and stir with a Teflon (registered trademark) meniscus stirring blade connected to a mechanical stirrer. Aluminum nitrate was dissolved. To this beaker, 13.2 g of Silica powder CARACTECT (registered trademark) G-10 (
(実施例7:担持型触媒Bの調製)
硝酸アルミニウム・九水和物(和光純薬工業株式会社製、特級)を0.59g使用したほかは、実施例6と同様にして担持型触媒Bを調製した。
(Example 7: Preparation of supported catalyst B)
A supported catalyst B was prepared in the same manner as in Example 6 except that 0.59 g of aluminum nitrate nonahydrate (special grade, manufactured by Wako Pure Chemical Industries, Ltd.) was used.
(実施例8:担持型触媒Cの調製)
硝酸アルミニウム・九水和物(和光純薬工業株式会社製、特級)を1.76g使用したほかは、実施例6と同様にして担持型触媒Cを調製した。
(Example 8: Preparation of supported catalyst C)
A supported catalyst C was prepared in the same manner as in Example 6 except that 1.76 g of aluminum nitrate nonahydrate (special grade, manufactured by Wako Pure Chemical Industries, Ltd.) was used.
(実施例9:担持型触媒Dの調製)
300mLナスフラスコに硝酸アルミニウム・九水和物(和光純薬工業株式会社製、特級)0.54gとイオン交換水180gを入れ、メカニカルスターラーに接続したテフロン(登録商標)半月板撹拌翼で撹拌して硝酸アルミニウムを溶解させた。このフラスコにシリカ粉であるキャリアクト(登録商標)G−10(粒径5μm、富士シリシア化学株式会社)8.2gと尿素4.7gを加えた。このスラリー液を80℃に加温し、6時間撹拌を継続した。この時点でのスラリー液のpHは約8であった。さらに18時間室温で撹拌を継続したのち、ろ過・水洗を3回繰り返した。最後にろ過した粉末を80℃のオーブン中で12時間風乾を行った。得られた粉末を実施例6と同様に成形及び焼成して担持型触媒Dを得た。
(Example 9: Preparation of supported catalyst D)
Place 0.54 g of aluminum nitrate nonahydrate (special grade, manufactured by Wako Pure Chemical Industries, Ltd.) and 180 g of ion-exchanged water in a 300 mL eggplant flask and stir with a Teflon (registered trademark) meniscus stirring blade connected to a mechanical stirrer. The aluminum nitrate was dissolved. To this flask, 8.2 g of carrier powder (registered trademark) G-10 (particle size: 5 μm, Fuji Silysia Chemical Ltd.) and 4.7 g of urea were added as silica powder. The slurry was heated to 80 ° C. and stirring was continued for 6 hours. At this point, the pH of the slurry was about 8. After further stirring for 18 hours at room temperature, filtration and washing with water were repeated three times. The finally filtered powder was air-dried in an oven at 80 ° C. for 12 hours. The obtained powder was shaped and calcined in the same manner as in Example 6 to obtain a supported catalyst D.
(実施例10:担持型触媒Eの調製)
300mLナスフラスコに15%塩酸(和光純薬工業株式会社製、特級)100gとシリカ粉であるキャリアクト(登録商標)G−10(粒径5μm、富士シリシア化学株式会社)15gを入れ、メカニカルスターラーに接続したテフロン(登録商標)半月板撹拌翼で撹拌した。このスラリー液を70℃に加温して6時間撹拌を継続したのち、ろ過及び水洗をろ液が中性になるまで繰り返した。最後にろ過した粉末を80℃のオーブン中で12時間風乾を行った。得られたシリカ粉末を担体に用いて、実施例6と同様にして担持型触媒Eを得た。
(Example 10: Preparation of supported catalyst E)
In a 300 mL eggplant flask, 100 g of 15% hydrochloric acid (manufactured by Wako Pure Chemical Industries, Ltd., special grade) and 15 g of Carriert® (registered trademark) G-10 (particle size: 5 μm, Fuji Silysia Chemical Co., Ltd.), which is silica powder, are placed. The mixture was stirred with a Teflon (registered trademark) meniscus stirring blade connected to the. The slurry was heated to 70 ° C. and stirring was continued for 6 hours, and then filtration and water washing were repeated until the filtrate became neutral. The finally filtered powder was air-dried in an oven at 80 ° C. for 12 hours. Using the obtained silica powder as a carrier, a supported catalyst E was obtained in the same manner as in Example 6.
