CN115141089A - Method for producing catalyst for production of acrolein and acrylic acid, and method for producing acrolein and acrylic acid using the catalyst - Google Patents
Method for producing catalyst for production of acrolein and acrylic acid, and method for producing acrolein and acrylic acid using the catalyst Download PDFInfo
- Publication number
- CN115141089A CN115141089A CN202210216207.7A CN202210216207A CN115141089A CN 115141089 A CN115141089 A CN 115141089A CN 202210216207 A CN202210216207 A CN 202210216207A CN 115141089 A CN115141089 A CN 115141089A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- mass
- nitrate hexahydrate
- raw material
- cobalt nitrate
- 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.)
- Pending
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- 239000003054 catalyst Substances 0.000 title claims abstract description 191
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 title claims abstract description 134
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 91
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 title claims abstract description 67
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 title claims abstract description 67
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical group O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 claims abstract description 161
- 239000002994 raw material Substances 0.000 claims abstract description 131
- 150000001875 compounds Chemical class 0.000 claims abstract description 74
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 44
- 239000010941 cobalt Substances 0.000 claims abstract description 44
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000000203 mixture Substances 0.000 claims abstract description 41
- 238000002411 thermogravimetry Methods 0.000 claims abstract description 39
- 230000003197 catalytic effect Effects 0.000 claims abstract description 34
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 31
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims abstract description 29
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims abstract description 29
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000002156 mixing Methods 0.000 claims abstract description 26
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 26
- 239000011733 molybdenum Substances 0.000 claims abstract description 26
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims abstract description 25
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 22
- 230000003647 oxidation Effects 0.000 claims abstract description 18
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 37
- 238000000034 method Methods 0.000 claims description 35
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 28
- 239000007789 gas Substances 0.000 claims description 25
- 229910052759 nickel Inorganic materials 0.000 claims description 25
- 229910052742 iron Inorganic materials 0.000 claims description 15
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 239000002131 composite material Substances 0.000 claims description 4
- 239000010936 titanium Substances 0.000 claims description 3
- 229910052721 tungsten Inorganic materials 0.000 claims description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 2
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 2
- 229910052783 alkali metal Inorganic materials 0.000 claims description 2
- 150000001340 alkali metals Chemical class 0.000 claims description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 2
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 2
- 229910052787 antimony Inorganic materials 0.000 claims description 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 2
- 229910052785 arsenic Inorganic materials 0.000 claims description 2
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims description 2
- 229910052796 boron Inorganic materials 0.000 claims description 2
- 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 claims description 2
- 239000011133 lead Substances 0.000 claims description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 2
- 229910052758 niobium Inorganic materials 0.000 claims description 2
- 239000010955 niobium Substances 0.000 claims description 2
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 239000011574 phosphorus Substances 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- 229910052714 tellurium Inorganic materials 0.000 claims description 2
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052716 thallium Inorganic materials 0.000 claims description 2
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 claims description 2
- 229910052718 tin Inorganic materials 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 2
- 239000010937 tungsten Substances 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- 230000009467 reduction Effects 0.000 description 57
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 37
- 239000007864 aqueous solution Substances 0.000 description 25
- 238000002360 preparation method Methods 0.000 description 23
- 238000006243 chemical reaction Methods 0.000 description 20
- 238000011282 treatment Methods 0.000 description 19
- 238000001035 drying Methods 0.000 description 18
- 238000003860 storage Methods 0.000 description 18
- 238000010298 pulverizing process Methods 0.000 description 16
- 238000010304 firing Methods 0.000 description 15
- 238000000465 moulding Methods 0.000 description 15
- 239000012018 catalyst precursor Substances 0.000 description 14
- 230000008093 supporting effect Effects 0.000 description 14
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 description 13
- WALXYTCBNHJWER-UHFFFAOYSA-N 2,4,6-tribromopyridine Chemical compound BrC1=CC(Br)=NC(Br)=C1 WALXYTCBNHJWER-UHFFFAOYSA-N 0.000 description 12
- 230000008859 change Effects 0.000 description 11
- 238000010438 heat treatment Methods 0.000 description 11
- 239000000243 solution Substances 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 229910002651 NO3 Inorganic materials 0.000 description 10
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 10
- 238000007689 inspection Methods 0.000 description 10
- 239000000463 material Substances 0.000 description 9
- 239000002002 slurry Substances 0.000 description 9
- 238000002474 experimental method Methods 0.000 description 8
- QZRHHEURPZONJU-UHFFFAOYSA-N iron(2+) dinitrate nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QZRHHEURPZONJU-UHFFFAOYSA-N 0.000 description 8
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 8
- 150000002823 nitrates Chemical class 0.000 description 8
- 238000005259 measurement Methods 0.000 description 7
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 6
- 230000003247 decreasing effect Effects 0.000 description 6
- 229910001882 dioxygen Inorganic materials 0.000 description 6
- -1 oxides Chemical class 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 239000012784 inorganic fiber Substances 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 230000018044 dehydration Effects 0.000 description 4
- 238000006297 dehydration reaction Methods 0.000 description 4
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 description 4
- 238000011068 loading method Methods 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000004455 differential thermal analysis Methods 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000004321 preservation Methods 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 229910052581 Si3N4 Inorganic materials 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 239000013626 chemical specie Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 238000011835 investigation Methods 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 2
- 150000004686 pentahydrates Chemical class 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 2
- 229910010271 silicon carbide Inorganic materials 0.000 description 2
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- QYIGOGBGVKONDY-UHFFFAOYSA-N 1-(2-bromo-5-chlorophenyl)-3-methylpyrazole Chemical compound N1=C(C)C=CN1C1=CC(Cl)=CC=C1Br QYIGOGBGVKONDY-UHFFFAOYSA-N 0.000 description 1
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 1
- 229910000014 Bismuth subcarbonate Inorganic materials 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- YQYBUJYBXOVWQW-UHFFFAOYSA-N [3-[4-(aminomethyl)-6-(trifluoromethyl)pyridin-2-yl]oxyphenyl]-(3,4-dihydro-1H-isoquinolin-2-yl)methanone Chemical compound NCC1=CC(=NC(=C1)C(F)(F)F)OC=1C=C(C=CC=1)C(=O)N1CC2=CC=CC=C2CC1 YQYBUJYBXOVWQW-UHFFFAOYSA-N 0.000 description 1
- GOKIPOOTKLLKDI-UHFFFAOYSA-N acetic acid;iron Chemical compound [Fe].CC(O)=O.CC(O)=O.CC(O)=O GOKIPOOTKLLKDI-UHFFFAOYSA-N 0.000 description 1
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 239000001099 ammonium carbonate Substances 0.000 description 1
- 235000012501 ammonium carbonate Nutrition 0.000 description 1
- 239000012378 ammonium molybdate tetrahydrate Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- FIXLYHHVMHXSCP-UHFFFAOYSA-H azane;dihydroxy(dioxo)molybdenum;trioxomolybdenum;tetrahydrate Chemical compound N.N.N.N.N.N.O.O.O.O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O[Mo](O)(=O)=O.O[Mo](O)(=O)=O.O[Mo](O)(=O)=O FIXLYHHVMHXSCP-UHFFFAOYSA-H 0.000 description 1
- XUFUCDNVOXXQQC-UHFFFAOYSA-L azane;hydroxy-(hydroxy(dioxo)molybdenio)oxy-dioxomolybdenum Chemical compound N.N.O[Mo](=O)(=O)O[Mo](O)(=O)=O XUFUCDNVOXXQQC-UHFFFAOYSA-L 0.000 description 1
- JHXKRIRFYBPWGE-UHFFFAOYSA-K bismuth chloride Chemical compound Cl[Bi](Cl)Cl JHXKRIRFYBPWGE-UHFFFAOYSA-K 0.000 description 1
- 229910000416 bismuth oxide Inorganic materials 0.000 description 1
- MGLUJXPJRXTKJM-UHFFFAOYSA-L bismuth subcarbonate Chemical compound O=[Bi]OC(=O)O[Bi]=O MGLUJXPJRXTKJM-UHFFFAOYSA-L 0.000 description 1
- 229940036358 bismuth subcarbonate Drugs 0.000 description 1
- 229910000380 bismuth sulfate Inorganic materials 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052878 cordierite Inorganic materials 0.000 description 1
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 description 1
- BEQZMQXCOWIHRY-UHFFFAOYSA-H dibismuth;trisulfate Chemical compound [Bi+3].[Bi+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O BEQZMQXCOWIHRY-UHFFFAOYSA-H 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- RAQDACVRFCEPDA-UHFFFAOYSA-L ferrous carbonate Chemical compound [Fe+2].[O-]C([O-])=O RAQDACVRFCEPDA-UHFFFAOYSA-L 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- 229910000358 iron sulfate Inorganic materials 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- SZQUEWJRBJDHSM-UHFFFAOYSA-N iron(3+);trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O SZQUEWJRBJDHSM-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- ZQKXQUJXLSSJCH-UHFFFAOYSA-N melamine cyanurate Chemical compound NC1=NC(N)=NC(N)=N1.O=C1NC(=O)NC(=O)N1 ZQKXQUJXLSSJCH-UHFFFAOYSA-N 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000002557 mineral fiber Substances 0.000 description 1
- 229940078494 nickel acetate Drugs 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 238000005839 oxidative dehydrogenation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 150000004685 tetrahydrates Chemical class 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/887—Molybdenum containing in addition other metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8876—Arsenic, antimony or bismuth
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
- C07C45/33—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties
- C07C45/34—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds
- C07C45/35—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds in propene or isobutene
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention provides a method for producing a catalyst excellent in catalytic activity and yield, which is used in a method for producing acrolein and acrylic acid by catalytic gas phase oxidation of propylene. The catalystA method for producing a catalyst for catalytic gas phase oxidation of propylene to produce acrolein and acrylic acid, comprising a step of mixing a raw material mixture containing a raw material compound of molybdenum, a raw material compound of bismuth, and a raw material compound of cobalt, wherein the raw material compound of cobalt is cobalt nitrate hexahydrate, and the cobalt nitrate hexahydrate has a mass loss rate L from 25 ℃ to 105 ℃ in thermogravimetric analysis 1 11 to 16 mass%.
Description
Technical Field
The present invention relates to a method for producing a catalyst for producing acrolein and acrylic acid, and a method for producing acrolein and acrylic acid using the catalyst.
Background
Many proposals have been made on catalysts used in the industrial production of acrolein and acrylic acid by the catalytic gas phase oxidation of propylene with molecular oxygen. For example, patent document 1 discloses a composite metal oxide catalyst as a catalyst for producing an unsaturated aldehyde and an unsaturated carboxylic acid, which specifies: molybdenum, bismuth and iron are used as essential catalytically active components, and ammonium molybdate tetrahydrate having an endothermic peak temperature within a predetermined temperature range is used as a molybdenum raw material.
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open publication No. 2018-153773
Disclosure of Invention
(problems to be solved by the invention)
However, although the yield of acrolein and acrylic acid is improved by the catalyst described in the above document 1, further improvement of the catalyst is desired in terms of catalytic performance such as catalytic activity and yield in the industrial-scale production of acrolein and acrylic acid.
Accordingly, an object of the present invention is to provide a method for producing a catalyst which is used in a method for producing acrolein and acrylic acid by catalytic gas phase oxidation of propylene and has excellent catalytic activity and yield. Another object of the present invention is to provide a process for producing acrolein and acrylic acid in high yield by catalytic gas phase oxidation of propylene with a molecular oxygen-containing gas in the presence of a catalyst excellent in catalytic activity and yield produced by the production process.
(means for solving the problems)
In order to solve the above problems, the present inventors have, in particular toIntensive studies have been made with a view to the properties of the raw material compounds used for the production of the catalyst. As a result, it has been found that the above problems can be solved by a method for producing a catalyst for catalytic gas phase oxidation of propylene to produce acrolein and acrylic acid, comprising a step of mixing a raw material mixture containing a raw material compound of molybdenum, a raw material compound of bismuth and a raw material compound of cobalt, wherein the raw material compound of cobalt is cobalt nitrate hexahydrate, and the cobalt nitrate hexahydrate has a mass reduction rate L from 25 ℃ to 105 ℃ in thermogravimetric analysis 1 11 to 16 mass%.
(effect of the invention)
According to the present invention, acrolein and acrylic acid production catalysts having excellent catalytic activity and yield can be produced on an industrial scale. In addition, acrolein and acrylic acid can be produced in high yields by catalytic gas phase oxidation of propylene using the obtained catalyst.
Detailed Description
Hereinafter, embodiments of the present invention will be described, but the present invention is not limited to the following embodiments. In the present specification, "X to Y" indicating a range means "X or more and Y or less".
One embodiment of the present invention is a method for producing a catalyst for catalytic gas phase oxidation of propylene to produce acrolein and acrylic acid (hereinafter, may be referred to as "catalyst for producing acrolein and acrylic acid"), including a step of mixing a raw material mixture containing a raw material compound of molybdenum, a raw material compound of bismuth, and a raw material compound of cobalt, the raw material compound of cobalt being cobalt nitrate hexahydrate, the cobalt nitrate hexahydrate represented by the following formula (a) having a mass reduction rate L from 25 ℃ to 105 ℃ in thermogravimetric analysis (TG) 1 11 to 16 mass%.
L 1 (mass%) = (W) 1 -W 2 )/W 1 ×100 (a)
Wherein the content of the first and second substances,
W 1 = cobalt nitrate hexahydrate mass at 25 ℃ (mg)
W 2 = mass of cobalt nitrate hexahydrate (mg) at 105 ℃.
The method for producing a catalyst for acrolein and acrylic acid production according to the present invention includes a step of mixing a raw material mixture containing a raw material compound of molybdenum, a raw material compound of bismuth, and a raw material compound of cobalt. Therefore, the catalyst for producing acrolein and acrylic acid of the present invention contains molybdenum, bismuth, and cobalt, that is, the catalyst for producing acrolein and acrylic acid of the present invention contains molybdenum, bismuth, and cobalt as essential catalytically active components.
The catalyst for acrolein and acrylic acid production of the present invention contains molybdenum, bismuth, and cobalt as essential components, and further preferably contains iron and/or nickel. In addition, the catalyst for producing acrolein and acrylic acid of the present invention preferably contains a composite oxide represented by the following general formula (1) (wherein the general formula (1) does not include oxygen representing an oxidation state). That is, the catalytically active component of the catalyst for producing acrolein and acrylic acid of the present invention preferably contains a composite oxide represented by the following general formula (1) (wherein the general formula (1) does not include oxygen representing an oxidation state).
Mo 12 Bi a Co b A c B d C e D f (1)
In the formula (1), mo is molybdenum, bi is bismuth, co is cobalt, A is at least 1 element selected from iron and nickel, B is at least 1 element selected from alkali metal, alkaline earth metal and thallium, C is at least 1 element selected from tungsten, silicon, aluminum, zirconium and titanium, D is at least 1 element selected from phosphorus, tellurium, antimony, tin, cerium, lead, niobium, manganese, arsenic, boron and zinc, a, B, C, D, e and f represent the atomic numbers of Bi, co, A, B, C and D, 0 & lta & lt 10 & gt, 0 & ltb & lt 20 & gt, 0 & ltc & lt 20 & gt, 0 & lt D & gt & lt 10 & gt, 0 & lt e & lt 30 & gt, 0 & lt f & lt 4 & gt.
The catalyst for producing acrolein and acrylic acid of the present invention is preferable because it contains the element a (at least 1 element selected from iron and nickel) as a catalyst component, thereby improving the catalytic activity and yield.
In the formula (1), a is preferably 0 < a.ltoreq.10, more preferably 0.2. Ltoreq. A.ltoreq.8, and further preferably 0.4. Ltoreq. A.ltoreq.6. In the formula (1), b is preferably 0 < b.ltoreq.20, more preferably 0.5. Ltoreq. B.ltoreq.15, still more preferably 1. Ltoreq. B.ltoreq.12. In one embodiment, b of formula (1) is preferably 1.5 < b.ltoreq.20, more preferably 2. Ltoreq.b.ltoreq.15, and still more preferably 2.5. Ltoreq.b.ltoreq.12. In the formula (1), c is preferably 0 < c.ltoreq.20, more preferably 0.2. Ltoreq. C.ltoreq.15, and further preferably 0.4. Ltoreq. C.ltoreq.12. In the formula (1), d is preferably 0. Ltoreq. D.ltoreq.10, more preferably 0. Ltoreq. D.ltoreq.6, and still more preferably 0. Ltoreq. D.ltoreq.4. In the formula (1), e is preferably 0. Ltoreq. E.ltoreq.30, more preferably 0. Ltoreq. E.ltoreq.20, and further preferably 0. Ltoreq. E.ltoreq.15. In the formula (1), f is preferably 0. Ltoreq. F.ltoreq.4, more preferably 0. Ltoreq. F.ltoreq.3, and still more preferably 0. Ltoreq. F.ltoreq.2.
Here, in the method for producing a catalyst for producing acrolein and acrylic acid of the present invention, the raw material compound of cobalt used is cobalt nitrate hexahydrate. That is, in the catalyst for producing acrolein and acrylic acid of the present invention, the raw material compound of cobalt contained as an essential catalytic active component is cobalt nitrate hexahydrate. The cobalt nitrate hexahydrate has a mass loss rate L from 25 ℃ to 105 ℃ in thermogravimetric analysis 1 (hereinafter, also referred to as "mass loss rate L of cobalt nitrate hexahydrate 1 ") 11 to 16 mass%. The mass reduction rate L is 1 Represented by the above formula (a). By using such cobalt nitrate hexahydrate as a raw material of a catalyst for producing acrolein and acrylic acid, the catalytic activity and yield of the obtained catalyst for producing acrolein and acrylic acid can be remarkably improved.
