JP4943307B2 - Method for producing catalyst for oxychlorination - Google Patents
Method for producing catalyst for oxychlorination Download PDFInfo
- Publication number
- JP4943307B2 JP4943307B2 JP2007305224A JP2007305224A JP4943307B2 JP 4943307 B2 JP4943307 B2 JP 4943307B2 JP 2007305224 A JP2007305224 A JP 2007305224A JP 2007305224 A JP2007305224 A JP 2007305224A JP 4943307 B2 JP4943307 B2 JP 4943307B2
- Authority
- JP
- Japan
- Prior art keywords
- acid
- catalyst
- slurry
- oxychlorination
- weight
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000003054 catalyst Substances 0.000 title claims description 118
- 238000004519 manufacturing process Methods 0.000 title claims description 30
- 239000002002 slurry Substances 0.000 claims description 94
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 65
- 238000001694 spray drying Methods 0.000 claims description 54
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 38
- 239000007864 aqueous solution Substances 0.000 claims description 37
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 27
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 22
- 239000010949 copper Substances 0.000 claims description 20
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 18
- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 claims description 18
- 229910052802 copper Inorganic materials 0.000 claims description 18
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 17
- 238000010304 firing Methods 0.000 claims description 17
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims description 15
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 15
- 239000002253 acid Substances 0.000 claims description 14
- 239000003513 alkali Substances 0.000 claims description 13
- 229910052736 halogen Inorganic materials 0.000 claims description 13
- 150000002367 halogens Chemical class 0.000 claims description 13
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 12
- 150000002910 rare earth metals Chemical class 0.000 claims description 12
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 claims description 9
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 9
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 9
- 230000032683 aging Effects 0.000 claims description 9
- 239000010419 fine particle Substances 0.000 claims description 9
- 239000000174 gluconic acid Substances 0.000 claims description 9
- 235000012208 gluconic acid Nutrition 0.000 claims description 9
- -1 rare earth salt Chemical class 0.000 claims description 8
- 150000003839 salts Chemical class 0.000 claims description 7
- FMHKPLXYWVCLME-UHFFFAOYSA-N 4-hydroxy-valeric acid Chemical compound CC(O)CCC(O)=O FMHKPLXYWVCLME-UHFFFAOYSA-N 0.000 claims description 6
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims description 6
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 6
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 6
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims description 6
- 239000011777 magnesium Substances 0.000 claims description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 6
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 6
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 claims description 6
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 6
- 150000001447 alkali salts Chemical class 0.000 claims description 5
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 4
- 229910052749 magnesium Inorganic materials 0.000 claims description 4
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 claims description 3
- RBNPOMFGQQGHHO-UHFFFAOYSA-N -2,3-Dihydroxypropanoic acid Natural products OCC(O)C(O)=O RBNPOMFGQQGHHO-UHFFFAOYSA-N 0.000 claims description 3
- VBSTXRUAXCTZBQ-UHFFFAOYSA-N 1-hexyl-4-phenylpiperazine Chemical compound C1CN(CCCCCC)CCN1C1=CC=CC=C1 VBSTXRUAXCTZBQ-UHFFFAOYSA-N 0.000 claims description 3
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 claims description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 3
- ALRHLSYJTWAHJZ-UHFFFAOYSA-N 3-hydroxypropionic acid Chemical compound OCCC(O)=O ALRHLSYJTWAHJZ-UHFFFAOYSA-N 0.000 claims description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 3
- RBNPOMFGQQGHHO-UWTATZPHSA-N D-glyceric acid Chemical compound OC[C@@H](O)C(O)=O RBNPOMFGQQGHHO-UWTATZPHSA-N 0.000 claims description 3
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 3
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 3
- JACRWUWPXAESPB-QMMMGPOBSA-N Tropic acid Natural products OC[C@H](C(O)=O)C1=CC=CC=C1 JACRWUWPXAESPB-QMMMGPOBSA-N 0.000 claims description 3
- 239000001361 adipic acid Substances 0.000 claims description 3
- 235000011037 adipic acid Nutrition 0.000 claims description 3
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims description 3
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 claims description 3
- UKXSKSHDVLQNKG-UHFFFAOYSA-N benzilic acid Chemical compound C=1C=CC=CC=1C(O)(C(=O)O)C1=CC=CC=C1 UKXSKSHDVLQNKG-UHFFFAOYSA-N 0.000 claims description 3
- 238000005660 chlorination reaction Methods 0.000 claims description 3
- 235000019253 formic acid Nutrition 0.000 claims description 3
- 239000001530 fumaric acid Substances 0.000 claims description 3
- 239000004310 lactic acid Substances 0.000 claims description 3
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 3
- 239000011976 maleic acid Substances 0.000 claims description 3
- 239000001630 malic acid Substances 0.000 claims description 3
- 235000011090 malic acid Nutrition 0.000 claims description 3
- 235000006408 oxalic acid Nutrition 0.000 claims description 3
- 239000011591 potassium Substances 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 235000002906 tartaric acid Nutrition 0.000 claims description 3
- 239000011975 tartaric acid Substances 0.000 claims description 3
- 239000002245 particle Substances 0.000 description 50
- 230000000694 effects Effects 0.000 description 32
- 238000002360 preparation method Methods 0.000 description 24
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 20
- 239000012798 spherical particle Substances 0.000 description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 20
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 19
- 230000007423 decrease Effects 0.000 description 18
- 239000000017 hydrogel Substances 0.000 description 13
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 12
- 239000005977 Ethylene Substances 0.000 description 12
- 239000011164 primary particle Substances 0.000 description 11
- 238000000034 method Methods 0.000 description 10
- 238000002485 combustion reaction Methods 0.000 description 9
- 239000000460 chlorine Substances 0.000 description 8
- 238000005260 corrosion Methods 0.000 description 8
- 230000007797 corrosion Effects 0.000 description 8
- MFUVDXOKPBAHMC-UHFFFAOYSA-N magnesium;dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MFUVDXOKPBAHMC-UHFFFAOYSA-N 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 238000001035 drying Methods 0.000 description 7
- 238000011156 evaluation Methods 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 6
- 229910052801 chlorine Inorganic materials 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000009826 distribution Methods 0.000 description 6
- 150000002823 nitrates Chemical class 0.000 description 6
- 229910017604 nitric acid Inorganic materials 0.000 description 6
- 239000011148 porous material Substances 0.000 description 6
- 238000001354 calcination Methods 0.000 description 5
- 230000005484 gravity Effects 0.000 description 5
- 239000011163 secondary particle Substances 0.000 description 5
- 229910002651 NO3 Inorganic materials 0.000 description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 4
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 4
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 4
- QQZMWMKOWKGPQY-UHFFFAOYSA-N cerium(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O QQZMWMKOWKGPQY-UHFFFAOYSA-N 0.000 description 4
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- GJKFIJKSBFYMQK-UHFFFAOYSA-N lanthanum(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GJKFIJKSBFYMQK-UHFFFAOYSA-N 0.000 description 4
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 229910001388 sodium aluminate Inorganic materials 0.000 description 4
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 3
- 238000007792 addition Methods 0.000 description 3
- 150000001735 carboxylic acids Chemical class 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 150000003840 hydrochlorides Chemical class 0.000 description 3
- 229940050906 magnesium chloride hexahydrate Drugs 0.000 description 3
- DHRRIBDTHFBPNG-UHFFFAOYSA-L magnesium dichloride hexahydrate Chemical compound O.O.O.O.O.O.[Mg+2].[Cl-].[Cl-] DHRRIBDTHFBPNG-UHFFFAOYSA-L 0.000 description 3
- 229940091250 magnesium supplement Drugs 0.000 description 3
- 239000011268 mixed slurry Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910002492 Ce(NO3)3·6H2O Inorganic materials 0.000 description 2
- 229910021193 La 2 O 3 Inorganic materials 0.000 description 2
- 229910002422 La(NO3)3·6H2O Inorganic materials 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- SXTLQDJHRPXDSB-UHFFFAOYSA-N copper;dinitrate;trihydrate Chemical compound O.O.O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O SXTLQDJHRPXDSB-UHFFFAOYSA-N 0.000 description 2
- 229960003280 cupric chloride Drugs 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 230000001629 suppression Effects 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 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 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- 229910000421 cerium(III) oxide Inorganic materials 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 159000000011 group IA salts Chemical class 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 150000002763 monocarboxylic acids Chemical class 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- KTUFCUMIWABKDW-UHFFFAOYSA-N oxo(oxolanthaniooxy)lanthanum Chemical compound O=[La]O[La]=O KTUFCUMIWABKDW-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 235000015320 potassium carbonate Nutrition 0.000 description 1
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
本発明は、アルミナと銅と必要に応じてアルカリ土類、アルカリ、希土類とを含んでなり、ハロゲン（塩素）の含有量が少ないオキシクロリネーション用触媒の製造方法に関する。
さらに詳しくは、活性成分原料等として塩化物を使用しないので装置の腐蝕等が無く、且つ、得られる触媒はハロゲン（塩素）含有量が少なくても高い活性および１，２−ジクロルエタン（以下、ＥＤＣと略記することがある。）の選択性およびエチレン燃焼抑制性を有するとともに流動性がよく、その流動性を長期に亘って維持することができ、同時に耐摩耗性等に優れたオキシクロリネーション用触媒の製造方法に関する。
The present invention relates to a method for producing an oxychlorination catalyst comprising alumina, copper and, if necessary, alkaline earth, alkali, rare earth, and having a low halogen (chlorine) content.
More specifically, since no chloride is used as an active ingredient raw material or the like, there is no corrosion of the apparatus, and the obtained catalyst has a high activity and 1,2-dichloroethane (hereinafter referred to as EDC) even if the halogen (chlorine) content is small. For oxychlorination, which has excellent selectivity and ethylene combustion suppression and fluidity, and can maintain its fluidity over a long period of time. The present invention relates to a method for producing a catalyst.
従来、オキシ塩素化法による脂肪族炭化水素の塩素化には一般に、多孔質なアルミナ、シリカアルミナ、粘土などの担体に金属塩を担持させた触媒が用いられていた。特に、エチレンのオキシクロリネーションによるＥＤＣの製造には、工業的には古くから塩化第二銅を含浸法によりアルミナ担体に担持させた流動床用触媒が用いられる。しかし、この触媒は活性成分である銅が移動あるいは昇華し、活性の低下や流動性の低下を引き起こし、この結果、触媒層の温度分布が不均一となり高温部においてエチレンの燃焼反応が進行し、ＥＤＣの選択性や収率が低下する等の問題があった。銅の移動、昇華を抑制する為に、さらには選択性を向上させるためにアルカリ金属、アルカリ土類金属、希土類金属等を添加することが行われている。 Conventionally, a catalyst in which a metal salt is supported on a carrier such as porous alumina, silica alumina, and clay is generally used for chlorination of an aliphatic hydrocarbon by an oxychlorination method. In particular, for production of EDC by oxychlorination of ethylene, a fluidized bed catalyst in which cupric chloride is supported on an alumina support by an impregnation method has been used industrially. However, in this catalyst, copper, which is an active component, moves or sublimes, causing a decrease in activity and a decrease in fluidity. As a result, the temperature distribution of the catalyst layer becomes non-uniform, and the combustion reaction of ethylene proceeds at a high temperature part. There was a problem that the selectivity and yield of EDC were lowered. In order to suppress copper migration and sublimation, addition of an alkali metal, an alkaline earth metal, a rare earth metal, or the like is performed in order to improve selectivity.
一方、担体成分と活性成分を同時に沈殿（以下、共沈法ということがある。）させ、噴霧乾燥して得た触媒が知られている（特許文献１参照）。さらに、共沈法で調合して得た触媒にアルカリ金属、アルカリ土類金属、希土類金属等を担持した触媒も知られている（特許文献２〜４参照）。
しかしながら、これらの触媒によっては、前記流動性の問題、活性および選択性の低下する問題は完全には解決されていない。
On the other hand, a catalyst obtained by simultaneous precipitation (hereinafter sometimes referred to as coprecipitation method) of a carrier component and an active component and spray drying is known (see Patent Document 1). Furthermore, a catalyst in which an alkali metal, an alkaline earth metal, a rare earth metal or the like is supported on a catalyst prepared by coprecipitation is also known (see Patent Documents 2 to 4).
However, according to these catalysts, the problem of fluidity, the problem of lowering the activity and selectivity are not completely solved.
本願出願人は、アルミナ源としてあらかじめ調製した擬ベーマイトアルミナスラリーを用い、これに銅等の活性成分、アルカリ、アルカリ土類、希土類等の助触媒成分を加え、噴霧乾燥して得られる触媒は前記流動性の低下が少なく、かつ、高い活性と選択性を示すことを開示している（特許文献５、６参照）。
しかしながら、前記した触媒は、触媒の製造にハロゲン（塩素）を大量に使用するために触媒製造装置の腐蝕が問題となることがあり、例えば、ステンレス鋼等の腐蝕により製造装置を損壊させ、ハロゲンガスや調合物を系外へ漏出する虞があった。他方、原料のハロゲン（塩素）化合物の使用量を低減したり、硫酸塩等の他の酸塩を使用すると活性や選択性、流動性等が不充分となることがあった。
The applicant of the present application uses a pseudo boehmite alumina slurry prepared in advance as an alumina source, and adds an active component such as copper, a promoter component such as alkali, alkaline earth, rare earth, etc. It discloses that there is little decrease in fluidity and high activity and selectivity (see Patent Documents 5 and 6).
However, since the catalyst described above uses a large amount of halogen (chlorine) in the production of the catalyst, corrosion of the catalyst production apparatus may cause a problem. For example, the production apparatus is damaged by corrosion of stainless steel or the like. There was a risk of leaking gases and preparations out of the system. On the other hand, or to reduce the amount of halogen (chlorine) the starting compounds of, other acid salt Using activity and selectivity of such sulfate, was sometimes flowability becomes insufficient.
更に、本願出願人は、アルミナ源としてあらかじめ調製した擬ベーマイトアルミナスラリーと硝酸第２銅を用いて触媒を調製すると、前記触媒製造装置の腐蝕の問題が無くなるとともに、得られた触媒は、従来と同様に高い活性と選択性を示すことを開示している（特許文献７参照）。
しかしながら、ＥＤＣのさらなる効率的、経済的生産の為に、さらに高活性、高選択性の触媒が求められている。
Further, the applicant of the present application prepared the catalyst using the pseudo boehmite alumina slurry prepared beforehand as the alumina source and cupric nitrate, and the corrosion problem of the catalyst production apparatus was eliminated. discloses that show selectivity with similarly high activity (see Patent Document 7).
However, a further highly active and highly selective catalyst is required for more efficient and economical production of EDC.
本発明者等は、鋭意検討した結果、アルミナ源としてあらかじめ調製した擬ベーマイトアルミナスラリーを用い、これに所定量のカルボン酸および／またはヒドロキシカルボン酸を加えて熟成し、これに硝酸第２銅を用いて触媒を調製すると前記触媒製造装置の腐蝕の問題が無くなると共に、得られた触媒が高い活性と選択性を示すことを見出して本発明を完成するに到った。
As a result of diligent investigations, the present inventors have used a pseudo boehmite alumina slurry prepared in advance as an alumina source, ripened by adding a predetermined amount of carboxylic acid and / or hydroxycarboxylic acid, and cupric nitrate was added thereto. When the catalyst was prepared using the catalyst, the problem of corrosion of the catalyst production apparatus was eliminated, and the obtained catalyst showed high activity and selectivity , and the present invention was completed.
本発明は、アルミナと銅と、必要に応じてアルカリ土類、アルカリ、希土類とを含んでなり、ハロゲン（塩素）の含有量が少なく、高活性で高選択性のオキシクロリネーション用触媒の製造方法を提供することを目的としている。 The present invention relates to the production of a highly active and highly selective catalyst for oxychlorination comprising alumina, copper and, if necessary, alkaline earth, alkali, rare earth, low halogen (chlorine) content. It aims to provide a method.
本発明は、アルミナと銅とを含んでなり、銅の含有量がＣｕＯとして５〜２０重量％の範囲にあり、ハロゲンの含有量が５重量％以下であるオキシクロリネーション用触媒の製造方法において、下記の工程（ａ）〜（ｄ）からなることを特徴とするものである。
（ａ）擬ベーマイトアルミナスラリーにカルボン酸および／またはヒドロキシカルボン酸を加えて熟成する工程
（ｂ）さらに酸と硝酸第二銅水溶液とを添加して噴霧乾燥用スラリーを調製する工程
（ｃ）前記スラリーを噴霧乾燥する工程
（ｄ）（ｃ）工程で得られた微粒子を焼成する工程
The present invention relates to a method for producing an oxychlorination catalyst comprising alumina and copper, wherein the copper content is in the range of 5 to 20% by weight as CuO, and the halogen content is 5% by weight or less. The method comprises the following steps (a) to (d).
(A) Step of aging by adding carboxylic acid and / or hydroxycarboxylic acid to pseudo boehmite alumina slurry (b) Step of further adding acid and cupric nitrate aqueous solution to prepare slurry for spray drying (c) Steps of spray drying slurry (d) Step of firing fine particles obtained in steps (c)
前記カルボン酸および／またはヒドロキシカルボン酸が、蟻酸、酢酸、蓚酸、アクリル酸（不飽和カルボン酸）、グルコン酸、リンゴ酸、シュウ酸、マロン酸、コハク酸、グルタール酸、アジピン酸、セバシン酸、マレイン酸、フマル酸、フタル酸、α−乳酸、β−乳酸、γ−ヒドロキシ吉草酸、グリセリン酸、酒石酸、クエン酸、トロパ酸、ベンジル酸から選ばれる１種または２種以上であることが好ましい。
前記工程（ａ）において、カルボン酸および／またはヒドロキシカルボン酸のモル数（ＭC）と擬ベーマイトアルミナスラリーのＡl2Ｏ3のモル数（ＭA）とのモル比（ＭC）／（ＭA）が０．００５〜０．１の範囲にあることが好ましい。
前記噴霧乾燥用スラリーのｐＨが３〜５の範囲にあることが好ましい。
The carboxylic acid and / or hydroxycarboxylic acid is formic acid, acetic acid, succinic acid, acrylic acid (unsaturated carboxylic acid), gluconic acid, malic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, sebacic acid, It is preferably one or more selected from maleic acid, fumaric acid, phthalic acid, α-lactic acid, β-lactic acid, γ-hydroxyvaleric acid, glyceric acid, tartaric acid, citric acid, tropic acid, and benzylic acid. .
In the step (a), the molar ratio (M C ) / (M of the number of moles of carboxylic acid and / or hydroxycarboxylic acid (M C ) and the number of moles of Al 2 O 3 (M A ) of the pseudoboehmite alumina slurry. A ) is preferably in the range of 0.005 to 0.1.
The pH of the spray drying slurry is preferably in the range of 3-5.
前記工程（ｂ）でさらにアルカリ土類塩水溶液を添加することにより、アルカリ土類の含有量が酸化物（ＭＯ：Ｍはアルカリ土類元素を示す）として０．１〜６重量％の範囲にあるオキシクロリネーション用触媒を得ることが好ましい。
前記アルカリ土類がマグネシウムであることが好ましい。
By further adding an alkaline earth salt aqueous solution in the step (b), the alkaline earth content falls within the range of 0.1 to 6% by weight as an oxide (MO: M represents an alkaline earth element). It is preferred to obtain some oxychlorination catalyst.
It is preferable that the alkaline earth is magnesium.
前記工程（ｂ）で、さらに希土類塩水溶液を添加することにより、希土類の含有量が酸化物（ＲＥ2Ｏ3：ＲＥは希土類元素を示す）として０.１〜６重量％の範囲にあるオキシクロリネーション用触媒を得ることが好ましい。 In the step (b), by further adding a rare earth salt aqueous solution, the content of the rare earth is in the range of 0.1 to 6% by weight as an oxide (RE 2 O 3 : RE represents a rare earth element). It is preferable to obtain a catalyst for chlorination.
前記工程（ｂ）で、さらにアルカリ塩水溶液を添加することにより、アルカリの含有量が酸化物（Ｎ2Ｏ：Ｎはアルカリ元素を示す）として０.１〜３重量％の範囲にあるオキシクロリネーション用触媒を得ることが好ましい。
前記アルカリがカリウムであることが好ましい。
In the step (b), an alkali salt aqueous solution is further added so that the alkali content is in the range of 0.1 to 3% by weight as an oxide (N 2 O: N represents an alkali element). It is preferable to obtain a catalyst for nation.
It is preferable that the alkali is potassium.
本発明によれば、触媒製造装置の腐蝕、ハロゲンガス等の大気への飛散を低減できるとともに、ハロゲンの含有量が少なく、このため活性、ＥＤＣ選択性、エチレン燃焼抑制特性、長期にわたる安定した流動性、耐摩耗性等に優れる触媒を製造することができる。
According to the present invention, the corrosion of the catalyst production apparatus, the scattering of halogen gas and the like to the atmosphere can be reduced, and the halogen content is low, so that the activity, EDC selectivity, ethylene combustion suppression characteristics, and stable flow over a long period of time are achieved. A catalyst having excellent properties, wear resistance and the like can be produced.
本発明に係るオキシクロリネーション用触媒の製造方法は、下記の工程（ａ）〜（ｄ）からなることを特徴としている。
（ａ）擬ベーマイトアルミナスラリーにカルボン酸および／またはヒドロキシカルボン酸を加えて熟成する工程
（ｂ）さらに酸と硝酸第二銅水溶液とを添加して噴霧乾燥用スラリーを調製する工程
（ｃ）前記スラリーを噴霧乾燥する工程
（ｄ）（ｃ）工程で得られた微粒子を焼成する工程
The method for producing an oxychlorination catalyst according to the present invention is characterized by comprising the following steps (a) to (d).
(A) Step of aging by adding carboxylic acid and / or hydroxycarboxylic acid to pseudo boehmite alumina slurry (b) Step of further adding acid and cupric nitrate aqueous solution to prepare slurry for spray drying (c) Steps of spray drying slurry (d) Step of firing fine particles obtained in steps (c)
工程（ａ）
本発明にはアルミナ源として擬ベーマイトアルミナを用いる。擬ベーマイトアルミナ（Ａl2Ｏ3・ｎＨ2Ｏ、ｎ：０.５〜２.５）は結晶性アルミナ水和物の一種で、通常、繊維状の一次粒子が束になった繊維状の二次粒子である。
本発明に用いる擬ベーマイトアルミナの一次粒子の大きさは、平均長さ（Ｌ1）が１〜１０ｎｍの範囲にあり、平均幅（Ｗ1）が０.５〜３ｎｍの範囲にあることが好ましい。
一次粒子の平均長さ（Ｌ1）が１ｎｍ未満の場合は、アルミナの溶解が進みすぎて最終的に得られる触媒の細孔容積および比表面積が小さくなるとともに活性が不充分となる。一次粒子の平均長さ（Ｌ1）が１０ｎｍを越えると得られる触媒の嵩密度が低下したり、耐摩耗性が不充分となる。
Step (a)
In the present invention, pseudoboehmite alumina is used as the alumina source. Pseudo-boehmite alumina (Al 2 O 3 .nH 2 O, n: 0.5 to 2.5) is a kind of crystalline alumina hydrate, and is usually a fibrous two-dimensional bundle of fibrous primary particles. Next particle.
The primary particles of pseudoboehmite alumina used in the present invention preferably have an average length (L 1 ) in the range of 1 to 10 nm and an average width (W 1 ) in the range of 0.5 to 3 nm. .
When the average length (L 1 ) of the primary particles is less than 1 nm, the dissolution of the alumina proceeds so much that the pore volume and specific surface area of the catalyst finally obtained become small and the activity becomes insufficient. When the average length (L 1 ) of the primary particles exceeds 10 nm, the bulk density of the resulting catalyst is lowered or the wear resistance is insufficient.
一次粒子の平均幅（Ｗ1）が０.５ｎｍ未満の場合は、平均長さ（Ｌ1）が１ｎｍ未満の場合と同様にアルミナの溶解が進みすぎて最終的に得られる触媒の細孔容積および比表面積が小さくなるとともに活性が不充分となる。
一次粒子の平均幅（Ｗ1）が３ｎｍを越えると、得られる触媒の嵩密度が低下したり、耐摩耗性が不充分となる。
このような 一次粒子の大きさは走査型電子顕微鏡写真を撮影して観察することによって求めることができる。
When the average width (W 1 ) of the primary particles is less than 0.5 nm, the pore volume of the catalyst finally obtained due to excessive dissolution of alumina as in the case where the average length (L 1 ) is less than 1 nm. And the specific surface area becomes smaller and the activity becomes insufficient.
When the average width (W 1 ) of the primary particles exceeds 3 nm, the bulk density of the resulting catalyst is lowered or the wear resistance is insufficient.
The size of such primary particles can be determined by taking and observing a scanning electron micrograph.
本発明に用いる擬ベーマイトアルミナとしては、前記の一次粒子の条件を満たすものであれば従来公知の擬ベーマイトアルミナを用いることができる。
このような擬ベーマイトアルミナは、例えば、アルカリ性アルミニウム塩水溶液と酸性物質とを反応させ、必要に応じて洗浄、熟成等することによって得ることができる。さらに具体的には、所望の濃度範囲のアルミン酸ナトリウム水溶液と硫酸アルミニウム水溶液とを所望の量比で反応させ、希アンモニア水を掛け水等して洗浄し、必要に応じて熟成することによって得ることができる。
As the pseudo boehmite alumina used in the present invention, conventionally known pseudo boehmite alumina can be used as long as it satisfies the conditions of the primary particles.
Such pseudo boehmite alumina can be obtained, for example, by reacting an alkaline aluminum salt aqueous solution with an acidic substance, and washing and aging as necessary. More specifically, it is obtained by reacting a sodium aluminate aqueous solution and an aluminum sulfate aqueous solution in a desired concentration range at a desired quantitative ratio, washing with diluted ammonia water, etc., and aging as necessary. be able to.
本発明では、前記のようにして得られる洗浄後の擬ベーマイトアルミナスラリーにカルボン酸および／またはヒドロキシカルボン酸を加えて熟成する。
カルボン酸としては、蟻酸、酢酸、蓚酸、アクリル酸（不飽和カルボン酸）、グルコン酸等のモノカルボン酸、リンゴ酸、シュウ酸、マロン酸、コハク酸、グルタール酸、アジピン酸、セバシン酸、マレイン酸、フマル酸、フタル酸等の多価カルボン酸等が挙げられる。
また、ヒドロキシカルボン酸（１分子内にカルボキシル基および水酸基を有する）としては、α−乳酸、β−乳酸、γ−ヒドロキシ吉草酸、グリセリン酸、酒石酸、クエン酸、トロパ酸、ベンジル酸等が挙げられる。これらカルボン酸および／またはヒドロキシカルボン酸は水溶液で添加することが好ましい。
In the present invention, aging is performed by adding carboxylic acid and / or hydroxycarboxylic acid to the washed pseudo-boehmite alumina slurry obtained as described above.
Carboxylic acids include monocarboxylic acids such as formic acid, acetic acid, succinic acid, acrylic acid (unsaturated carboxylic acid), gluconic acid, malic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, sebacic acid, maleic acid Examples thereof include polyvalent carboxylic acids such as acid, fumaric acid and phthalic acid.
Examples of the hydroxycarboxylic acid (having a carboxyl group and a hydroxyl group in one molecule) include α-lactic acid, β-lactic acid, γ-hydroxyvaleric acid, glyceric acid, tartaric acid, citric acid, tropic acid, and benzylic acid. It is done. These carboxylic acids and / or hydroxycarboxylic acids are preferably added in an aqueous solution.
カルボン酸および／またはヒドロキシカルボン酸のモル数（ＭC）と擬ベーマイトアルミナスラリーのＡl2Ｏ3のモル数（ＭA）とのモル比（ＭC）／（ＭA）が０．００５〜０．１、さらには０．０１０〜０．０５の範囲にあることが好ましい。
モル比（ＭC）／（ＭA）が０．００５未満の場合は：カルボン酸および／またはヒドロキシルカルボン酸の効果が薄く、触媒の比表面積向上効果が得られない場合があり、活性、選択性の向上効果が充分得られない場合がある。
モル比（ＭC）／（ＭA）が０．１を越えると、触媒の初期活性は高いものの、容易に失活するとともに選択性が低下する傾向があり、コストパフォーマンスが低下する。
The molar ratio (M C ) / (M A ) between the number of moles of carboxylic acid and / or hydroxycarboxylic acid (M C ) and the number of moles of Al 2 O 3 (M A ) in the pseudoboehmite alumina slurry is 0.005 It is preferable that it exists in the range of 0.1, Furthermore, 0.010-0.05.
When the molar ratio (M C ) / (M A ) is less than 0.005: the effect of the carboxylic acid and / or hydroxyl carboxylic acid is weak and the specific surface area improvement effect of the catalyst may not be obtained. The effect of improving the properties may not be sufficiently obtained.
When the molar ratio (M C ) / (M A ) exceeds 0.1, the initial activity of the catalyst is high, but it tends to be easily deactivated and the selectivity tends to decrease, resulting in a decrease in cost performance.
本発明に用いる擬ベーマイトアルミナスラリーの濃度は、カルボン酸および／またはヒドロキシカルボン酸を添加して静置または撹拌しながら熟成できれば特に制限はないが、後述する噴霧乾燥するスラリーの濃度調整を再度必要としない点で、概ねＡl2Ｏ3として２〜２０重量％、さらには５〜１８重量％の範囲にあることが好ましい。
擬ベーマイトアルミナスラリーの濃度がＡl2Ｏ3として２重量％未満の場合は、噴霧乾燥用スラリーの濃度が低くなり、得られる微小球状粒子の微細粒子が多くなり、流動性が低下したり、触媒をサイクロンで捕捉できないために触媒の損失が多くなる。
擬ベーマイトアルミナスラリーの濃度がＡl2Ｏ3として２０重量％を越えると、噴霧乾燥用スラリーの濃度が高くなりすぎて粘度が高くなり噴霧乾燥が困難な場合があり、噴霧乾燥できたとしても活性成分の分散性が不充分となり、得られる触媒の性能が不充分となったり、耐摩耗性や嵩比重（ＣＢＤ）が低下することがある。
The concentration of the pseudo boehmite alumina slurry used in the present invention is not particularly limited as long as carboxylic acid and / or hydroxycarboxylic acid can be added and ripened while standing or stirring, but it is necessary to adjust the concentration of the slurry for spray drying described later again In view of this, it is preferable that the Al 2 O 3 content is generally in the range of 2 to 20% by weight, more preferably 5 to 18% by weight.
When the concentration of the pseudo boehmite alumina slurry is less than 2% by weight as Al 2 O 3 , the concentration of the slurry for spray drying becomes low, the fine particles of the resulting fine spherical particles increase, the fluidity decreases, and the catalyst Since the cyclone cannot be captured by the cyclone, the catalyst loss increases.
If the concentration of the pseudo boehmite alumina slurry exceeds 20% by weight as Al 2 O 3 , the concentration of the slurry for spray drying becomes too high and the viscosity becomes so high that spray drying may be difficult. Insufficient dispersibility of the components may result in insufficient performance of the resulting catalyst, and wear resistance and bulk specific gravity (CBD) may be reduced.
熟成は、５０〜１００℃、好ましくは６０〜９５℃で、撹拌下または静置下で行うことが好ましい。あるいは、温度を昇温、または降温する際のみ撹拌することもできる。
熟成温度が５０℃未満の場合は、カルボン酸および／またはヒドロキシカルボン酸と擬ベーマイトの反応が不十分となり、触媒の比表面積向上効果が得られない場合があり、活性、選択性の向上効果が充分得られない場合がある。熟成温度が１００℃を越えると、擬ベーマイトの結晶が成長してしまい、触媒の比表面積が低下する場合があり、活性、選択性の向上効果が得られない場合がある。
The aging is preferably performed at 50 to 100 ° C., preferably 60 to 95 ° C. with stirring or standing. Alternatively, stirring can be performed only when the temperature is raised or lowered.
When the aging temperature is less than 50 ° C., the reaction between the carboxylic acid and / or hydroxycarboxylic acid and pseudoboehmite becomes insufficient, and the effect of improving the specific surface area of the catalyst may not be obtained. It may not be obtained sufficiently. When the aging temperature exceeds 100 ° C., pseudoboehmite crystals grow and the specific surface area of the catalyst may decrease, and the effect of improving activity and selectivity may not be obtained.
工程（ｂ）
工程（ａ）で得られた擬ベーマイトアルミナスラリーに酸を加える。酸としては塩酸、硝酸、硫酸等の鉱酸の他、酢酸等の有機酸を用いることができる。なかでも硝酸は擬ベーマイトアルミナスラリーの凝集粒子（二次粒子）を均一化することができ、耐摩耗性や嵩比重（ＣＢＤ）の高い触媒を得ることができる。同時に、触媒製造時に製造装置を腐蝕することがなく、ハロゲン含有量が少ない触媒を得ることができる。
Step (b)
An acid is added to the pseudo boehmite alumina slurry obtained in step (a). As the acid, in addition to mineral acids such as hydrochloric acid, nitric acid and sulfuric acid, organic acids such as acetic acid can be used. Among these, nitric acid can make the aggregated particles (secondary particles) of the pseudo boehmite alumina slurry uniform, and a catalyst having high wear resistance and high bulk specific gravity (CBD) can be obtained. At the same time, a catalyst having a low halogen content can be obtained without corroding the production apparatus during catalyst production.
酸の添加量はスラリー中のＡl2Ｏ3１モル当たり０.００１〜０.１モル、さらには０.００５〜０.０５モルの範囲にあることが好ましい。
酸の添加量が０.００１モル未満の場合は、擬ベーマイトアルミナスラリーの凝集粒子（二次粒子）が不均一なままであり、得られる触媒の耐摩耗性や嵩比重（ＣＢＤ）が低下することがある。また、擬ベーマイトスラリーのｐＨが６を越えることがあり、ついで添加する銅成分や、必要に応じて添加するアルカリ土類、希土類成分の多くが噴霧乾燥前に沈着し、アルミナ担体上に各成分を高分散沈着させることができず、活性、エチレンの酸化抑制効果および長期流動性等が低下する傾向がある。酸の添加量が０.１モルを越えると、多くの擬ベーマイトアルミナが酸と反応して溶解し、得られる触媒の比表面積や細孔容積が低下し、活性が不充分となる傾向にある。
なお、酸は通常、濃度が１０〜３５重量％の酸が用いられる。このときの擬ベーマイトスラリーのｐＨは概ね２〜６、さらには３〜５の範囲にあることが好ましい。
The amount of acid added is preferably in the range of 0.001 to 0.1 mole, more preferably 0.005 to 0.05 mole, per mole of Al 2 O 3 in the slurry.
When the amount of acid added is less than 0.001 mol, the aggregated particles (secondary particles) of the pseudo boehmite alumina slurry remain non-uniform, and the wear resistance and bulk specific gravity (CBD) of the resulting catalyst are reduced. Sometimes. In addition, the pH of the pseudo boehmite slurry may exceed 6, and then most of the copper component to be added, alkaline earth and rare earth components to be added as necessary are deposited before spray drying, and each component is deposited on the alumina support. Cannot be highly dispersed and deposited, and the activity, the effect of inhibiting the oxidation of ethylene, and long-term fluidity tend to decrease. If the amount of acid added exceeds 0.1 mol, many pseudoboehmite aluminas react with the acid and dissolve, the specific surface area and pore volume of the resulting catalyst tend to decrease, and the activity tends to be insufficient. .
The acid is usually an acid having a concentration of 10 to 35% by weight. The pH of the pseudo boehmite slurry at this time is preferably in the range of approximately 2 to 6, more preferably 3 to 5.
ついで、硝酸第二銅水溶液を添加する。
硝酸第二銅水溶液の使用量は最終的に得られる触媒中の銅の含有量が酸化物（ＣｕＯ）として５〜２０重量％、好ましくは１０〜１５重量％の範囲となるように用いる。
触媒中の銅の含有量が５重量％未満の場合は、活性が不充分となり、ＥＤＣの収率が低下する。触媒中の銅の含有量が２０重量％を越えると、原料エチレンの燃焼が顕著になり、ＥＤＣの収率が低下するとともに、銅が多すぎて触媒粒子の外部表面に移動したり、昇華し、流動性低下の原因となることがある。
Next, an aqueous cupric nitrate solution is added.
The cupric nitrate aqueous solution is used so that the copper content in the finally obtained catalyst is 5 to 20% by weight, preferably 10 to 15% by weight as an oxide (CuO).
When the content of copper in the catalyst is less than 5% by weight, the activity is insufficient and the yield of EDC is lowered. When the content of copper in the catalyst exceeds 20% by weight, the combustion of the raw material ethylene becomes remarkable, the EDC yield decreases, and there is too much copper to move to the external surface of the catalyst particles or sublimate. , May cause a decrease in fluidity.
工程（ｂ）では、必要に応じて、硝酸第二銅水溶液と同時にまたは硝酸第二銅水溶液を添加した後にアルカリ土類塩水溶液、希土類塩水溶液、アルカリ塩水溶液の少なくとも１種を添加することが好ましい。
アルカリ土類塩としてはマグネシウム、カルシウム、バリウム等の硝酸塩、塩酸塩、硫酸塩等が用いられるが、なかでも硝酸塩を用いた場合は触媒製造装置の腐蝕を低減でき、ハロゲン含有量が少ない触媒を得ることができる。特に硝酸マグネシウムを用いると、活性の低下がなく、耐摩耗性に優れた触媒を得ることができる。
In the step (b), if necessary, at least one of an alkaline earth salt aqueous solution, a rare earth salt aqueous solution, and an alkaline salt aqueous solution may be added simultaneously with the cupric nitrate aqueous solution or after the addition of the cupric nitrate aqueous solution. preferable.
As alkaline earth salts, nitrates, hydrochlorides, sulfates, etc. of magnesium, calcium, barium, etc. are used. Especially, when nitrates are used, corrosion of the catalyst production equipment can be reduced and a catalyst with low halogen content can be used. Obtainable. In particular, when magnesium nitrate is used, a catalyst excellent in wear resistance can be obtained without a decrease in activity.
アルカリ土類塩水溶液の使用量は最終的に得られる触媒中のアルカリ土類の含有量が０.１〜６重量％、好ましくは０．２〜４重量％の範囲となるように用いる。アルカリ土類の含有量が０.１重量％未満の場合は、得られる触媒の嵩密度、耐摩耗性が低下する傾向がある。アルカリ土類の含有量が６重量％を越えると、得られる触媒の細孔容積が低下し、活性が不充分となることがある。また、硝酸マグネシウムを用いる場合には、得られる触媒中のマグネシウムの含有量がＭｇＯとして０．２〜３．５重量％の範囲となるようにすることが好ましい。 The amount of the alkaline earth salt aqueous solution used is such that the content of the alkaline earth in the finally obtained catalyst is 0.1 to 6% by weight, preferably 0.2 to 4% by weight. When the content of alkaline earth is less than 0.1% by weight, the bulk density and wear resistance of the resulting catalyst tend to decrease. When the content of alkaline earth exceeds 6% by weight, the pore volume of the resulting catalyst is lowered, and the activity may be insufficient. When magnesium nitrate is used, it is preferable that the magnesium content in the resulting catalyst is in the range of 0.2 to 3.5% by weight as MgO.
希土類塩としては、ランタン、セリウム等の硝酸塩、塩酸塩、硫酸塩等が用いられるが、なかでも硝酸塩を用いた場合は触媒製造装置の腐蝕を低減でき、ハロゲン含有量が少なく、ＥＤＣの選択性に優れ、エチレンの燃焼を抑制することができる触媒を得ることができる。
希土類金属塩水溶液の使用量は最終的に得られる触媒中の希土類の含有量が０.１〜６重量％、好ましくは１〜５重量％の範囲となるように用いる。
希土類の含有量が０.１重量％未満の場合は、ＥＤＣの選択性が低下するとともに、エチレンの燃焼を抑制する効果が不充分となるためにＥＤＣの収率も低下する。希土類の含有量が６重量％を越えると、Ｃｌの反応率が低下しＥＤＣの収率が低下する。
As the rare earth salts, nitrates such as lanthanum and cerium, hydrochlorides, sulfates, etc. are used. In particular, when nitrates are used, the corrosion of the catalyst production apparatus can be reduced, the halogen content is low, and the selectivity of EDC is reduced. And a catalyst capable of suppressing the combustion of ethylene can be obtained.
The amount of the rare earth metal salt aqueous solution used is such that the rare earth content in the finally obtained catalyst is in the range of 0.1 to 6% by weight, preferably 1 to 5% by weight.
When the rare earth content is less than 0.1% by weight, the selectivity of EDC is lowered and the effect of suppressing the combustion of ethylene is insufficient, so that the yield of EDC is also lowered. If the rare earth content exceeds 6% by weight, the reaction rate of Cl decreases and the yield of EDC decreases.
アルカリ塩としては、ナトリウム、カリウム等の硝酸塩、塩酸塩、硫酸塩等が用いられるが、なかでも硝酸塩が好ましく、特に硝酸カリウムを用いた場合はハロゲン含有量が少なく、ＥＤＣの選択性に優れ、エチレンの燃焼を抑制することができる触媒を得ることができる。
アルカリ塩水溶液の使用量は最終的に得られる触媒中のアルカリの含有量が０.１〜３重量％、好ましくは０．５〜２重量％の範囲となるように用いる。アルカリの含有量が０.１重量％未満の場合は、エチレンの燃焼を抑制する効果が不充分となるためにＥＤＣの収率が低下する。アルカリの含有量が３重量％を越えると、Ｃｌの反応率が低下しＥＤＣの収率が低下する。
As the alkali salt, nitrates such as sodium and potassium, hydrochlorides, sulfates and the like are used. Among them, nitrates are preferable, and particularly when potassium nitrate is used, the halogen content is small, the selectivity of EDC is excellent, and ethylene is used. It is possible to obtain a catalyst capable of suppressing the combustion of NO.
The alkali salt aqueous solution is used so that the alkali content in the finally obtained catalyst is in the range of 0.1 to 3% by weight, preferably 0.5 to 2% by weight. When the alkali content is less than 0.1% by weight, the effect of suppressing the combustion of ethylene becomes insufficient, so that the yield of EDC is lowered. If the alkali content exceeds 3% by weight, the reaction rate of Cl decreases and the yield of EDC decreases.
各水溶液の濃度は特に制限はないが、通常１〜３０重量％の水溶液が用いられる。また、各水溶液の添加順序も特に制限はなく、アルカリ塩水溶液以外は混合水溶液として使用することもできる。
上記のようにして調製した噴霧乾燥用スラリーのｐＨは１．５〜５．５、さらには３〜５の範囲にあることが好ましい。ｐＨが１.５未満の場合は、擬ベーマイトアルミナの溶解が進みすぎているために得られる触媒の比表面積や細孔容積が低下し、活性が不充分となる傾向にある。ｐＨが５．５を越えると、高い割合で銅が噴霧乾燥前に水酸化物として沈殿するために、アルミナ担体上に銅成分を高分散沈着させることができず、活性や長期流動性が低下する傾向がある。
The concentration of each aqueous solution is not particularly limited, but a 1 to 30% by weight aqueous solution is usually used. Moreover, there is no restriction | limiting in particular in the addition order of each aqueous solution, It can also be used as mixed aqueous solution except alkali salt aqueous solution.
The pH of the slurry for spray drying prepared as described above is preferably in the range of 1.5 to 5.5, more preferably 3 to 5. If the pH is less than 1.5, the specific surface area and pore volume of the resulting catalyst are lowered due to the excessive dissolution of pseudoboehmite alumina, and the activity tends to be insufficient. When the pH exceeds 5.5, copper is precipitated as a hydroxide before spray drying at a high rate, so that the copper component cannot be highly dispersed and deposited on the alumina support, and the activity and long-term fluidity are reduced. Tend to.
また、噴霧乾燥用スラリーの濃度は固形分として５〜２５重量％、さらには１０〜２０重量％の範囲にあることが好ましい。濃度が５重量％未満の場合は、噴霧乾燥して得られる球状微粒子の平均粒子径が小さくなるとともに２０μｍ以下の微小粒子が増大することがあり、また水分が多いために噴霧乾燥の熱エネルギーを多く必要とし経済的でない。濃度が２５重量％を越えると、スラリーの粘度が高すぎて噴霧乾燥が困難となることがある。
なお、噴霧乾燥用スラリーは、必要に応じてホモジナイザー、コロイドミル等により乳化処理、均一化処理等を行ってもよい。
Moreover, it is preferable that the density | concentration of the slurry for spray drying exists in the range of 5-25 weight% as solid content, and also 10-20 weight%. When the concentration is less than 5% by weight, the average particle size of the spherical fine particles obtained by spray drying may decrease, and the fine particles of 20 μm or less may increase. Needs a lot and is not economical. If the concentration exceeds 25% by weight, the viscosity of the slurry may be too high and spray drying may be difficult.
Note that the slurry for spray drying may be subjected to an emulsification treatment, a homogenization treatment, or the like using a homogenizer, a colloid mill, or the like, if necessary.
工程（ｃ）
工程（ｂ）で得た噴霧乾燥用スラリーをついで噴霧乾燥する。噴霧乾燥する方法としては、従来公知のオキシクロリネーション用流動触媒と同様に微小球状の流動触媒が得られれば特に制限はないが、例えば熱風気流中にディスク回転式、ノズル式等の種々の噴霧乾燥機を用いることができる。
このとき、熱風気流温度は１５０〜５００℃、さらには２００〜３５０℃の範囲にあることが好ましい。熱風気流温度が１５０℃未満の場合は、乾燥が不充分となることがある。熱風気流温度が５００℃を越えると、乾燥が急激に起こるために、活性成分や助触媒成分が粒子表面に偏在することがある。
Step (c)
The spray drying slurry obtained in step (b) is then spray dried. The spray drying method is not particularly limited as long as a microspherical fluid catalyst can be obtained in the same manner as a conventionally known fluid catalyst for oxychlorination. For example, various sprays such as a disk rotary type and a nozzle type are used in a hot air stream. A dryer can be used.
At this time, the hot air stream temperature is preferably in the range of 150 to 500 ° C, more preferably 200 to 350 ° C. When the hot air flow temperature is less than 150 ° C., drying may be insufficient. When the hot air flow temperature exceeds 500 ° C., drying occurs rapidly, so that active components and promoter components may be unevenly distributed on the particle surface.
噴霧乾燥して得られる微小球状粒子は、平均粒子径が５０〜８０μｍ、さらには５５〜７５μｍの範囲にあることが好ましい。平均粒子径が５０μｍ未満の場合は、後述する焼成工程で焼成して得られる触媒の平均粒子径が４０μｍ未満となることがあり、充分な流動性が得られなかったり、触媒の損失が増加することがある。微小球状粒子の平均粒子径が８０μｍを越える場合は、焼成工程で焼成して得られる触媒の平均粒子径が７５μｍを越えることがあり、平均粒子径が小さい場合と同様に充分な流動性が得られないことがある。 The fine spherical particles obtained by spray drying preferably have an average particle size in the range of 50 to 80 μm, more preferably 55 to 75 μm. When the average particle size is less than 50 μm, the average particle size of the catalyst obtained by calcination in the calcination step described later may be less than 40 μm, and sufficient fluidity may not be obtained or the loss of the catalyst will increase. Sometimes. When the average particle size of the fine spherical particles exceeds 80 μm, the average particle size of the catalyst obtained by calcination in the calcination step may exceed 75 μm, and sufficient fluidity can be obtained as in the case where the average particle size is small. It may not be possible.
また、微小球状粒子の粒子径分布は、概ね正規分布しており、粒子径が３０μｍ未満の微粒子が１０重量％以下であることが好ましく、粒子径が９０μｍを越える粒子が２０重量％以下であることが好ましい。なお、必要に応じてさらに分級することもできる。
上記した平均粒子径、粒子径分布は、例えばマイクロメッシュシーブ法によって求めることができる。
The particle size distribution of the microspherical particles is generally a normal distribution, and the fine particles having a particle size of less than 30 μm are preferably 10% by weight or less, and the particles having a particle size exceeding 90 μm are 20% by weight or less. It is preferable. Further classification can be performed as necessary.
The above-mentioned average particle size and particle size distribution can be determined by, for example, a micromesh sieve method.
工程（ｄ）
噴霧乾燥して得た微小球状粒子は、ついで焼成することによってオキシクロリネーション用触媒を得ることができる。
このとき、焼成温度は３５０〜８５０℃、特に５００〜７００℃の範囲にあることが好ましい。焼成温度が３５０℃未満の場合は、擬ベーマイトアルミナの脱水および結晶化が不充分となり、また活性成分や助触媒成分との結合が不充分となるためか活性および選択性が不充分となる。焼成温度が８５０℃を越えると、活性成分である銅が完全に酸化物化し活性が不充分となる。
焼成時間は焼成温度によって変えることができ、特に限定されないが、概ね０.１〜２４時間の範囲である。
Step (d)
The fine spherical particles obtained by spray drying can then be calcined to obtain an oxychlorination catalyst.
At this time, the firing temperature is preferably in the range of 350 to 850 ° C, particularly 500 to 700 ° C. When the calcination temperature is less than 350 ° C., the dehydration and crystallization of the pseudo boehmite alumina are insufficient, and the activity and selectivity are insufficient due to insufficient bonding with the active component and the promoter component. When the firing temperature exceeds 850 ° C., copper as the active component is completely oxidized and the activity becomes insufficient.
The firing time can be changed depending on the firing temperature and is not particularly limited, but is generally in the range of 0.1 to 24 hours.
このようにして、本発明に係るオキシクロリネーション用触媒を得ることができる。
得られたオキシクロリネーション用触媒は、銅の含有量が酸化物（ＣｕＯ）として５〜２０重量％の範囲にあり、アルカリ土類の含有量が酸化物として０.１〜６重量％の範囲にあり、アルカリの含有量が酸化物として０.１〜３重量％の範囲にあり、希土類の含有量が酸化物として０．１〜６重量％の範囲にあり、アルミナの含有量は概ね６０〜８５重量％の範囲にある。また、触媒中の塩素の含有量は５重量％以下となる。
In this way, the oxychlorination catalyst according to the present invention can be obtained.
The obtained catalyst for oxychlorination has a copper content in the range of 5 to 20% by weight as an oxide (CuO), and an alkaline earth content in the range of 0.1 to 6% by weight as an oxide. The alkali content is in the range of 0.1 to 3% by weight as the oxide, the rare earth content is in the range of 0.1 to 6% by weight as the oxide, and the alumina content is approximately 60%. It is in the range of -85% by weight. Further, the chlorine content in the catalyst is 5% by weight or less.
本発明方法によって得られたオキシクロリネーション用触媒は、平均粒子径が４０〜７５μｍの範囲にある。また、触媒の粒子径分布は、概ね正規分布しており、粒子径が３０μｍ未満の微粒子が１０重量％以下であり、粒子径が９０μｍを越える粒子が２０重量％以下である。触媒の比表面積は１５０〜３００ｍ2／ｇの範囲にある。また、触媒の細孔容積は０．２５〜０．４０ｍｌ／ｇの範囲にある。
更に、触媒の嵩比重（ＣＢＤ）は０．９０〜１．２０ｇ／ｍｌの範囲にある。嵩比重（ＣＢＤ）は、所定の条件で加熱処理をした触媒を定量容器（例えば、メスシリンダー）へ一定量を充填し、充分に振動を加え最も細密に充填された状態での嵩体積を測定し、触媒の充填量を嵩体積で除して求めることができる。
以下、本発明を実施例により説明するが、本発明はこれら実施例に限定されるものではない。
The oxychlorination catalyst obtained by the method of the present invention has an average particle size in the range of 40 to 75 μm. Further, the particle size distribution of the catalyst is generally normal distribution, fine particles having a particle size of less than 30 μm are 10% by weight or less, and particles having a particle size exceeding 90 μm are 20% by weight or less. The specific surface area of the catalyst is in the range of 150 to 300 m 2 / g. The pore volume of the catalyst is in the range of 0.25 to 0.40 ml / g.
Further, the bulk specific gravity (CBD) of the catalyst is in the range of 0.90 to 1.20 g / ml. Bulk specific gravity (CBD) measures the bulk volume in a state in which a fixed amount of catalyst that has been heat-treated under specified conditions is filled into a quantitative container (for example, a graduated cylinder), and is vibrated sufficiently. Then, it can be obtained by dividing the amount of catalyst filling by the bulk volume.
EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited to these Examples.
［オキシクロリネーション用触媒(1)の調製］
噴霧乾燥用スラリー(1)の調製
濃度がＡｌ2Ｏ3として５重量％のアルミン酸ナトリウム水溶液７４．７ｋｇとＡｌ2Ｏ3に換算した濃度が２．５重量％の硫酸アルミニウム水溶液７４．７ｋｇとを混合してアルミナヒドロゲルスラリーを調製した。このとき、アルミナヒドロゲルスラリーの調合温度は６０℃、ｐＨは９．５であった。
ついで、アルミナヒドロゲルスラリーを濾過し、６０℃の純水を掛けて洗浄し、Ａｌ2Ｏ3としての濃度が１５重量％の擬ベーマイトアルミナスラリー５．６０ｋｇを得た。
ついで、グルコン酸０．０５ｋｇを純水０．３５ｋｇに溶解させた水溶液をアルミナヒドロゲルスラリーに添加し、８０℃で５Ｈｒ熟成した。擬ベーマイトアルミナスラリーの一部を乾燥し、走査型電子顕微鏡写真で観察した結果、平均長さ２．８ｎｍ、平均幅１ｎｍの繊維状一次粒子が束になった繊維状二次粒子であった。
[Preparation of Oxychlorination Catalyst (1)]
Preparation Concentration of spray drying the slurry (1) as the Al 2 O 3 5% strength by weight in terms of an aqueous sodium aluminate solution 74.7kg and Al 2 O 3 of 2.5 weight% of aluminum sulfate aqueous solution 74.7kg Were mixed to prepare an alumina hydrogel slurry. At this time, the preparation temperature of the alumina hydrogel slurry was 60 ° C., and the pH was 9.5.
Subsequently, the alumina hydrogel slurry was filtered and washed with pure water at 60 ° C. to obtain 5.60 kg of pseudo boehmite alumina slurry having a concentration of 15% by weight as Al 2 O 3 .
Next, an aqueous solution in which 0.05 kg of gluconic acid was dissolved in 0.35 kg of pure water was added to the alumina hydrogel slurry and aged at 80 ° C. for 5 hours. As a result of drying a part of the pseudo boehmite alumina slurry and observing with a scanning electron micrograph, it was fibrous secondary particles in which fibrous primary particles having an average length of 2.8 nm and an average width of 1 nm were bundled.
別途、純水０．４５ｋｇに濃度６３重量％の硝酸０．１０ｋｇを加えた希硝酸へ、濃度９７重量％の硝酸第二銅三水物（Cu(NO3)2・3H2O）０．３１ｋｇ、濃度９９重量％の硝酸ランタン六水物（La(NO3)3・6H2O）０．０４ｋｇ、濃度９８重量％の硝酸セリウム六水物（Ce(NO3)3・6H2O）０．０４ｋｇ及び濃度９８重量％の硝酸マグネシウム六水物（Mg(NO3)2・6H2O）０．２０ｋｇを溶解し、［ＣｕＯ＋Ｌａ２Ｏ３＋Ｃｅ２Ｏ３＋ＭｇＯ］としての濃度が１４重量％の混合硝酸塩水溶液１．１４ｋｇを調製した。
上記の洗浄した擬ベーマイトアルミナスラリーの温度を５０℃に調整した後、混合硝酸塩水溶液を混合した。
ついで、混合スラリーをホモジナイザーを用いて均一化処理して噴霧乾燥用スラリー(1)７．１４ｋｇを調製した。このときのスラリーのｐＨは３．５であった。
Separately, dilute nitric acid obtained by adding 0.10 kg of nitric acid having a concentration of 63 wt% to 0.45 kg of pure water to a cupric nitrate trihydrate (Cu (NO 3 ) 2 .3H 2 O) having a concentration of 97 wt%. 31 kg, 99 wt% lanthanum nitrate hexahydrate (La (NO 3 ) 3 · 6H 2 O) 0.04 kg, 98 wt% cerium nitrate hexahydrate (Ce (NO 3 ) 3 · 6H 2 O) 0.04 kg and 0.20 kg of magnesium nitrate hexahydrate (Mg (NO 3 ) 2 .6H 2 O) with a concentration of 98% by weight dissolved in 1.14 kg of a mixed nitrate aqueous solution having a concentration of 14% by weight as [CuO + La2O3 + Ce2O3 + MgO] Was prepared.
After adjusting the temperature of the washed pseudo-boehmite alumina slurry to 50 ° C., a mixed nitrate aqueous solution was mixed.
Next, the mixed slurry was homogenized using a homogenizer to prepare 7.14 kg of slurry for spray drying (1). The pH of the slurry at this time was 3.5.
噴霧乾燥
噴霧乾燥用スラリー(1)を温度２２０℃の熱風気流中に噴霧して微小球状粒子(1)を得た。
微小球状粒子(1)の平均粒子径は６５μｍであり、２０μｍ以下が１０重量％、１４９μｍ以上が５重量％であった。
The slurry (1) for spray drying and spray drying was sprayed into a hot air stream having a temperature of 220 ° C. to obtain microspherical particles (1).
The average particle size of the microspherical particles (1) was 65 μm, 10% by weight at 20 μm or less and 5% by weight at 149 μm or more.
焼成
ついで、微小球状粒子(1)を回転式焼成炉にて、６５０℃で０．５時間焼成してオキシクロリネーション用触媒(1)を調製した。
オキシクロリネーション用触媒(1)の平均粒子径、ＣＢＤ、アルミナの結晶形、組成については、以下に述べる実施例、比較例と共に表１に示した。
Firing then, spherical particles of (1) in a rotary calciner to prepare a catalyst for oxychlorination (1) was calcined 0.5 hours at 650 ° C..
The average particle diameter, CBD, crystal form of alumina, and composition of the oxychlorination catalyst (1) are shown in Table 1 together with Examples and Comparative Examples described below.
［評価］
耐摩耗性
特許７３７，４２９号公報に記載の方法に準拠し、触媒充填量５０ｇ、ノズル径０.４０６ｍｍφ、空気流量０.４２５ｍ3／時間の条件で流動させ、流動開始後５〜２０時間の１５時間に、流動層容器から飛散して回収された微粒子の重量割合（％）を表示した。
触媒性能評価
次の（１）活性評価と（２）流動性評価を行い、評価結果を以下に述べる実施例、比較例と共に表１に示した。
[Evaluation]
In accordance with the method described in Japanese Patent No. 737,429, abrasion resistance , the catalyst was flowed under the conditions of a catalyst filling amount of 50 g, a nozzle diameter of 0.406 mmφ, and an air flow rate of 0.425 m 3 / hour. The weight percentage (%) of the fine particles scattered and collected from the fluidized bed container in 15 hours was displayed.
Catalyst performance evaluation The following (1) activity evaluation and (2) fluidity evaluation were performed, and the evaluation results are shown in Table 1 together with Examples and Comparative Examples described below.
（１）活性評価
固定流動床式反応器を用い、これにオキシクロリネーション用触媒(1)を５ｇ充填し、温度２２０℃で、窒素ガスを２８.８ｍｌ／ｍｉｎで供給しながら流動化させ、ついで窒素ガスに代えて反応用混合ガス（エチレン３９.２ｖｏｌ％、塩酸４６.１ｖｏｌ％、酸素１４.７ｖｏｌ％）を６２.５ｍｌ／ｍｉｎで供給して反応を行った。このとき、ＷＨＳＶ＝７５０(L/Hr./kg Cat.)であった。
生成ガスをガスクロマトグラフにて分析し、次式により活性、選択性、収率および燃焼性を計算した。
・活性: 塩酸転化率＝（供給塩酸−未反応塩酸）／供給塩酸Ｘ１００（モル％）
・選択性: EDC選択率＝ＥＤＣの実生成量／理論的ＥＤＣ生成量×１００（モル％）
・収率（塩酸基準）:ＥＤＣ収率＝塩酸転化率 ×ＥＤＣ選択率（モル％）
・燃焼性: エチレン燃焼率＝（ＣＯ＋ＣＯ2）モル数／Ｃ2Ｈ2モル数Ｘ１００（モル％）
(1) Activity evaluation Using a fixed fluidized bed reactor, 5 g of the catalyst for oxychlorination (1) is charged, fluidized while supplying nitrogen gas at 28.8 ml / min at a temperature of 220 ° C, Next, instead of nitrogen gas, a reaction gas mixture (ethylene 39.2 vol%, hydrochloric acid 46.1 vol%, oxygen 14.7 vol%) was supplied at 62.5 ml / min to carry out the reaction. At this time, WHSV = 750 (L / Hr. / Kg Cat.).
The product gas was analyzed with a gas chromatograph, and the activity, selectivity, yield and flammability were calculated according to the following equations.
Activity: Hydrochloric acid conversion rate = (feed hydrochloric acid−unreacted hydrochloric acid) / feed hydrochloric acid X100 (mol%)
Selectivity: EDC selectivity = actual production amount of EDC / theoretical EDC production amount × 100 (mol%)
Yield (based on hydrochloric acid): EDC yield = hydrochloric acid conversion rate × EDC selectivity (mol%)
・ Flammability: Ethylene combustion rate = (CO + CO 2 ) moles / C 2 H 2 moles X100 (mol%)
（２）流動性評価
前記反応中に、流動層下部温度と流動層上部温度との温度差（ΔＴ：℃）を測定し、以下の基準で評価した。
ΔＴが３℃未満で、良好な流動性を示した ： ◎
ΔＴが３℃以上、５℃未満で、比較的良好な流動性を示した： ○
ΔＴが５℃以上、７℃未満で、問題のない流動性を示した ： △
ΔＴが７℃以上で、流動性に問題があった ： ×
(2) Fluidity evaluation During the reaction, the temperature difference (ΔT: ° C) between the fluidized bed lower part temperature and the fluidized bed upper part temperature was measured and evaluated according to the following criteria.
ΔT was less than 3 ° C. and showed good fluidity: ◎
ΔT was 3 ° C. or higher and lower than 5 ° C. and showed relatively good fluidity: ○
ΔT was 5 ° C. or higher and lower than 7 ° C., showing no problem fluidity: Δ
ΔT was 7 ° C. or higher, and there was a problem with fluidity: ×
［オキシクロリネーション用触媒(2)の調製］
噴霧乾燥用スラリー(2)の調製
実施例１のアルミナヒドロゲルに添加するグルコン酸０．０５ｋｇ、純水０．３５ｋｇをグルコン酸０．０２ｋｇ、純水０．３８ｋｇに代えた以外は同様にして噴霧乾燥用スラリー(2)７．１４ｋｇを調製した。このときのスラリーのｐＨは３．５であった。
噴霧乾燥
噴霧乾燥用スラリー(2)を温度２２０℃の熱風気流中に噴霧して微小球状粒子(2)を得た。
微小球状粒子(2)の平均粒子径は６５μｍであり、２０μｍ以下が１０重量％、１４９μｍ以上が５重量％であった。
焼成
ついで、微小球状粒子(2)を回転式焼成炉にて、６５０℃で０．５時間焼成してオキシクロリネーション用触媒(2)を調製した。
[Preparation of Oxychlorination Catalyst (2)]
Preparation of slurry for spray drying (2) Spraying was carried out in the same manner except that 0.05 kg of gluconic acid and 0.35 kg of pure water added to the alumina hydrogel of Example 1 were replaced with 0.02 kg of gluconic acid and 0.38 kg of pure water. 7.14 kg of drying slurry (2) was prepared. The pH of the slurry at this time was 3.5.
The slurry (2) for spray drying and spray drying was sprayed into a hot air stream having a temperature of 220 ° C. to obtain microspherical particles (2).
The average particle size of the microspherical particles (2) was 65 μm, 10% by weight at 20 μm or less and 5% by weight at 149 μm or more.
Firing then, the spherical particles (2) in a rotary calciner to prepare a catalyst for oxychlorination (2) was calcined 0.5 hours at 650 ° C..
［オキシクロリネーション用触媒(3)の調製］
噴霧乾燥用スラリー(3)の調製
実施例１のアルミナヒドロゲルに添加するグルコン酸０．０５ｋｇ、純水０．３５ｋｇをグルコン酸０．０８ｋｇ、純水０．３２ｋｇに代えた以外は同様にして噴霧乾燥用スラリー(3)７．１４ｋｇを調製した。このときのスラリーのｐＨは３．３であった。
噴霧乾燥
噴霧乾燥用スラリー(3)を温度２２０℃の熱風気流中に噴霧して微小球状粒子(3)を得た。
微小球状粒子(3)の平均粒子径は６５μｍであり、２０μｍ以下が１０重量％、１４９μｍ以上が５重量％であった。
焼成
ついで、微小球状粒子(3)を回転式焼成炉にて、６５０℃で０．５時間焼成してオキシクロリネーション用触媒(3)を調製した。
[Preparation of Oxychlorination Catalyst (3)]
Preparation of slurry for spray drying (3) Spraying was carried out in the same manner except that 0.05 kg of gluconic acid and 0.35 kg of pure water added to the alumina hydrogel of Example 1 were replaced with 0.08 kg of gluconic acid and 0.32 kg of pure water. 7.14 kg of drying slurry (3) was prepared. At this time, the pH of the slurry was 3.3.
Spray drying slurry (3) was sprayed into a hot air stream at 220 ° C. to obtain fine spherical particles (3).
The average particle diameter of the microspherical particles (3) was 65 μm, and 10% by weight was 20 μm or less, and 5% by weight was 149 μm or more.
Firing then, the spherical particles (3) in a rotary calciner to prepare a catalyst for oxychlorination (3) was calcined 0.5 hours at 650 ° C..
噴霧乾燥用スラリー(4)の調製
［オキシクロリネーション用触媒(4)の調製］
実施例１のアルミナヒドロゲルに添加するグルコン酸０．０５ｋｇを９９．５％クエン酸０．０５ｋｇに代えた以外は同様にして噴霧乾燥用スラリー(4)７．１４ｋｇを調製した。このときのスラリーのｐＨは３．５であった。
噴霧乾燥
噴霧乾燥用スラリー(4)を温度２２０℃の熱風気流中に噴霧して微小球状粒子(4)を得た。
微小球状粒子(4)の平均粒子径は６５μｍであり、２０μｍ以下が１０重量％、１４９μｍ以上が５重量％であった。
焼成
ついで、微小球状粒子(4)を回転式焼成炉にて、６５０℃で０．５時間焼成してオキシクロリネーション用触媒(4)を調製した。
Preparation of slurry for spray drying (4) [ Preparation of catalyst for oxychlorination (4)]
7.14 kg of slurry for spray drying (4) was prepared in the same manner except that 0.05 kg of gluconic acid added to the alumina hydrogel of Example 1 was replaced with 0.05 kg of 99.5% citric acid. The pH of the slurry at this time was 3.5.
Spray drying slurry (4) was sprayed into a hot air stream at 220 ° C. to obtain fine spherical particles (4).
The average particle size of the microspherical particles (4) was 65 μm, and 10% by weight was 20 μm or less, and 5% by weight was 149 μm or more.
Firing then, spherical particles (4) in a rotary calciner to prepare a catalyst for oxychlorination (4) and calcined for 0.5 hours at 650 ° C..
［オキシクロリネーション用触媒(5)の調製］
噴霧乾燥用スラリー(5)の調製
実施例１の純水０．４５ｋｇ、濃度９９重量％の硝酸ランタン六水物０．０４ｋｇ、濃度９８重量％の硝酸セリウム六水物０．０４ｋｇの代わりに純水０．３１ｋｇ、濃度３０重量％ＲＥＣｌ3の塩化希土類溶液０．１５ｋｇに代えた以外は同様にして噴霧乾燥用スラリー(5)７．１４ｋｇを調製した。このときのスラリーのｐＨは３．５であった。
噴霧乾燥
噴霧乾燥用スラリー(5)を温度２２０℃の熱風気流中に噴霧して微小球状粒子(5)を得た。
微小球状粒子(5)の平均粒子径は６５μｍであり、２０μｍ以下が１０重量％、１４９μｍ以上が５重量％であった。
焼成
ついで、微小球状粒子(5)を回転式焼成炉にて、６５０℃で０．５時間焼成してオキシクロリネーション用触媒(5)を調製した。
オキシクロリネーション用触媒(5)の平均粒子径、ＣＢＤ、アルミナの結晶形、組成、耐摩耗性は表１に示した。
[Preparation of catalyst for oxychlorination (5)]
Preparation of slurry for spray drying (5) 0.45 kg of pure water of Example 1, 0.04 kg of lanthanum nitrate hexahydrate having a concentration of 99% by weight, 0.04 kg of cerium nitrate hexahydrate having a concentration of 98% by weight A spray drying slurry (5) (7.14 kg) was prepared in the same manner except that the water was replaced with 0.31 kg of water and 0.15 kg of a rare earth chloride solution having a concentration of 30 wt% RECl 3 . The pH of the slurry at this time was 3.5.
The spray drying slurry (5) was sprayed into a hot air stream at a temperature of 220 ° C. to obtain microspherical particles (5).
The average particle size of the microspherical particles (5) was 65 μm, 20% or less was 10% by weight, and 149 μm or more was 5% by weight.
Firing then, the spherical particles (5) in a rotary calciner to prepare a catalyst for oxychlorination (5) and then calcined for 0.5 hours at 650 ° C..
Table 1 shows the average particle size, CBD, crystal form of alumina, composition, and wear resistance of the oxychlorination catalyst (5).
［オキシクロリネーション用触媒(6)の調製］
噴霧乾燥用スラリー(6)の調製
実施例１の純水０．４５ｋｇ、濃度９９重量％の硝酸ランタン六水物０．０４ｋｇ、濃度９８重量％の硝酸セリウム六水物０．０４ｋｇ、濃度９８重量％の硝酸マグネシウム六水物０．２０ｋｇの代わりに、純水０．３６ｋｇ、濃度３０重量％の塩化希土類溶液０．１５ｋｇ、濃度９８％の塩化マグネシュウム六水物０．１５ｋｇを用いた以外は同様にして噴霧乾燥用スラリー(6)７．１４ｋｇを調製した。このときのスラリーのｐＨは３．３であった。
噴霧乾燥
噴霧乾燥用スラリー(6)を温度２２０℃の熱風気流中に噴霧して微小球状粒子(6)を得た。
微小球状粒子(6)の平均粒子径は６５μｍであり、２０μｍ以下が１０重量％、１４９μｍ以上が５重量％であった。
焼成
ついで、微小球状粒子(6)を回転式焼成炉にて、６５０℃で０．５時間焼成してオキシクロリネーション用触媒(6)を調製した。
[Preparation of Oxychlorination Catalyst (6)]
Preparation of slurry for spray drying (6) 0.45 kg of pure water of Example 1, 0.04 kg of lanthanum nitrate hexahydrate with a concentration of 99% by weight, 0.04 kg of cerium nitrate hexahydrate with a concentration of 98% by weight, concentration of 98% by weight The same procedure except that 0.36 kg of pure water, 0.15 kg of rare earth chloride solution with a concentration of 30% by weight, and 0.15 kg of magnesium chloride hexahydrate with a concentration of 98% were used instead of 0.20 kg of magnesium nitrate hexahydrate of 0.1%. Thus, 7.14 kg of slurry for spray drying (6) was prepared. At this time, the pH of the slurry was 3.3.
Spray drying slurry (6) was sprayed into a hot air stream at a temperature of 220 ° C. to obtain fine spherical particles (6).
The average particle size of the microspherical particles (6) was 65 μm, and 10% by weight was 20 μm or less, and 5% by weight was 149 μm or more.
Firing then, the spherical particles (6) in a rotary calciner to prepare a catalyst for oxychlorination (6) and then calcined for 0.5 hours at 650 ° C..
［オキシクロリネーション用触媒(7)の調製］
噴霧乾燥用スラリー(7)の調製
実施例１の純水０．４５ｋｇ、濃度９８重量％の硝酸マグネシウム六水物０．２０ｋｇの代わりに純水０．５６ｋｇ、濃度９９重量％の炭酸カリウム（K2CO3）０．０２ｋｇを用いた以外は同様にして噴霧乾燥用スラリー(7)７．１４ｋｇを調製した。このときのスラリーのｐＨは３．７であった。
噴霧乾燥
噴霧乾燥用スラリー(7)を温度２２０℃の熱風気流中に噴霧して微小球状粒子(7)を得た。
微小球状粒子(7)の平均粒子径は６５μｍであり、２０μｍ以下が１０重量％、１４９μｍ以上が５重量％であった。
焼成
ついで、微小球状粒子(7)を回転式焼成炉にて、６５０℃で０．５時間焼成してオキシクロリネーション用触媒(7)を調製した。
[Preparation of Oxychlorination Catalyst (7)]
Preparation of slurry for spray drying (7) 0.45 kg of pure water of Example 1, 0.56 kg of pure water instead of 0.20 kg of magnesium nitrate hexahydrate having a concentration of 98% by weight, potassium carbonate having a concentration of 99% by weight (K2CO3 ) 7.14 kg of a slurry for spray drying (7) was prepared in the same manner except that 0.02 kg was used. At this time, the pH of the slurry was 3.7.
Spray drying slurry (7) was sprayed into a hot air stream at 220 ° C. to obtain fine spherical particles (7).
The average particle size of the microspherical particles (7) was 65 μm, 10% by weight at 20 μm or less and 5% by weight at 149 μm or more.
Firing then, the spherical particles (7) in a rotary calciner to prepare a catalyst for oxychlorination (7) and then calcined for 0.5 hours at 650 ° C..
［オキシクロリネーション用触媒(R1)の調製］
噴霧乾燥用スラリー(R1)の調製
濃度がＡｌ2Ｏ3として５重量％のアルミン酸ナトリウム水溶液７４．７ｋｇとＡｌ2Ｏ3に換算した濃度が２．５重量％の硫酸アルミニウム水溶液７４．７ｋｇとを混合してアルミナヒドロゲルスラリーを調製した。このとき、アルミナヒドロゲルスラリーの調合温度は６０℃、ｐＨは９．５であった。
ついで、アルミナヒドロゲルスラリーを濾過し、６０℃の純水を掛けて洗浄し、Ａｌ2Ｏ3としての濃度が１５重量％の擬ベーマイトアルミナスラリー５．６０ｋｇを得た。
擬ベーマイトアルミナスラリーの一部を乾燥し、走査型電子顕微鏡写真で観察した結果、平均長さ３ｎｍ、平均幅１ｎｍの繊維状一次粒子が束になった繊維状二次粒子であった。
[Preparation of catalyst for oxychlorination (R1)]
Preparation concentration slurry for spray-drying (R1) as the Al 2 O 3 5% strength by weight in terms of an aqueous sodium aluminate solution 74.7kg and Al 2 O 3 of 2.5 weight% of aluminum sulfate aqueous solution 74.7kg Were mixed to prepare an alumina hydrogel slurry. At this time, the preparation temperature of the alumina hydrogel slurry was 60 ° C., and the pH was 9.5.
Subsequently, the alumina hydrogel slurry was filtered and washed with pure water at 60 ° C. to obtain 5.60 kg of pseudo boehmite alumina slurry having a concentration of 15% by weight as Al 2 O 3 .
As a result of drying a part of the pseudo boehmite alumina slurry and observing it with a scanning electron micrograph, it was fibrous secondary particles in which fibrous primary particles having an average length of 3 nm and an average width of 1 nm were bundled.
別途、純水１．２４ｋｇに濃度３５重量％の塩酸０．１１ｋｇを加えた希塩酸へ、濃度９８重量％の塩化第二銅二水物０．２７ｋｇ、濃度３０重量％の塩化希土類溶液０．１８ｋｇおよび濃度９８％の塩化マグネシュウム六水物０．１６ｋｇを溶解し、［ＣｕＯ＋Ｌａ2Ｏ3＋Ｃｅ2Ｏ3＋ＭｇＯ］としての濃度が１５重量％の混合塩酸塩水溶液１．９６ｋｇを調製した。
上記の洗浄した擬ベーマイトアルミナスラリーの温度を５０℃に調整した後、混合塩酸塩水溶液を混合した。
ついで、混合スラリーをホモジナイザーを用いて均一化処理して噴霧乾燥用スラリー(R1）７．５６ｋｇを調製した。このときのスラリーのｐＨは３．２であった。
Separately, 0.27 kg of 98 wt% cupric chloride dihydrate and 0.18 kg of rare earth chloride solution of 30 wt% concentration were added to dilute hydrochloric acid obtained by adding 0.11 kg of 35 wt% hydrochloric acid to 1.24 kg of pure water. Then, 0.16 kg of 98% magnesium chloride hexahydrate was dissolved to prepare 1.96 kg of a mixed hydrochloride aqueous solution having a concentration of 15% by weight as [CuO + La 2 O 3 + Ce 2 O 3 + MgO].
After adjusting the temperature of the washed pseudo-boehmite alumina slurry to 50 ° C., the mixed hydrochloride aqueous solution was mixed.
Next, the mixed slurry was homogenized using a homogenizer to prepare 7.56 kg of a slurry for spray drying (R1). At this time, the pH of the slurry was 3.2.
噴霧乾燥
噴霧乾燥用スラリー(R1)を温度２２０℃の熱風気流中に噴霧して微小球状粒子(R1)を得た。微小球状粒子(R1)の平均粒子径は６５μｍであり、２０μｍ以下が１０重量％、１４９μｍ以上が５重量％であった。
焼成
ついで、微小球状粒子(R1)を回転式焼成炉にて、５５０℃で０．５時間焼成してオキシクロリネーション用触媒(R1)を調製した。
The slurry for spray drying (R1) was sprayed into a hot air stream at a temperature of 220 ° C. to obtain fine spherical particles (R1). The average particle diameter of the microspherical particles (R1) was 65 μm, and 10% by weight was 20 μm or less and 5% by weight was 149 μm or more.
Firing then, the spherical particles (R1) in a rotary calciner to prepare a catalyst for oxychlorination (R1) and calcined for 0.5 hours at 550 ° C..
［オキシクロリネーション用触媒(R2)の調製］
噴霧乾燥用スラリー(R2)の調製
比較例１の純水１．２４ｋｇ、濃度９８重量％の塩化マグネシュウム六水物０．１６ｋｇの代わりに純水１．４２ｋｇ、濃度９７重量％の塩化カリウム（KCl）０．０２ｋｇを用いた以外は同様にして噴霧乾燥用スラリー(R2) ７．５６ｋｇを調製した。このときのスラリーのｐＨは３．４であった。
噴霧乾燥
噴霧乾燥用スラリー(R2)を温度２２０℃の熱風気流中に噴霧して微小球状粒子(R2)を得た。微小球状粒子(R2)の平均粒子径は６５μｍであり、２０μｍ以下が１０重量％、１４９μｍ以上が５重量％であった。
焼成
ついで、微小球状粒子(R2)を回転式焼成炉にて、５５０℃で０．５時間焼成してオキシクロリネーション用触媒(R2)を調製した。
[Preparation of Oxychlorination Catalyst (R2)]
Preparation of slurry for spray drying (R2) 1.24 kg of pure water in Comparative Example 1 and 0.16 kg of magnesium chloride hexahydrate having a concentration of 98% by weight 1.42 kg of pure water and potassium chloride having a concentration of 97% by weight (KCl) ) 7.56 kg of slurry for spray drying (R2) was prepared in the same manner except that 0.02 kg was used. The pH of the slurry at this time was 3.4.
The slurry for spray drying (R2) was sprayed into a hot air stream at 220 ° C. to obtain microspherical particles (R2). The average particle diameter of the microspherical particles (R2) was 65 μm, and 10% by weight was 20 μm or less, and 5% by weight was 149 μm or more.
Firing then, the spherical particles (R2) in a rotary calciner to prepare a catalyst for oxychlorination (R2) and then calcined for 0.5 hours at 550 ° C..
［オキシクロリネーション用触媒(R3)の調製］
噴霧乾燥用スラリー(R3)の調製
濃度がＡｌ2Ｏ3として５重量％のアルミン酸ナトリウム水溶液７４．７ｋｇとＡｌ2Ｏ3に換算した濃度が２．５重量％の硫酸アルミニウム水溶液７４．７ｋｇとを混合してアルミナヒドロゲルスラリーを調製した。このとき、アルミナヒドロゲルスラリーの調合温度は６０℃、ｐＨは９．５であった。
ついで、アルミナヒドロゲルスラリーを濾過し、６０℃の純水を掛けて洗浄し、Ａｌ2Ｏ3としての濃度が１５重量％の擬ベーマイトアルミナスラリー５．６０ｋｇを得た。
擬ベーマイトアルミナスラリーの一部を乾燥し、走査型電子顕微鏡写真で観察した結果、平均長さ３ｎｍ、平均幅１ｎｍの繊維状一次粒子が束になった繊維状二次粒子であった。
[Preparation of Oxychlorination Catalyst (R3)]
Preparation Concentration of spray drying a slurry (R3) as the Al 2 O 3 5% strength by weight in terms of an aqueous sodium aluminate solution 74.7kg and Al 2 O 3 of 2.5 weight% of aluminum sulfate aqueous solution 74.7kg Were mixed to prepare an alumina hydrogel slurry. At this time, the preparation temperature of the alumina hydrogel slurry was 60 ° C., and the pH was 9.5.
Subsequently, the alumina hydrogel slurry was filtered and washed with pure water at 60 ° C. to obtain 5.60 kg of pseudo boehmite alumina slurry having a concentration of 15% by weight as Al 2 O 3 .
As a result of drying a part of the pseudo boehmite alumina slurry and observing it with a scanning electron micrograph, it was fibrous secondary particles in which fibrous primary particles having an average length of 3 nm and an average width of 1 nm were bundled.
別途、純水０．３８ｋｇに濃度６３重量％の硝酸０．１０ｋｇを加えた希硝酸へ、濃度９７重量の硝酸第二銅三水物％（Cu(NO3)2・3H2O）０．３１ｋｇ、濃度９９重量％の硝酸ランタン六水物（La(NO3)3・6H2O）０．０４ｋｇ、濃度９８重量％の硝酸セリウム六水物（Ce(NO3)3・6H2O）０．０４ｋｇ及び濃度９８重量％の硝酸マグネシウム六水物（Mg(NO3)2・6H2O）０．２０ｋｇを溶解し、［ＣｕＯ＋Ｌａ２Ｏ３＋Ｃｅ２Ｏ３＋ＭｇＯ］としての濃度が１５重量％の混合硝酸塩水溶液１．０７ｋｇを調製した。
上記の洗浄した擬ベーマイトアルミナスラリーの温度を５０℃に調整した後、混合硝酸塩水溶液を混合した。
ついで、混合スラリーをホモジナイザーを用いて均一化処理して噴霧乾燥用スラリー(R3)６．６７ｋｇを調製した。このときのスラリーのｐＨは３．５であった。
Separately, dilute nitric acid obtained by adding 0.10 kg of nitric acid having a concentration of 63 wt% to 0.38 kg of pure water, and cupric nitrate trihydrate% (Cu (NO 3 ) 2 .3H 2 O) having a concentration of 97 wt. 31 kg, 99 wt% lanthanum nitrate hexahydrate (La (NO 3 ) 3 · 6H 2 O) 0.04 kg, 98 wt% cerium nitrate hexahydrate (Ce (NO 3 ) 3 · 6H 2 O) 0.04 kg and 0.20 kg of magnesium nitrate hexahydrate (Mg (NO 3 ) 2 .6H 2 O) having a concentration of 98% by weight are dissolved, and 1.07 kg of a mixed nitrate aqueous solution having a concentration of 15% by weight as [CuO + La 2 O 3 + Ce 2 O 3 + MgO] Was prepared.
After adjusting the temperature of the washed pseudo-boehmite alumina slurry to 50 ° C., a mixed nitrate aqueous solution was mixed.
Next, the mixed slurry was homogenized using a homogenizer to prepare 6.67 kg of slurry for spray drying (R3). The pH of the slurry at this time was 3.5.
噴霧乾燥
噴霧乾燥用スラリー(R3)を温度２２０℃の熱風気流中に噴霧して微小球状粒子(R3)を得た。
微小球状粒子(R3)の平均粒子径は６５μｍであり、２０μｍ以下が１０重量％、１４９μｍ以上が５重量％であった。
焼成
ついで、微小球状粒子(R3)を回転式焼成炉にて、６５０℃で０．５時間焼成してオキシクロリネーション用触媒(R3)を調製した。
The slurry for spray drying (R3) was sprayed into a hot air stream having a temperature of 220 ° C. to obtain fine spherical particles (R3).
The average particle diameter of the microspherical particles (R3) was 65 μm, and 10% by weight was 20 μm or less, and 5% by weight was 149 μm or more.
Firing then, the spherical particles (R3) in a rotary calciner to prepare a catalyst for oxychlorination (R3) and calcined for 0.5 hours at 650 ° C..
Claims (9)
（ａ）擬ベーマイトアルミナスラリーにカルボン酸および／またはヒドロキシカルボン酸を加えて熟成する工程
（ｂ）さらに酸と硝酸第二銅水溶液とを添加して噴霧乾燥用スラリーを調製する工程
（ｃ）前記スラリーを噴霧乾燥する工程
（ｄ）（ｃ）工程で得られた微粒子を焼成する工程 In the method for producing an oxychlorination catalyst comprising alumina and copper, wherein the copper content is in the range of 5 to 20% by weight as CuO and the halogen content is 5% by weight or less, the following steps A method for producing an oxychlorination catalyst comprising (a) to (d).
(A) Step of aging by adding carboxylic acid and / or hydroxycarboxylic acid to pseudo boehmite alumina slurry (b) Step of further adding acid and cupric nitrate aqueous solution to prepare slurry for spray drying (c) Steps of spray drying slurry (d) Step of firing fine particles obtained in steps (c)
The carboxylic acid and / or hydroxycarboxylic acid is formic acid, acetic acid, succinic acid, acrylic acid , gluconic acid, malic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, sebacic acid, maleic acid, fumaric acid, 2. For oxychlorination according to claim 1, which is one or more selected from phthalic acid, α-lactic acid, β-lactic acid, γ-hydroxyvaleric acid, glyceric acid, tartaric acid, citric acid, tropic acid and benzylic acid. A method for producing a catalyst.
The method for producing a catalyst for oxychlorination according to any one of claims 1 to 3, wherein the pH of the slurry for spray drying is in the range of 3 to 5.
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