(比較例3:担持型触媒Fの調製)
シリカ粉であるキャリアクト(登録商標)G−10(粒径5μm、富士シリシア化学株式会社)20gに対し、硝酸アルミニウム・九水和物(和光純薬工業株式会社製、特級)1.34gを含む水溶液を含浸担持させ、エバポレーターで大部分の水を除いたのちに80℃のオーブン中で12時間風乾を行った。得られた粉末を実施例6と同様に成形及び焼成して担持型触媒Fを得た。
(Comparative Example 3: Preparation of supported catalyst F)
Silica powder Carriertect (registered trademark) G-10 (
[脱水反応]
以下、反応実施例を示す。触媒寿命は、原料のアリル型不飽和アルコール(式(1)及び式(2)の合計)の転化率と反応時間とのグラフから、転化率が約100%から低下して、98.5%となるまでの時間を読み取り、その値とした。平均コーク付着速度は、反応後に抜き出した触媒を用いて以下のように算出する。TG−DTAを用いて、反応後の抜出触媒の室温から650℃の区間の質量減少を、乾燥空気流通下、10℃/分の速度で昇温しながら測定する。室温から300℃までの質量減少をx%、300℃から650℃までの質量減少をy%とした場合に、下式に当てはめて平均コーク付着速度を算出する。
The reaction examples are shown below. From the graph of the conversion rate and the reaction time of the raw material allyl-type unsaturated alcohol (the sum of the formulas (1) and (2)), the conversion rate decreased from about 100% to 98.5%. The time to be read was taken as the value. The average coke adhesion rate is calculated as follows using the catalyst extracted after the reaction. Using TG-DTA, the mass reduction of the extracted catalyst after the reaction in the section from room temperature to 650 ° C. is measured while increasing the temperature at a rate of 10 ° C./min under a flow of dry air. When the mass decrease from room temperature to 300 ° C. is x% and the mass decrease from 300 ° C. to 650 ° C. is y%, the average coke adhesion rate is calculated by applying the following equation.
(反応実施例1)
複合型触媒Aに対して3−ブテン−2−オール/2−ブテン−1−オール混合溶液を基質とし、窒素ガス及び水蒸気を希釈剤として反応を行った。触媒は5mL使用した。基質の3−ブテン−2−オール及び2−ブテン−1−オールのモル比率は6:4であり、合計導入量は触媒1mLあたり毎時1.35gであった。水蒸気の導入量は触媒1mLあたり毎時0.84L、窒素ガス導入量は触媒1mLあたり毎時0.42Lで反応温度は300℃に設定した(SV=1680[/h])。結果を表1に示す。
(Reaction Example 1)
The composite catalyst A was reacted using a mixed solution of 3-buten-2-ol / 2-buten-1-ol as a substrate and nitrogen gas and water vapor as diluents. 5 mL of catalyst was used. The molar ratio of the substrates 3-buten-2-ol and 2-buten-1-ol was 6: 4, and the total amount introduced was 1.35 g per hour per mL of catalyst. The amount of steam introduced was 0.84 L / hr of catalyst, the amount of nitrogen gas introduced was 0.42 L / hr of catalyst, and the reaction temperature was 300 ° C. (SV = 1680 [/ h]). The results are shown in Table 1.
(反応実施例2〜10、反応比較例1〜3)
表1又は表2に示す触媒を使用し、反応実施例1と同様にして脱水反応を行った。結果を表1又は表2に示す。
(Reaction Examples 2 to 10, Reaction Comparative Examples 1 to 3)
A dehydration reaction was performed in the same manner as in Reaction Example 1 using the catalyst shown in Table 1 or 2. The results are shown in Table 1 or Table 2.
反応実施例1〜10と反応比較例1〜3のアルミニウム分散度に対する触媒寿命を図1に、1,3−ブタジエンの選択率を図2に示す。これらの図から理解できるように、複合型触媒ではアルミニウム分散度が0.10〜0.30の触媒、担持型触媒ではアルミニウム分散度が0.20〜0.45の触媒を用いると、非常に高選択的かつ長寿命で1,3−ブタジエンを得ることができる。
Claims (7)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2016088589A JP6656074B2 (en) | 2016-04-26 | 2016-04-26 | Method for producing conjugated diene compound by dehydration of allylic unsaturated alcohol |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2016088589A JP6656074B2 (en) | 2016-04-26 | 2016-04-26 | Method for producing conjugated diene compound by dehydration of allylic unsaturated alcohol |
Publications (2)
Publication Number | Publication Date |
---|---|
JP2017197458A true JP2017197458A (en) | 2017-11-02 |
JP6656074B2 JP6656074B2 (en) | 2020-03-04 |
Family
ID=60237376
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2016088589A Active JP6656074B2 (en) | 2016-04-26 | 2016-04-26 | Method for producing conjugated diene compound by dehydration of allylic unsaturated alcohol |
Country Status (1)
Country | Link |
---|---|
JP (1) | JP6656074B2 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2022196025A1 (en) * | 2021-03-19 | 2022-09-22 | 日揮触媒化成株式会社 | Silica-alumina powder, method for producing silica-alumina powder, fluid catalytic cracking catalyst and method for producing same |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2015048336A (en) * | 2013-09-03 | 2015-03-16 | 東レ株式会社 | Method for producing butadiene and/or 3-butene-2-ol |
JP2015054818A (en) * | 2013-09-10 | 2015-03-23 | 東レ株式会社 | Method for producing 1,3-butadiene and/or 3-butene-2-ol |
WO2015146789A1 (en) * | 2014-03-25 | 2015-10-01 | Jx日鉱日石エネルギー株式会社 | Dehydration catalyst and method for producing conjugated diene |
WO2015173780A1 (en) * | 2014-05-16 | 2015-11-19 | Versalis S.P.A. | Process for the production of alkenols and use thereof for the production of 1,3-butadiene |
-
2016
- 2016-04-26 JP JP2016088589A patent/JP6656074B2/en active Active