Here, the mass loss rate L of cobalt nitrate hexahydrate 1 The numerical value is a value showing a change in mass accompanying dehydration and thermal decomposition of hygroscopic water and crystal water caused by a temperature change (heating) from 25 ℃ to 105 ℃ in thermogravimetric analysis. Among them, the mass change due to dehydration of crystal water in the temperature change from 25 ℃ to 105 ℃ of cobalt nitrate hexahydrate, and the mass change accompanying thermal decomposition are considered as values inherent to cobalt nitrate hexahydrate. Thus, in the thermogravimetric analysis, the mass loss rate L of cobalt nitrate hexahydrate in each of the measurement samples of cobalt nitrate hexahydrate 1 When the value of (2) is varied, it is considered that the variation (difference) of the value is mainly derived from the moisture-absorbed water of cobalt nitrate hexahydrateThe amount of the components is divided. The mass loss rate L of cobalt nitrate hexahydrate was determined by theoretical investigation based on the change in mass due to dehydration of crystal water 1 About 6 to 37%, and considering the change in mass due to dehydration of the hygroscopic water based on the change in mass, the mass loss rate L of the cobalt nitrate hexahydrate 1 A wider range of values may be taken. It should be noted that the mechanism of the weight loss from 25 ℃ to 105 ℃ of the cobalt nitrate hexahydrate is merely an assumption, and does not limit the technical scope of the present invention. The catalyst for producing acrolein and acrylic acid of the present invention is obtained by using the mass reduction rate L 1 Cobalt nitrate hexahydrate in a specific range is produced as a raw material, and the cobalt nitrate hexahydrate exerts an effect.
It is known that nitrates such as cobalt nitrate hexahydrate, which are generally used as a raw material compound of a catalyst, tend to absorb moisture, and the moisture content of cobalt nitrate hexahydrate varies in a wide range depending on the storage state thereof, and as a result, the mass reduction rate L of cobalt nitrate hexahydrate 1 But also within wide limits. However, up to now, the moisture content and the storage method have not been studied in detail for cobalt nitrate hexahydrate as a raw material used in a catalyst for producing acrolein and acrylic acid.
The present inventors have found that if the moisture content of cobalt nitrate hexahydrate is high, the mass loss rate L thereof is high 1 Higher, in use, the mass reduction rate L 1 In the case of producing acrolein and a catalyst for acrylic acid production from high cobalt nitrate hexahydrate, if propylene is subjected to catalytic gas phase oxidation using the catalyst for acrolein and acrylic acid production, the yield of acrolein and acrylic acid becomes low. Further, it was found that when the moisture content of cobalt nitrate hexahydrate was decreased, the mass reduction rate L thereof was increased 1 Becomes low and the mass reduction rate L is used 1 When acrolein and acrylic acid production catalyst are produced with low cobalt nitrate hexahydrate, similarly, if propylene is subjected to catalytic gas phase oxidation using the catalyst for acrolein and acrylic acid production, the yield of acrolein and acrylic acid is lowered.
As a result of various investigations, it was found that cobalt nitrate hexahydrate was used as a raw materialMass loss rate L of the compound 1 11 to 16% by mass, the catalytic activity and yield of the resulting catalyst for producing acrolein and acrylic acid can be significantly improved. That is, the present inventors have found that the moisture content of cobalt nitrate hexahydrate varies depending on the storage condition of cobalt nitrate hexahydrate, and the mass reduction rate L of cobalt nitrate hexahydrate 1 When the catalyst is changed in a wide range, the performance such as catalytic activity and yield of the obtained catalyst for producing acrolein and acrylic acid varies in a wide range, and therefore, it is a main cause that a high-performance catalyst for producing acrolein and acrylic acid cannot be stably produced. According to the invention, by using a specific mass reduction rate L 1 The cobalt nitrate hexahydrate can industrially stably produce a catalyst for producing acrolein and acrylic acid, which has excellent catalytic activity and yield. Thus, acrolein and acrylic acid can be produced industrially stably with high yield by using the catalyst. The reason why the above-described effects are exhibited by the configuration of the present invention is not necessarily clear, but is considered as follows.
Mass loss rate L of cobalt nitrate hexahydrate 1 The main cause of the influence on the catalytic activity and yield is not determined, but it is considered that the mass loss rate L is a factor 1 In contrast, co produced when cobalt nitrate hexahydrate was dissolved in water 2+ 、Co 2+ With OH - Of (e.g. CoOH) + 、Co(OH) 2 、Co 2 OH 3+ Etc.), whereby the reactivity of other elements, particularly molybdenum as a main raw material, and cobalt changes.
Presume the mass loss rate L in cobalt nitrate hexahydrate 1 Low (e.g. mass loss rate L of cobalt nitrate hexahydrate from 25 ℃ to 105 ℃ by thermogravimetric analysis 1 Less than 11 mass%), among chemical species generated when cobalt nitrate hexahydrate is dissolved in water, with Co 2+ In contrast, coOH + 、Co(OH) 2 、Co 2 OH 3+ Like Co 2+ The existing ratio of other dissolved species increases, whereby Co 2+ The existing ratio of molybdenum is decreased and the reactivity of molybdenum with cobalt is decreased. In additionIn addition, the mass loss rate L in cobalt nitrate hexahydrate was estimated 1 High (e.g. mass loss rate L of cobalt nitrate hexahydrate from 25 ℃ to 105 ℃ by thermogravimetric analysis 1 More than 16% by mass), co is contained in the chemical species generated when the cobalt nitrate hexahydrate is dissolved in water 2+ The concentration of (a) decreases and the reactivity of molybdenum with cobalt decreases. However, this mechanism is merely an assumption and, of course, does not limit the technical scope of the present invention.
It is known that although nitrate generally has high hygroscopicity, the mass reduction rate L is controlled in nitrate other than cobalt (for example, nitrates of bismuth, iron, and nickel) 1 The effect of improving the performance of the catalyst was not exhibited, which was confirmed in examples (examples 6 to 8) described later. The reason is not clear, but it can be said that only cobalt nitrate hexahydrate and mass loss rate L 1 In relation thereto, significantly contributes to the catalytic performance.
As described above, when the catalyst for acrolein and acrylic acid production is produced, the catalyst is produced by using the catalyst having a mass reduction rate L of 11 to 16 mass% 1 The cobalt nitrate hexahydrate is used as a cobalt raw material, and can remarkably improve the catalytic activity and yield of the obtained catalyst for producing acrolein and acrylic acid.
Mass loss rate L of cobalt nitrate hexahydrate 1 Preferably more than 11% by mass, more preferably 11.1% by mass or more, further preferably more than 11.1% by mass, more preferably 11.3% by mass or more, particularly preferably 11.5% by mass or more, and most preferably 12% by mass or more. In addition, the mass loss rate L of cobalt nitrate hexahydrate 1 Preferably less than 16% by mass, more preferably 15.5% by mass or less, still more preferably 15% by mass or less, yet more preferably 14.5% by mass or less, particularly preferably 14.3% by mass or less, and most preferably less than 14.1% by mass. In a preferred embodiment, the mass reduction rate L of cobalt nitrate hexahydrate 1 Is 14.0 mass% or less.
Here, the mass loss rate L for cobalt nitrate hexahydrate 1 The measurement method of (2) will be described. As a measurement sample, it was prepared in an aluminum panThe sample obtained by accurately weighing 20mg of cobalt nitrate hexahydrate was obtained. After the measurement sample was set in a sample holder of a thermogravimetric analysis (TG) apparatus, the temperature was measured at a temperature rising rate of 2 ℃/min from 25 ℃ or lower to 300 ℃ to calculate a mass loss rate L from 25 ℃ to 105 ℃ 1 . The thermogravimetric analysis (TG) device used for the analysis may be of a standard, or may be a thermogravimetric-differential thermal analysis device (TG-DTA) configured to be able to simultaneously measure the thermogravimetric analysis (TG) and the Differential Thermal Analysis (DTA).
Further, from the results of the thermogravimetric analysis, the mass loss rate L from 105 ℃ to 300 ℃ was calculated 2 (hereinafter referred to as "mass loss rate L of cobalt nitrate hexahydrate 2 ") and a mass loss rate L of cobalt nitrate hexahydrate from 25 ℃ to 300 ℃ 3 (hereinafter referred to as "mass loss rate L of cobalt nitrate hexahydrate 3 "). In the present invention, the mass loss rate L of cobalt nitrate hexahydrate 3 Preferably 62 to 75% by mass, more preferably 65 to 73% by mass, still more preferably 66 to 72% by mass, yet more preferably 66.3 to 71.0% by mass, particularly preferably 66.5 to 70.5% by mass, and most preferably 66.8 to 70.0% by mass. In the production of acrolein and a catalyst for acrylic acid production, by using the mass reduction rate L having the above range 3 The cobalt nitrate hexahydrate is used as a cobalt raw material, and can remarkably improve the catalytic activity and yield of the obtained catalyst for producing acrolein and acrylic acid.
Further, from the results of the thermogravimetric analysis, the mass loss rate L of cobalt nitrate hexahydrate at 25 ℃ to 105 ℃ was calculated 1 Mass loss rate L relative to cobalt nitrate hexahydrate at 25 ℃ to 300 ℃ 3 Ratio R (hereinafter referred to as "mass loss rate L of cobalt nitrate hexahydrate 1 R ") of the first group.
In one embodiment of the invention, the mass reduction rate L of cobalt nitrate hexahydrate 1 The ratio R of (A) to (B) is 0.147 to 0.258. In the present invention, the mass loss rate L of cobalt nitrate hexahydrate 1 The ratio R of (A) is preferably 0.163 to 0.225, more preferably 0.164 to 0.210, still more preferably 0.165 to 0.205, and still more preferably 0.165 to 0.202, particularly preferably 0.166 to 0.201, and most preferably 0.166 or more and less than 0.201. In one embodiment, the rate of mass loss L of cobalt nitrate hexahydrate 1 The ratio R of (A) is 0.170 or more and less than 0.201. In the production of acrolein and a catalyst for acrylic acid production, the mass reduction rate L having the above-mentioned range is used as a raw material compound of cobalt 1 The cobalt nitrate hexahydrate of the ratio R can remarkably improve the catalytic activity and yield of the obtained catalyst for producing acrolein and acrylic acid.
The method for producing a catalyst for producing acrolein and acrylic acid according to the present invention includes a step of mixing a raw material mixture containing a raw material compound of molybdenum, a raw material compound of bismuth, and a raw material compound of cobalt. The raw material compound of molybdenum is a compound containing molybdenum, the raw material compound of bismuth is a compound containing bismuth, and the raw material compound of cobalt is a compound containing cobalt. Therefore, in the method for producing a catalyst for acrolein and acrylic acid production of the present invention, it is necessary to use a molybdenum-containing compound, a bismuth-containing compound, and a cobalt-containing compound as raw materials, the cobalt raw material compound being a mass reduction rate L 1 The cobalt nitrate hexahydrate can be produced by a method generally used for producing a known catalyst for producing acrolein and acrylic acid, in addition to the cobalt nitrate hexahydrate in a specific range. Hereinafter, preferred embodiments of the method for producing the catalyst for producing acrolein and acrylic acid according to the present invention will be described.
For example, the method for producing a catalyst for acrolein and acrylic acid production of the present invention includes at least one of the following steps (1) and (2) to (6): (1) A raw material mixing step of mixing raw material compounds containing an element constituting a catalytically active component (hereinafter referred to as "catalyst component element") to obtain a raw material mixture; (2) A drying step of heating the raw material mixture to obtain a dried product; (3) A pulverization step in which the dried product is pulverized to obtain a pulverized product; (4) A molding step of molding the pulverized product to obtain a molded body; (5) A loading step in which the pulverized material is loaded on an inactive carrier; and (6) a firing step of firing the molded article or the support. Alternatively, the 1 st firing step may be added after the (2) drying step or the (3) pulverizing step, and firing may be performed 2 times together with the (6). The "step of mixing a raw material mixture containing a raw material compound of molybdenum, a raw material compound of bismuth, and a raw material compound of cobalt" corresponds to "(1) a raw material mixing step of mixing raw material compounds containing a catalyst component element to obtain a raw material mixture.
In a preferred embodiment, the method for producing a catalyst for producing acrolein and acrylic acid of the present invention comprises the following steps before the raw material mixing step: (A1) An inspection step in which the mass reduction rate L of cobalt nitrate hexahydrate is measured by TG or TG-DTA 1 Carrying out measurement; (B1) A regulating step in which the mass reduction rate L of the cobalt nitrate hexahydrate in the inspecting step 1 When the content of the cobalt nitrate hexahydrate is less than 11% by mass or exceeds 16% by mass, the mass loss rate L of the cobalt nitrate hexahydrate is used 1 The mass reduction rate L of cobalt nitrate hexahydrate was adjusted so as to be 11 to 16 mass% 1 。
(A1) Inspection step
The inspection step was carried out by measuring TG or TG-DTA of cobalt nitrate hexahydrate used as a raw material and confirming the mass loss rate L 1 The step (2) is preferably performed before 10 to 3 hours from the raw material mixing step. In the inspection step, the mass reduction rate L of cobalt nitrate hexahydrate was confirmed 1 In the case of 11 to 16% by mass, it is preferable that the mass reduction rate L is set to the mass reduction rate L until the raw material mixing step 1 The cobalt nitrate hexahydrate used as the raw material was preserved in an unchanged manner. As a method of preservation, any method may be used as long as the mass reduction rate L is 1 The method which does not change is not particularly limited, and a known method may be used. For example, the storage method may be a method in which a required amount or an amount equal to or larger than a required amount of cobalt nitrate hexahydrate used as a raw material is filled in a hopper, nitrogen is substituted, and then the raw material is stored in a sealed state, or a method in which an amount equal to or larger than a required amount of cobalt nitrate hexahydrate used as a raw material is dissolved in an aqueous solution and stored in a sealed state as an aqueous solution.
(B1) Adjustment step
The adjustment step is a step in which the mass reduction rate L of the cobalt nitrate hexahydrate is confirmed in the inspection step 1 When the amount is less than 11% by mass or exceeds 16% by mass, the amount is decreased by the mass loss rate L 1 And a step of treating cobalt nitrate hexahydrate used as a raw material.
Examples of the treatment performed in the adjustment step include a treatment for appropriately adjusting the humidity of a storage place, the storage amount (amount filled in a container), the storage period, and the like when cobalt nitrate hexahydrate is stored. These treatments may be performed alone or in combination. Here, in the adjustment step, the mass loss rate L in the cobalt nitrate hexahydrate 1 Less than 11% by mass and the rate of mass loss L of cobalt nitrate hexahydrate 1 When the amount exceeds 16% by mass, the above treatments are performed under different conditions.
For example, the mass loss rate L in cobalt nitrate hexahydrate 1 When the content is less than 11% by mass, the cobalt nitrate hexahydrate is preferably subjected to moisture absorption treatment. As a treatment method for making the moisture absorption, in the above treatment, the treatment is performed under a condition of absorbing moisture. For example, the treatment method for absorbing moisture may be a method in which the required amount or an amount equal to or larger than the required amount of cobalt nitrate hexahydrate used as a raw material is stored in a roofed warehouse at a temperature of-10 to 50 ℃ and a relative humidity of 40 to 100% RH for 1 to 24 hours, or the cobalt nitrate hexahydrate is charged into a hopper and then allowed to stand in the atmosphere for 1 to 24 hours. Mass loss rate L according to cobalt nitrate hexahydrate during storage 1 The adjustment is proper. Further, by increasing or decreasing the amount of storage (the amount of storage in the container), the time required for the treatment can be arbitrarily changed.
In addition, the mass loss rate L in, for example, cobalt nitrate hexahydrate 1 When the content exceeds 16% by mass, it is preferable to dry the cobalt nitrate hexahydrate. As a method of drying, in the above-mentioned treatment, the treatment is performed under a drying condition. For example, the treatment for drying can be carried out by subjecting the cobalt nitrate hexahydrate used as the starting material to a temperature of-10E to EA method comprising storing the mixture in a roofed warehouse at 40 ℃ and a relative humidity of 0 to 60% RH for 1 to 24 hours or vacuum-drying the mixture for 1 to 24 hours after filling the warehouse in a hopper. Mass loss rate L according to cobalt nitrate hexahydrate during storage 1 The adjustment is proper. Further, by increasing or decreasing the amount of preservation (the amount of the preservation filled in the container), the time required for the treatment can be arbitrarily changed.
Preferably, the mass loss rate L is determined based on the mass loss rate L confirmed in the inspection step 1 After the cobalt nitrate hexahydrate is treated in the adjustment step, (A1) the mass reduction rate L of the cobalt nitrate hexahydrate by TG or TG-DTA is again carried out 1 And (5) an inspection step of performing measurement. That is, it is preferable to repeat the (A1) inspection step and the (B1) adjustment step until the mass loss rate L of cobalt nitrate hexahydrate 1 The content is 11 to 16% by mass. The mass loss rate L in the form of cobalt nitrate hexahydrate 1 When the adjustment is performed so as to be 11 to 16 mass%, the data at the time of the adjustment is acquired and collected to some extent, and the mass loss rate L obtained by the adjustment can be estimated based on the data 1 The numerical value of (c).
The mass reduction rate L of the cobalt nitrate hexahydrate is confirmed through the inspection step or the inspection step and the adjustment step 1 When the content is 11 to 16% by mass, at least one of (1) and (2) to (6) in the following steps is performed using the cobalt nitrate hexahydrate: (1) a raw material mixing step; (2) a drying step; (3) a pulverization step; (4) a molding process; (5) a loading step; and (6) a firing step. Hereinafter, each step will be described.
(1) Raw material mixing step
In the present invention, the raw material mixing step is a step of mixing raw material compounds (for example, a raw material compound of molybdenum, a raw material compound of bismuth, a raw material compound of cobalt, a raw material compound of iron, and a raw material compound of nickel) containing each of the catalyst component elements constituting the catalyst for producing acrolein and acrylic acid alone or in plural to obtain a raw material mixture containing all the catalyst component elements. In the raw material mixing step of the present invention, at least the raw material compound of molybdenum, the raw material compound of bismuth, and the raw material compound of cobalt are mixed to obtain the raw material mixture, but the order of mixing them is not particularly limited, and the raw material mixture may contain a raw material compound of molybdenum, a raw material compound of bismuth, and a raw material compound containing an element as a catalyst component other than the raw material compound of cobalt.
The raw material compound of the catalyst component element that can be used in the present invention is essentially a raw material compound of molybdenum, a raw material compound of bismuth, and a raw material compound of cobalt, and the raw material compound of cobalt is the mass reduction rate L 1 There are no particular restrictions on the cobalt nitrate hexahydrate other than those in the specific ranges, and salts such as oxides, hydroxides, ammonium salts, nitrates, carbonates, sulfates, chlorides, and organic acid salts of the metal elements that are generally used in such catalysts, aqueous solutions, sols, and the like of these, or mixtures of these can be used in combination. Among them, ammonium salts and nitrates are suitable as raw materials for the elements of the respective catalyst components.
Examples of the raw material compound of molybdenum include ammonium paramolybdate, ammonium dimolybdate, ammonium tetramolybdate, molybdenum trioxide, and the like, and among them, ammonium paramolybdate is preferable. Examples of the raw material compound of bismuth include bismuth chloride, bismuth nitrate, bismuth sulfate, bismuth acetate, bismuth oxide, and bismuth subcarbonate, and among these, bismuth nitrate is preferable. Examples of the raw material compound of iron include iron chloride, iron nitrate, iron sulfate, iron acetate, iron oxide, and iron carbonate, and among them, iron nitrate is preferable. Examples of the raw material compound of nickel include nickel chloride, nickel nitrate, nickel sulfate, nickel acetate, nickel oxide, and basic nickel carbonate, and among these, nickel nitrate is preferable.
The raw material mixture may be prepared by a method generally used for such a catalyst, and the raw material compounds may be dissolved or suspended in a solvent such as water to prepare a solution or slurry, and then sequentially mixed. Alternatively, one raw material compound may be divided into a plurality of solutions or slurries and mixed. Further, the respective raw material compounds may be directly added to the solution or slurry without being dissolved, and mixed. The mixing conditions (mixing order, temperature, pressure, pH, etc.) of the raw material compounds are not particularly limited. The obtained solution or slurry may be concentrated to form a cake as necessary in order to be applied to a drying method in the subsequent drying step.
In the production method of the present invention, as the raw material compound of cobalt, the mass loss rate L from 25 ℃ to 105 ℃ in thermogravimetric analysis is used 1 11 to 16 mass% of cobalt nitrate hexahydrate. Here, as described above, since cobalt nitrate hexahydrate is hygroscopic, the mass reduction rate L is usually maintained in a storage state 1 The change in the amount of time is subtle. Therefore, when the respective raw material compounds are mixed so as to have a desired composition of the catalyst component in the raw material mixing step, it is preferable to consider the mass reduction rate L for the cobalt nitrate hexahydrate 1 The values of (a) are weighed and used. In the case of producing a catalyst on an industrial scale, it is necessary to perform a raw material mixing step a plurality of times to adjust the composition of the catalyst component in each time to be the same, but if the mass reduction rate L is taken into consideration 1 The amount of cobalt nitrate hexahydrate used may vary slightly from time to time. In this case, the amount of cobalt nitrate hexahydrate used and the mass loss rate L thereof can be considered 1 The amount of water used for the preparation of the solution or slurry is adjusted so that the total water content in the system of the raw material mixture is the same, but the mass reduction rate L is used only when 1 When the amount of cobalt nitrate hexahydrate is 11 to 16% by mass, the total water content in the system may not be adjusted in the same manner for each time.
In the production method of the present invention, when respective nitrates are used as the raw material compounds of bismuth, iron or nickel, the mass reduction rates L of these nitrates are as described above 1 The catalyst performance is hardly affected, and therefore the mass reduction rate L based on these nitrates is not particularly required 1 The total water content in the system is adjusted, but these mass reduction rates L may be considered 1 To be appropriately adjusted.
(2) Drying step
The drying step in the present invention is a step of subjecting at least one of the raw material mixture obtained in the raw material mixing step, the pulverized material obtained in the pulverizing step described later, the molded product obtained in the molding step described later, or the carrier obtained in the supporting step described later to a heat treatment at a temperature preferably in the range of 100 to 300 ℃, more preferably 150 to 200 ℃.
In the drying step, when the raw material mixture obtained in the raw material mixing step is subjected to a heating treatment to obtain a dried product, the heating treatment method for obtaining the dried product is not particularly limited, and may be appropriately selected in accordance with the form of the raw material mixture. For example, when the raw material mixture is in the form of a solution or slurry, a dried product in the form of granules or powder may be obtained using a spray dryer, a drum dryer, or the like, or the solution or slurry may be put into a tub or the like and dried using a box dryer. When the raw material mixture is in the form of a cake obtained by concentrating a solution or slurry, a block-like or sheet-like dried product can be obtained by performing a heating treatment in an air stream, an inert gas stream such as nitrogen, or the like, or in an atmosphere using a box dryer, a tunnel dryer, or the like. When a box dryer or a tunnel dryer is used, for example, the drying time is preferably 3 to 30 hours, more preferably 5 to 20 hours. When a solution or slurry of the raw material mixture is put in a drum or the like and dried, or when the raw material mixture in a cake form is dried, a method may be used as long as a dry matter that can be pulverized in the subsequent pulverization step is obtained as necessary.
In the case where the pulverized material obtained in the pulverizing step described later, the molded product obtained in the molding step described later, or the carrier obtained in the carrying step described later is subjected to a heat treatment, a box-type dryer, a tunnel-type dryer, or the like may be used, and the dried material may be prepared by performing the heat treatment in an air stream, a stream of an inert gas such as nitrogen, or the like under a gas flow or an atmosphere.
(3) Grinding step
The pulverization step in the present invention means a step of pulverizing a dried product obtained by heating the raw material mixture, as necessary. In the production method of the present invention, the dried product obtained in the drying step is preferably pulverized into a desired particle size.
In the pulverizing step, the pulverizing method is not particularly limited, and may be selected so as to be suitable for the form of the dried product. For example, the dried product may be pulverized by using various hammer mills, jet mills, ball mills, or the like to obtain a pulverized product having a desired particle diameter which can be used in the subsequent molding step or supporting step. The pulverized product was used as a catalyst precursor. In addition, the catalyst precursor may be obtained by pulverizing, drying or calcining, and in this case, the catalyst precursor may be obtained by pulverizing, drying or calcining.
The particle size of the pulverized product (catalyst precursor) obtained through the pulverization step is not particularly limited, but is in the range of 0.1 to 500 μm, preferably 10 to 300 μm, in order to maintain good moldability or supporting property in the molding step or supporting step described later.
(4) Molding step or (5) supporting step
The forming step in the present invention is a step of forming the pulverized material obtained in the pulverizing step, a dried material obtained by drying the pulverized material again, or a calcined material thereof into a predetermined shape as a catalyst precursor. The supporting step in the present invention is a step of supporting the pulverized product obtained in the pulverizing step as the catalyst precursor, the dried product obtained by drying the pulverized product again, or a calcined product thereof on an inactive carrier having a predetermined shape.
Examples of the method for molding the catalyst include a method of molding a catalyst precursor into a predetermined shape by extrusion molding, tablet molding, or the like. These methods may be appropriately selected and used in combination. The catalyst precursor may be mixed with a powdery inactive material and used in the molding step.
Further, as a method for supporting the catalyst, for example, a method described in Japanese patent application laid-open Nos. 6-381 and 10-28877, etc., can be used to support the catalyst precursor on the inactive carrier.
Examples of the inactive carrier for supporting the catalyst precursor include alumina, silica-alumina, titania, magnesia, steatite, cordierite, silica-magnesia, silicon carbide, silicon nitride, zeolite, and the like. The shape is also not particularly limited, and known shapes such as spherical, annular, granular, and amorphous shapes can be used. When the carrier is spherical, the diameter is preferably in the range of 2 to 10mm, and the amount of the catalytically active component supported on the inactive carrier is preferably in the range of 20 to 300% by mass.
The catalyst shape is not particularly limited, and may be any of spherical, cylindrical, annular, amorphous, and the like, when the catalyst is spherical, the diameter is preferably in the range of 4 to 12 mm. Of course, in the case of a spherical shape, it is not necessary to be a perfect sphere, but it is sufficient that the spherical shape is substantially spherical, and in the case of a cylindrical shape and an annular shape, the sectional shape is not necessarily a perfect circle, either, but it is sufficient that the spherical shape is substantially circular.
In the molding step and the supporting step, a molding aid for improving moldability, a supporting aid for improving a supporting state, a binder, and the like may be used. Specific examples thereof include organic compounds such as ethylene glycol, glycerin, propionic acid, maleic acid, benzyl alcohol, propanol, butanol and phenols, nitric acid, ammonium nitrate and ammonium carbonate.
In addition, for the purpose of improving mechanical strength, inorganic fibers such as glass fibers, ceramic fibers, metal fibers, mineral fibers, carbon fibers, silica, alumina, titanium oxide, silicon carbide, and silicon nitride, which are generally known, may be added to the catalyst as a reinforcing material.
The method of adding these inorganic fibers is not particularly limited, and any method may be used as long as the inorganic fibers can be uniformly dispersed and contained in the catalyst. For example, the inorganic fiber may be added to the raw material mixture containing the catalyst component element, or the inorganic fiber may be added to the catalyst precursor obtained by drying and pulverizing the raw material mixture containing the catalyst component element.
In addition, a pore-forming agent may be added for the purpose of forming appropriate fine pores in the catalyst. The pore-forming agent is not particularly limited, and starch, cellulose, urea, polyvinyl alcohol, melamine cyanurate, and the like can be used.
(6) Firing Process
In the present invention, the firing step is a step of subjecting the molded article obtained in the molding step or the carrier obtained in the carrying step to a heating treatment at a high temperature.
The firing furnace used in the firing step is not particularly limited, and a box-type firing furnace, a tunnel-type firing furnace, or the like, which is generally used, may be used. The firing temperature is 350 to 600 ℃, preferably 400 to 550 ℃, more preferably 420 to 500 ℃, and the firing time is 1 to 15 hours, preferably 2 to 10 hours. The firing atmosphere may be an oxidizing atmosphere, and is preferably a gas atmosphere containing molecular oxygen. As the molecular oxygen-containing gas, air is preferably used.
Next, the method for producing acrolein and acrylic acid according to the present invention will be described. The method for producing acrolein and acrylic acid of the present invention is a method for catalytic gas phase oxidation of propylene using the catalyst obtained by the production method of the present invention, that is, a method comprising a step of obtaining the catalyst by the production method of the present invention and a step of catalytic gas phase oxidation of propylene using the catalyst. In the method for producing acrolein and acrylic acid of the present invention, it is preferable that the catalyst obtained by the production method of the present invention is filled in a reaction tube in a reactor, and a raw material gas containing propylene and molecular oxygen is introduced into the reaction tube to perform a catalytic gas phase oxidation reaction.
The reactor for producing acrolein and acrylic acid by catalytic gas phase oxidation of propylene in the present invention is not particularly limited as long as it is a fixed bed reactor, and a fixed bed multitubular reactor, a plate reactor, and the like which are generally used can be used, and a fixed bed multitubular reactor is preferred. The inner diameter of the reaction tube in the fixed-bed multitubular reactor is usually 15 to 50mm, more preferably 20 to 40mm, and still more preferably 22 to 38mm.
The fixed-bed multitubular reactor does not necessarily need to be packed with a single catalyst in each reaction tube, and a plurality of known catalysts may be packed so as to form layers (hereinafter, sometimes referred to as "reaction zones") separately. For example, a method of filling catalysts having different supporting ratios so that the supporting ratio is increased from the raw material gas inlet side to the outlet side, a method of diluting a part of the catalyst with an inactive carrier or the like, or a method of combining these methods may be employed. In this case, the number of reaction zones is appropriately determined depending on the reaction conditions and the scale of the reactor, but if the number of reaction zones is too large, the operation of filling the catalyst becomes complicated, and the like, and therefore, it is industrially preferable to be about 2 to 6.
The reaction conditions in the present invention are not particularly limited, and any reaction conditions can be used as long as they are generally used in such reactions. For example, propylene in an amount of preferably 1 to 15% by volume, more preferably 4 to 12% by volume; preferably 0.5 to 25% by volume, more preferably 2 to 20% by volume, of molecular oxygen; preferably 0 to 30% by volume, more preferably 0 to 25% by volume, of water vapor; and a mixed gas composed of an inert gas such as nitrogen and the like as the balance, at a temperature of 250 to 450 ℃ and a pressure of 0.1 to 1.0MPa, at 300 to 5000Hr -1 The space velocity (in the normal state) may be in contact with the catalyst.
The grade of propylene as the reaction raw material gas is not particularly limited, and polymer grade, chemical grade propylene, or the like can be used. Further, a mixed gas containing propylene obtained by an oxidative dehydrogenation reaction of propane may be used, or air, oxygen, or the like may be added to the mixed gas as necessary.
[ examples ] A method for producing a compound
The present invention will be described in further detail with reference to the following examples and comparative examples. However, the technical scope of the present invention is not limited to the following examples. Unless otherwise specified, "%" and "part" mean "% by mass" and "part by mass", respectively. In the following examples, the operation was carried out at room temperature (20 to 25 ℃ C.) unless otherwise specified. The conversion and yield in examples and comparative examples were determined by the following formulas.
Conversion [ mol% ]
= (mol number of propylene reacted)/(mol number of propylene supplied) × 100
Yield [ mol% ]
= (total mol number of produced acrolein and produced acrylic acid)/(mol number of supplied propylene) × 100.
[ experiment 1 experiment on cobalt starting material Compound ]
[ preparation of cobalt nitrate hexahydrate ]
The cobalt nitrate hexahydrate was appropriately combined with the treatments (humidity at the storage site, storage amount (amount filled in the container), storage period) of the adjustment step, thereby preparing the mass reduction rate L shown in table 1 1 Cobalt nitrate hexahydrate.
[ measurement of the Mass loss Rate ]
As a sample for determining the mass loss rate, cobalt nitrate hexahydrate (W) in an amount (about 20 mg) required for thermogravimetric analysis was precisely weighed in an aluminum pan 1 : cobalt nitrate hexahydrate mass at room temperature) to prepare the assay samples. Then, the measurement sample was set in a sample holder of a thermogravimetric analysis (TG) device (device name: 2000S, manufactured by McScience), and then the temperature was increased from room temperature of 25 ℃ or lower to 300 ℃ at a rate of 2 ℃ per minute, and the mass of the sample was measured as a function of the temperature. The mass loss rate L of cobalt nitrate hexahydrate was determined from the change in mass of the sample 1 And the mass loss rate L of cobalt nitrate hexahydrate 2 Calculated by the following formulae (a) and (b). In addition, the mass loss rate L of cobalt nitrate hexahydrate 1 The ratio R of (A) is calculated by the following formula (c). The mass loss rate L of cobalt nitrate hexahydrate 3 Is the mass reduction rate L of cobalt nitrate hexahydrate 1 Mass loss rate L with cobalt nitrate hexahydrate 2 And (4) summing.
L 1 (mass%) = (W) 1 -W 2 )/W 1 ×100 (a)
L 2 (mass%) = (W) 2 -W 3 )/W 1 ×100 (b)
R＝L 1 /(L 1 +L 2 )＝L 1 /L 3 (c)
Wherein, W 1 = cobalt nitrate hexahydrate mass at 25 ℃ (mg)
W 2 = cobalt nitrate hexahydrate mass at 105 ℃ (mg)
W 3 = mass of cobalt nitrate hexahydrate (mg) at 300 ℃.
[ catalyst production example 1: preparation of catalyst (1)
340 parts of cobalt (II) nitrate hexahydrate and 82 parts of nickel (II) nitrate hexahydrate were dissolved in 400 parts of ion-exchanged water to prepare Co and Ni aqueous solutions. The mass loss rate L of the cobalt nitrate hexahydrate calculated by thermogravimetric analysis of the cobalt nitrate hexahydrate used at this time 1 11.2 mass%, the mass loss rate L of cobalt nitrate hexahydrate 3 66.9% by mass, the mass loss rate L of cobalt nitrate hexahydrate 1 Is 0.167. Further, the mass loss rate L of nickel nitrate hexahydrate at 25 ℃ to 105 ℃ calculated by thermogravimetric analysis of nickel nitrate hexahydrate used 1 14.7% by mass, the mass loss rate L of nickel nitrate hexahydrate at 25 ℃ to 300 ℃ 3 41.4% by mass, the mass reduction rate L of nickel nitrate hexahydrate at 25 ℃ to 105 ℃ 1 Mass loss rate L relative to nickel nitrate hexahydrate at 25 ℃ to 300 ℃ 3 The ratio R of (A) is 0.355. In addition, for nitrates other than cobalt nitrate hexahydrate, W can also be measured by performing the same thermogravimetric analysis 1 Mass of nitrate (mg) at 25 ℃ W 2 = mass of nitrate (mg) at 105 ℃ W 3 = mass (mg) of nitrate at 300 ℃ and the mass loss rate L of nitrate at 25 ℃ to 105 ℃ is calculated from the respective formulae (a) to (c) 1 Mass reduction rate L of nitrate at 105 ℃ to 300 ℃ 2 And a mass reduction rate L of nitrate of 25 ℃ to 105 ℃ 1 Mass reduction rate L relative to nitrate from 25 ℃ to 300 ℃ 3 The ratio of (A) to (B).
Next, 99 parts of iron nitrate (iron (III) nitrate nonahydrate) and 119 parts of bismuth (III) nitrate pentahydrate were dissolved in 65 parts of 65 mass% nitric acid and ion-exchangedAnd (3) preparing an aqueous solution of Fe and Bi in 300 parts of aqueous nitric acid solution. The mass loss rate L of the iron nitrate from 25 ℃ to 105 ℃ calculated by thermogravimetric analysis of the iron nitrate used at this time 1 28.5 mass percent mass reduction rate L of iron nitrate from 25 ℃ to 300 ℃ 3 63.5% by mass, the mass reduction rate L of iron nitrate at 25 to 105 ℃ 1 Mass reduction rate L relative to iron nitrate of 25 to 300 DEG C 3 Is 0.449. Further, the mass loss rate L of bismuth (III) nitrate pentahydrate from 25 ℃ to 105 ℃ calculated by thermogravimetric analysis of the bismuth (III) nitrate pentahydrate used 1 13.0 mass%, and the mass reduction rate L of bismuth nitrate (III) pentahydrate from 25 ℃ to 300 ℃ 3 53.2% by mass, the mass loss rate L of bismuth (III) nitrate pentahydrate from 25 ℃ to 105 ℃ 1 The mass reduction rate L relative to bismuth (III) nitrate pentahydrate from 25 ℃ to 300 DEG C 3 Is 0.244. Further, 400 parts of ammonium paramolybdate (VI) tetrahydrate was added to 1500 parts of ion-exchanged water and dissolved with stirring to prepare an Mo aqueous solution. The separately prepared Fe and Bi aqueous solutions and Mo aqueous solutions were added dropwise to the Co and Ni aqueous solutions and mixed, then 3 parts of titanium oxide was mixed, and then an aqueous solution prepared by dissolving 1.9 parts of potassium nitrate in 30 parts of ion-exchanged water was added to obtain a suspension (raw material mixture). And heating the obtained suspension, stirring the suspension into a cake, and naturally cooling the cake to obtain a blocky solid matter.
The solid matter in the form of a lump was carried into a tunnel dryer, dried at 170 ℃ for 14 hours, and then pulverized to 500 μm or less to obtain a catalyst precursor powder. 300 parts of alumina spherical carrier having an average particle diameter of 5.0mm was put into a rotary granulator, and then powder of a catalyst precursor was gradually put into the granulator together with a 20 mass% ammonium nitrate aqueous solution as a binder to support the catalyst precursor on the carrier, followed by firing at 470 ℃ for 6 hours in an air atmosphere, thereby obtaining a catalyst (1). The catalyst (1) has a metal element composition of "Mo" excluding oxygen and the carrier 12 Bi 1.3 Co 6.1 Ni 1.5 Fe 1.3 Ti 0.2 K 0.1 ”。
The loading rate of the catalyst (1) calculated by the following formula (d) was 130 mass%.
A loading rate (% by mass) = (mass of catalyst-mass of support)/(mass of support) × 100 formula (d).
[ catalyst production example 2: preparation of catalyst (2)
In catalyst production example 2, the mass loss rate L of cobalt nitrate hexahydrate calculated by thermogravimetric analysis of cobalt nitrate hexahydrate used 1 13.0 mass%, the mass loss rate L of cobalt nitrate hexahydrate 3 68.8% by mass, the mass loss rate L of cobalt nitrate hexahydrate 1 The ratio R of (A) is 0.189.
In catalyst production example 2, L was considered to be the same as the catalyst (1) in order to obtain the same cobalt composition in the obtained catalyst 1 The amount of cobalt nitrate hexahydrate and L thereof were considered to be 346 parts, so that the total water content in the system in the preparation of the aqueous Co and Ni solutions was the same 1 A catalyst was prepared in the same manner as in catalyst production example 1 except that 394 parts of water was used for the preparation of the Co and Ni aqueous solutions, to obtain a catalyst (2).
[ catalyst production example 3: preparation of catalyst (3)
In catalyst production example 3, the mass loss rate L of cobalt nitrate hexahydrate calculated by thermogravimetric analysis of cobalt nitrate hexahydrate used 1 14.0 mass%, the mass loss rate L of cobalt nitrate hexahydrate 3 69.9% by mass, the mass loss rate L of cobalt nitrate hexahydrate 1 The ratio R of (A) to (B) is 0.200.
In catalyst production example 3, L was considered to be the same as the catalyst (1) in order to obtain the same cobalt composition in the obtained catalyst 1 The value of (3) is 349 parts of cobalt nitrate hexahydrate, and the amount of cobalt nitrate hexahydrate and its L are considered to equalize the total water content in the system in the preparation of Co and Ni aqueous solutions 1 A catalyst was prepared in the same manner as in catalyst production example 1 except that the amount of water used in the preparation of the aqueous solution of Co and Ni was 391 parts, to obtain a catalyst (3).
[ catalyst production example 4: preparation of catalyst (4)
In catalyst production example 4, the mass loss rate L of cobalt nitrate hexahydrate calculated by thermogravimetric analysis of cobalt nitrate hexahydrate used 1 14.2 mass%, the mass loss rate L of cobalt nitrate hexahydrate 3 70.1% by mass, the mass loss rate L of cobalt nitrate hexahydrate 1 The ratio R of (A) is 0.203.
In catalyst production example 4, L was considered to be the same as the catalyst (1) in order to obtain the same cobalt composition in the obtained catalyst 1 The value of (2) is 350 parts, and the amount of cobalt nitrate hexahydrate and its L are considered to equalize the total water content in the system in the production of aqueous solutions of Co and Ni 1 A catalyst was prepared in the same manner as in catalyst production example 1 except that the amount of water used in the preparation of the aqueous solutions of Co and Ni was 390 parts, to obtain a catalyst (4).
[ catalyst production example 5: preparation of catalyst (5)
Catalyst production example 5 mass loss rate L of cobalt nitrate hexahydrate calculated by thermogravimetric analysis of cobalt nitrate hexahydrate used 1 15.8 mass%, mass loss rate L of cobalt nitrate hexahydrate 3 70.9% by mass, the mass loss rate L of cobalt nitrate hexahydrate 1 Is 0.223.
In catalyst production example 5, L was considered to be the same as that of catalyst (1) in order to obtain the same cobalt composition in the obtained catalyst 1 The value of (2) is 355 parts of cobalt nitrate hexahydrate, and the amount of cobalt nitrate hexahydrate and its L are considered to equalize the total water content in the system in the production of aqueous solutions of Co and Ni 1 A catalyst was prepared in the same manner as in catalyst production example 1 except that the amount of water used in the preparation of the aqueous solution of Co and Ni was 385 parts, to obtain a catalyst (5).
Catalyst production example 6: preparation of catalyst (6)
In catalyst production example 6, the mass loss rate L of cobalt nitrate hexahydrate calculated by thermogravimetric analysis of cobalt nitrate hexahydrate used 1 10.7% by mass, the mass loss rate L of cobalt nitrate hexahydrate 3 66.2% by mass, the mass loss rate L of cobalt nitrate hexahydrate 1 Is 0.162.
In catalyst production example 6, L was considered to be the same as that of catalyst (1) in order to obtain the same cobalt composition in the obtained catalyst 1 Assuming that the total water content in the system for producing the aqueous solution of Co and Ni was the same, the amount of cobalt nitrate hexahydrate and L thereof were considered to be 338 parts 1 A catalyst was prepared in the same manner as in catalyst preparation example 1 except that the amount of water used in the preparation of the Co and Ni aqueous solution was 402 parts, to obtain a catalyst (6).
Catalyst production example 7: preparation of catalyst (7)
In catalyst production example 7, the mass loss rate L of cobalt nitrate hexahydrate calculated by thermogravimetric analysis of cobalt nitrate hexahydrate used 1 16.5 mass%, the mass loss rate L of cobalt nitrate hexahydrate 3 72.1% by mass, the mass loss rate L of cobalt nitrate hexahydrate 1 Is 0.229.
In catalyst production example 7, L was considered to be the same in order to make the cobalt composition in the obtained catalyst the same 1 The amount of cobalt nitrate hexahydrate and L thereof were considered to be 358 parts so that the total water content in the system in the production of aqueous solutions of Co and Ni would be the same 1 A catalyst was prepared in the same manner as in catalyst production example 1 except that the amount of water used in the preparation of the aqueous solutions of Co and Ni was 382 parts, to obtain a catalyst (7).
Experiment 2 experiment on raw material compounds of iron, bismuth and nickel
Next, the raw materials of iron, bismuth and nickel were processed in the same manner as the raw material of cobalt of experiment 1 based on the mass reduction rate L 1 Catalysts (8) to (10) were produced in which the amounts of the raw materials for the respective elements were adjusted. The raw materials of the respective elements were operated in the same manner as in the cobalt nitrate hexahydrate of experiment 1, and the humidity of the storage place, the storage amount (amount filled in the container) and the storage period were adjusted by appropriately combining the raw materials to prepare the mass reduction rates L shown in table 2 1 Each raw material (iron nitrate nonahydrate)Bismuth (III) nitrate pentahydrate, and nickel nitrate hexahydrate).
[ catalyst production example 8: preparation of catalyst (8) ]
In catalyst production example 8, the mass loss rate L of iron nitrate nonahydrate from 25 ℃ to 105 ℃ was calculated by thermogravimetric analysis of the iron nitrate nonahydrate used 1 38.2 mass%, and a mass reduction rate L of iron nitrate nonahydrate at 25 to 300 DEG C 3 81.0% by mass, a mass reduction rate L of iron nitrate nonahydrate at 25 to 105 ℃ 1 Mass loss rate L relative to iron nitrate nonahydrate from 25 ℃ to 300 ℃ 3 The ratio R of (A) is 0.472.
In catalyst production example 8, L was considered to be the same as that of catalyst (1) in terms of Fe composition in the obtained catalyst 1 The amount of iron nitrate nonahydrate was set to 109 parts, and the amount of iron nitrate nonahydrate and L thereof were considered to equalize the total water content in the system 1 A catalyst (8) was obtained by preparing the catalyst in the same manner as in catalyst preparation example 1, except that the amount of water used in the preparation of the aqueous solution of Fe and Bi was 291 parts.
Catalyst production example 9: preparation of catalyst (9)
In catalyst production example 9, the mass loss rate L of bismuth (III) nitrate pentahydrate from 25 ℃ to 105 ℃ calculated by thermogravimetric analysis of the bismuth (III) nitrate pentahydrate used 1 18.6% by mass, the mass loss rate L of bismuth nitrate (III) pentahydrate from 25 ℃ to 300 ℃ 3 59.4% by mass, a mass loss rate L of bismuth (III) nitrate pentahydrate from 25 ℃ to 105 ℃ 1 The mass reduction rate L relative to bismuth (III) nitrate pentahydrate from 25 ℃ to 300 ℃ 3 Is 0.313.
In catalyst production example 9, L was considered to be the same as that of catalyst (1) in terms of Bi composition in the obtained catalyst 1 The amount of bismuth (III) nitrate pentahydrate was 126 parts, and the amount of bismuth (III) nitrate pentahydrate and L thereof were considered to equalize the total water content in the system 1 The amount of water used for preparing the aqueous solution of Fe and Bi was 294 parts, except forCatalyst production example 1 a catalyst was prepared in the same manner to obtain a catalyst (9).
Catalyst production example 10: preparation of catalyst (10)
In catalyst production example 10, the mass loss rate L of nickel nitrate hexahydrate at 25 ℃ to 105 ℃ was calculated from thermogravimetric analysis of nickel nitrate hexahydrate used 1 19.9% by mass, the mass loss rate L of nickel nitrate hexahydrate at 25 ℃ to 300 ℃ 3 47.6 mass%, mass reduction rate L of nickel nitrate hexahydrate at 25 to 105 ℃ 1 Mass loss rate L relative to nickel nitrate hexahydrate at 25 ℃ to 300 ℃ 3 Is 0.418.
In catalyst production example 10, L was considered to be the same as that of catalyst (1) in order to obtain the same Ni composition in the obtained catalyst 1 The amount of nickel nitrate hexahydrate and its L were considered to be 86 parts, so that the total water content in the system was the same 1 A catalyst was prepared in the same manner as in catalyst production example 1 except that the amount of water used for preparing the aqueous solution of Co and Ni was 397 parts, thereby obtaining a catalyst (10).
[ reactor ]
A reactor comprising a reaction tube made of stainless steel having a total length of 3000mm and an inner diameter of 25mm and a shell for allowing a heat medium covering the reaction tube to flow was prepared in the vertical direction, and each of the obtained catalysts (1) to (10) was dropped from the upper part of the reaction tube and filled so that the layer growth became 2500 mm.
[ Oxidation reaction ]
In examples 1 to 5 and comparative examples 1 and 2, the space velocity was 1600hr from the lower part of the reactor filled with each of the catalysts (1) to (7) respectively -1 A mixed gas containing 7.0 vol% of propylene, 13 vol% of oxygen, 8.5 vol% of water vapor and the balance of nitrogen was introduced (as a standard state) to carry out the propylene oxidation reaction at a heat medium temperature of 310 ℃. The results are shown in table 1. In examples 6 to 8, the catalysts (8) to (10) were packed, and the propylene oxidation reaction was carried out under the same conditions. The results are shown in Table 2.
[ TABLE 1 ]
[ TABLE 2 ]
The results of experiment 1 (Table 1) show that the mass reduction rate L is used 1 In examples 1 to 5 in which the catalysts (1) to (5) were 11 to 16% by mass, the propylene conversion rate was 97.0mol% or more, and the yields of acrolein and acrylic acid were 91.5mol% or more. On the other hand, the mass reduction rate L is used 1 In comparative examples 1 and 2 in which the amount of the catalysts (6) and (7) was less than 11% by mass or more than 16% by mass, the propylene conversion was less than 97.0mol%, and the yields of acrolein and acrylic acid were less than 91.5mol%. Therefore, it is known that the mass reduction rate L is used 1 The catalysts (1) to (5) produced from 11 to 16 mass% of cobalt nitrate hexahydrate are excellent in catalytic activity and yield in the production of acrolein and acrylic acid, and by using the catalysts, acrolein and acrylic acid can be produced in high yield.
From the results of experiment 2 (Table 2), it was found that the mass reduction rate L of the nitrate of the raw material other than cobalt 1 Has no influence on the conversion rate of propylene and the yield of acrolein and acrylic acid, or has a mass reduction rate L with cobalt nitrate hexahydrate 1 Compared to a small effect.
The present application is based on Japanese patent application No. 2021-057249, applied on 3/30/2021, and Japanese patent application No. 2021-207846, applied on 12/22/2021, the disclosures of which are incorporated herein by reference in their entirety.
Claims (3)
1. A process for producing a catalyst for use in the catalytic gas phase oxidation of propylene to produce acrolein and acrylic acid,
the method for producing the catalyst comprises a step of mixing a raw material mixture containing a raw material compound of molybdenum, a raw material compound of bismuth and a raw material compound of cobalt,
the raw material compound of the cobalt is cobalt nitrate hexahydrate,
a mass loss rate L from 25 ℃ to 105 ℃ in thermogravimetric analysis of the cobalt nitrate hexahydrate represented by the following formula (a) 1 Is 11 to 16% by mass,
L 1 ＝(W 1 -W 2 )/W 1 ×100 (a)，
wherein, W 1 The mass of cobalt nitrate hexahydrate at 25 ℃,
W 2 to achieve a mass of cobalt nitrate hexahydrate at 105 c,
wherein L is 1 The unit of (A) is mass%, W 1 And W 2 The unit of (a) is in mg.
2. The method for producing a catalyst according to claim 1, wherein the catalyst comprises a composite oxide represented by the following general formula (1),
Mo 12 Bi a Co b A c B d C e D f (1)，
in formula (1), mo is molybdenum, bi is bismuth, co is cobalt, A is at least 1 element selected from iron and nickel, B is at least 1 element selected from alkali metals, alkaline earth metals and thallium, C is at least 1 element selected from tungsten, silicon, aluminum, zirconium and titanium, D is at least 1 element selected from phosphorus, tellurium, antimony, tin, cerium, lead, niobium, manganese, arsenic, boron and zinc, a, B, C, D, e and f represent the atomic numbers of Bi, co, A, B, C and D, 0 < a < 10, 0 < B < 20, 0 < C < 20, 0 < D < 10, 0 < e < 30, 0 < f < 4, and formula (1) does not include oxygen representing the oxidation state.
3. A process for producing acrolein and acrylic acid, which comprises subjecting propylene to catalytic gas phase oxidation using the catalyst obtained by the production process according to claim 1 or 2.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2021-057249 | 2021-03-30 | ||
| JP2021057249 | 2021-03-30 | ||
| JP2021-207846 | 2021-12-22 | ||
| JP2021207846A JP2022155470A (en) | 2021-03-30 | 2021-12-22 | Method for producing catalyst for producing acrolein and acrylic acid, and method for producing acrolein and acrylic acid using the catalyst |
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| Publication Number | Publication Date |
|---|---|
| CN115141089A true CN115141089A (en) | 2022-10-04 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210216207.7A Pending CN115141089A (en) | 2021-03-30 | 2022-03-07 | Method for producing catalyst for production of acrolein and acrylic acid, and method for producing acrolein and acrylic acid using the catalyst |
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| Country | Link |
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| CN (1) | CN115141089A (en) |
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