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2015048336A (en) * | 2013-09-03 | 2015-03-16 | 東レ株式会社 | Method for producing butadiene and/or 3-butene-2-ol |
JP2015054818A (en) * | 2013-09-10 | 2015-03-23 | 東レ株式会社 | Method for producing 1,3-butadiene and/or 3-butene-2-ol |
WO2015146789A1 (en) * | 2014-03-25 | 2015-10-01 | Jx日鉱日石エネルギー株式会社 | Dehydration catalyst and method for producing conjugated diene |
WO2015173780A1 (en) * | 2014-05-16 | 2015-11-19 | Versalis S.P.A. | Process for the production of alkenols and use thereof for the production of 1,3-butadiene |
Non-Patent Citations (1)
Title |
---|
REACTION KINETICS, MECHANISMS AND CATALYSIS, vol. 112(2), JPN6019051452, 2014, pages 467 - 475, ISSN: 0004185771 * |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2022196025A1 (en) * | 2021-03-19 | 2022-09-22 | 日揮触媒化成株式会社 | Silica-alumina powder, method for producing silica-alumina powder, fluid catalytic cracking catalyst and method for producing same |
Also Published As
Publication number | Publication date |
---|---|
JP6656074B2 (en) | 2020-03-04 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP7305558B2 (en) | Catalyst, method for producing the same, and method for producing a diene compound using the catalyst | |
Yang et al. | Cu/ZnO x@ UiO-66 synthesized from a double solvent method as an efficient catalyst for CO 2 hydrogenation to methanol | |
US20220161235A1 (en) | Catalyst, and method for producing 1,3-butadiene using same | |
JP7174947B2 (en) | Solid catalyst and method for producing butadiene | |
JP6678429B2 (en) | Method for producing conjugated diene compound and catalyst for dehydrating allylic unsaturated alcohol | |
JP6656074B2 (en) | Method for producing conjugated diene compound by dehydration of allylic unsaturated alcohol | |
JP5877853B2 (en) | Mixed oxide composition and method for producing isoolefin | |
JP2019043909A (en) | Method for producing aliphatic carboxylic acid ester | |
JP6684641B2 (en) | Method for producing conjugated diene compound and dehydration catalyst for allylic unsaturated alcohol | |
Zhang et al. | Ti-SBA-15 supported Cu–MgO catalyst for synthesis of isobutyraldehyde from methanol and ethanol | |
JP7197507B2 (en) | Catalyst, method for producing the same, and method for producing a diene compound using the catalyst | |
JP6869020B2 (en) | Method for producing conjugated diene compound | |
WO2020262486A1 (en) | Catalyst and method for producing diene compound | |
JP2017186272A (en) | Manufacturing method of diene compound | |
WO2022196717A1 (en) | Catalyst, methhod for producing catalyst, method for producing diene compound, method for producing polymer, method for producing polymer molded article, method for measuring catalyst performance, and method for prolonging service life | |
JP6462498B2 (en) | Process for producing unsaturated alcohol and catalyst | |
JP6684635B2 (en) | Method for producing diene compound | |
US20230158475A1 (en) | Catalyst and method for producing diene compound | |
JP7060994B2 (en) | Manufacturing method of p-xylene | |
KR101839568B1 (en) | Metal loaded catalyst, preparation method of the same, and preparation method of c4 olefin using the same | |
WO2022230791A1 (en) | Method for producing propylene | |
WO2024028334A1 (en) | Catalyst for the production of 1,3-butadiene having high activity | |
JP2003190786A (en) | Silica gel for carrier of olefin hydration catalyst and catalyst for olefin hydration | |
KR20220013326A (en) | Amorphous metal-phosphate catalyst and method for preparing thereof | |
JP2023117810A (en) | Method for producing cyclopentadiene |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20190205 |
|
A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20191114 |
|
TRDD | Decision of grant or rejection written | ||
A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20200107 |
|
A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20200204 |
|
R150 | Certificate of patent or registration of utility model |
Ref document number: 6656074 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
S111 | Request for change of ownership or part of ownership |
Free format text: JAPANESE INTERMEDIATE CODE: R313111 |
|
R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
S531 | Written request for registration of change of domicile |
Free format text: JAPANESE INTERMEDIATE CODE: R313531 |
|
R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |