JPH09122490A - Catalyst precursor for synthesizing methacrolein and methacrylic acid - Google Patents
Catalyst precursor for synthesizing methacrolein and methacrylic acidInfo
- Publication number
- JPH09122490A JPH09122490A JP7283925A JP28392595A JPH09122490A JP H09122490 A JPH09122490 A JP H09122490A JP 7283925 A JP7283925 A JP 7283925A JP 28392595 A JP28392595 A JP 28392595A JP H09122490 A JPH09122490 A JP H09122490A
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- catalyst precursor
- methacrylic acid
- precursor
- ray diffraction
- 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
Links
- 239000012018 catalyst precursor Substances 0.000 title claims abstract description 40
- STNJBCKSHOAVAJ-UHFFFAOYSA-N Methacrolein Chemical compound CC(=C)C=O STNJBCKSHOAVAJ-UHFFFAOYSA-N 0.000 title claims abstract description 18
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 230000002194 synthesizing effect Effects 0.000 title abstract description 3
- 239000003054 catalyst Substances 0.000 claims abstract description 50
- 238000002441 X-ray diffraction Methods 0.000 claims abstract description 18
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical group [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 11
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 7
- 239000001301 oxygen Substances 0.000 claims abstract description 7
- 239000011701 zinc Chemical group 0.000 claims abstract description 6
- 229910017052 cobalt Chemical group 0.000 claims abstract description 5
- 239000010941 cobalt Chemical group 0.000 claims abstract description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical group [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000011777 magnesium Substances 0.000 claims abstract description 5
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 5
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 5
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical group [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical group [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052792 caesium Inorganic materials 0.000 claims abstract description 4
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000011133 lead Substances 0.000 claims abstract description 4
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 4
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical group [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 abstract description 4
- 239000011574 phosphorus Substances 0.000 claims abstract description 4
- 229910052701 rubidium Inorganic materials 0.000 claims abstract description 4
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052714 tellurium Inorganic materials 0.000 claims abstract description 4
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 claims abstract description 4
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims abstract description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052796 boron Inorganic materials 0.000 claims abstract description 3
- 229910052732 germanium Inorganic materials 0.000 claims abstract description 3
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000011591 potassium Substances 0.000 claims abstract description 3
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 3
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 3
- 239000010703 silicon Substances 0.000 claims abstract description 3
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 3
- 239000011734 sodium Substances 0.000 claims abstract description 3
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 3
- 239000011593 sulfur Substances 0.000 claims abstract description 3
- 229910052716 thallium Inorganic materials 0.000 claims abstract description 3
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000011135 tin Substances 0.000 claims abstract description 3
- 229910052718 tin Inorganic materials 0.000 claims abstract description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 18
- 230000015572 biosynthetic process Effects 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 12
- 229910052742 iron Inorganic materials 0.000 claims description 9
- 238000003786 synthesis reaction Methods 0.000 claims description 7
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 5
- 229910052797 bismuth Inorganic materials 0.000 claims description 5
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 5
- 229910052750 molybdenum Inorganic materials 0.000 claims description 5
- 239000011733 molybdenum Substances 0.000 claims description 5
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 4
- 229910052787 antimony Chemical group 0.000 claims description 3
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical group [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 3
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical group [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 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical group [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 2
- 229910052758 niobium Inorganic materials 0.000 claims description 2
- 239000010955 niobium Chemical group 0.000 claims description 2
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical group [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 239000010936 titanium Chemical group 0.000 claims description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical group [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 239000010937 tungsten Chemical group 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- 239000002243 precursor Substances 0.000 abstract description 4
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 15
- 239000000243 solution Substances 0.000 description 15
- 238000000034 method Methods 0.000 description 14
- 238000003756 stirring Methods 0.000 description 14
- 238000002156 mixing Methods 0.000 description 11
- 239000002002 slurry Substances 0.000 description 11
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 10
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 9
- 238000001354 calcination Methods 0.000 description 9
- 239000011259 mixed solution Substances 0.000 description 9
- 239000002994 raw material Substances 0.000 description 9
- 239000006185 dispersion Substances 0.000 description 8
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 7
- 230000003197 catalytic effect Effects 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 238000005755 formation reaction Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 229910001882 dioxygen Inorganic materials 0.000 description 5
- 238000001035 drying Methods 0.000 description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000011268 mixed slurry Substances 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- NLSCHDZTHVNDCP-UHFFFAOYSA-N caesium nitrate Chemical compound [Cs+].[O-][N+]([O-])=O NLSCHDZTHVNDCP-UHFFFAOYSA-N 0.000 description 2
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 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 2
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-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
- 150000002823 nitrates Chemical class 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- KYYSIVCCYWZZLR-UHFFFAOYSA-N cobalt(2+);dioxido(dioxo)molybdenum Chemical compound [Co+2].[O-][Mo]([O-])(=O)=O KYYSIVCCYWZZLR-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- RLJMLMKIBZAXJO-UHFFFAOYSA-N lead nitrate Chemical compound [O-][N+](=O)O[Pb]O[N+]([O-])=O RLJMLMKIBZAXJO-UHFFFAOYSA-N 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000005078 molybdenum compound Substances 0.000 description 1
- 150000002752 molybdenum compounds Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000001028 reflection method Methods 0.000 description 1
- RTHYXYOJKHGZJT-UHFFFAOYSA-N rubidium nitrate Inorganic materials [Rb+].[O-][N+]([O-])=O RTHYXYOJKHGZJT-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid 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
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- LAJZODKXOMJMPK-UHFFFAOYSA-N tellurium dioxide Chemical compound O=[Te]=O LAJZODKXOMJMPK-UHFFFAOYSA-N 0.000 description 1
- KHAUBYTYGDOYRU-IRXASZMISA-N trospectomycin Chemical compound CN[C@H]([C@H]1O2)[C@@H](O)[C@@H](NC)[C@H](O)[C@H]1O[C@H]1[C@]2(O)C(=O)C[C@@H](CCCC)O1 KHAUBYTYGDOYRU-IRXASZMISA-N 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、メタクロレイン及
びメタクリル酸合成用触媒前駆体に関する。更に詳しく
はイソブチレン又は三級ブタノールを分子状酸素により
気相接触酸化して、メタクロレイン及びメタクリル酸を
合成する際に使用する触媒の前駆体に関する。TECHNICAL FIELD The present invention relates to a catalyst precursor for methacrolein and methacrylic acid synthesis. More specifically, it relates to a precursor of a catalyst used in the gas-phase catalytic oxidation of isobutylene or tertiary butanol with molecular oxygen to synthesize methacrolein and methacrylic acid.
【０００２】[0002]
【従来の技術】従来、イソブチレン又は三級ブタノール
を高温気相下で接触酸化してメタクロレイン及びメタク
リル酸を製造する際に用いられる触媒に関しては、特開
昭５５−４３１０号公報、特開昭５６−４６８３２号公
報、特開昭５５−５７５３３号公報、特開昭６０−２８
８２４号公報等数多くの提案がなされている。2. Description of the Related Art Conventionally, catalysts used in the production of methacrolein and methacrylic acid by catalytically oxidizing isobutylene or tertiary butanol under a high temperature gas phase are disclosed in JP-A-55-4310 and JP-A-55-4310. 56-46832, JP-A-55-57533, JP-A-60-28
Many proposals have been made such as Japanese Patent No. 824.
【０００３】しかしながらこれらは主として触媒を構成
する成分及びその含有量比率に関するものであり、かか
るメタクロレイン及びメタクリル酸を製造するのに用い
る触媒の前駆体の詳細な構造にまで言及されているもの
はない。However, these are mainly related to the components constituting the catalyst and the content ratio thereof, and even the detailed structures of the precursors of the catalyst used for producing such methacrolein and methacrylic acid are mentioned. Absent.
【０００４】Ｍｏ−Ｂｉ−Ｆｅ系を必須成分として有す
る複合酸化物触媒はイソブチレン又は三級ブタノールを
分子状酸素により気相接触酸化して、メタクロレイン及
びメタクリル酸を合成する際の触媒として多用されてい
るものであるが、その触媒の前駆体、いわゆる仮焼成段
階における構造と最終的な触媒性能との関係について詳
しい報告例がほとんどないのが実状である。工業的見地
から、高活性・高選択性な触媒を再現性よく得るため
に、好ましい触媒前駆体構造に関する更なる新規な知見
が望まれている。A complex oxide catalyst having a Mo-Bi-Fe system as an essential component is often used as a catalyst for synthesizing methacrolein and methacrylic acid by vapor-phase catalytic oxidation of isobutylene or tertiary butanol with molecular oxygen. However, there are few detailed reports on the relationship between the catalyst precursor, that is, the structure at the so-called calcination stage and the final catalyst performance. From an industrial point of view, in order to obtain a highly active and highly selective catalyst with good reproducibility, further new findings regarding a preferable catalyst precursor structure are desired.
【０００５】[0005]
【発明が解決しようとする課題】本発明は、メタクロレ
イン及びメタクリル酸合成用触媒として十分な触媒性能
を安定にしかも再現性よく付与することができる触媒前
駆体を提供することを目的とする。SUMMARY OF THE INVENTION It is an object of the present invention to provide a catalyst precursor capable of stably and reproducibly providing sufficient catalytic performance as a catalyst for methacrolein and methacrylic acid synthesis.
【０００６】[0006]
【課題を解決するための手段】本発明は、下記一般式
（Ｉ）で表される触媒成分から構成され、且つＸ線回折
（対陰極Ｃｕ−Ｋα）における２θ＝約９．５°のピー
ク強度の２θ＝約２６．４°のピーク強度に対する比で
定義されるＫ値が１．２以下であることを特徴とするメ
タクロレイン及びメタクリル酸合成用触媒前駆体であ
る。The present invention comprises a catalyst component represented by the following general formula (I) and has a peak at 2θ = about 9.5 ° in X-ray diffraction (cathode Cu-Kα). The catalyst precursor for methacrolein and methacrylic acid synthesis is characterized in that the K value defined by the ratio of the intensity to the peak intensity at 2θ = about 26.4 ° is 1.2 or less.
【０００７】 ＭｏaＢｉbＦｅcＡdＸeＹfＺgＯh （Ｉ） （式中、Ｍｏ、Ｂｉ、Ｆｅ及びＯはそれぞれモリブデ
ン、ビスマス、鉄及び酸素を表し、Ａはニッケル及びコ
バルトからなる群より選ばれた少なくとも１種の元素、
Ｘはマグネシウム、亜鉛、マンガン、スズ及び鉛からな
る群より選ばれた少なくとも１種の元素、Ｙはリン、ホ
ウ素、イオウ、テルル、ケイ素、ゲルマニウム、セリウ
ム、ニオブ、チタン、ジルコニウム、タングステン及び
アンチモンからなる群より選ばれた少なくとも１種の元
素、Ｚはナトリウム、カリウム、ルビジウム、セシウム
及びタリウムからなる群より選ばれた少なくとも１種の
元素を表す。ただし、ａ、ｂ、ｃ、ｄ、ｅ、ｆ、ｇ及び
ｈは各元素の原子比を表し、ａ＝１２のとき、０．１≦
ｂ≦５、０．１≦ｃ≦５、１≦ｄ≦１２、０≦ｅ≦１
０、０≦ｆ≦１０、０．０１≦ｇ≦３であり、ｈは前記
各成分の原子比を満足するのに必要な酸素原子数であ
る。） 本発明は、本発明者らがメタクロレイン及びメタクリル
酸合成用触媒を調製する方法において、調製過程におけ
る触媒前駆体について種々の構造解析を行った結果、驚
くべきことにその詳細な理由については定かではない
が、２００〜４００℃の温度範囲で仮焼成した触媒前駆
体が、Ｘ線回折（対陰極Ｃｕ−Ｋα）における２θ＝約
９．５°のピーク強度の２θ＝約２６．４°のピーク強
度に対する比で定義されるＫ値がある一定値以下である
ものが、従来提案されているメタクロレイン及びメタク
リル酸合成用触媒とは異なる常に安定なしかも再現性良
好な触媒となし得るという知見に基づいて到達したもの
である。Mo a Bi b Fe c A d X e Y f Z g O h (I) (wherein Mo, Bi, Fe and O represent molybdenum, bismuth, iron and oxygen, respectively, and A is nickel and cobalt. At least one element selected from the group consisting of
X is at least one element selected from the group consisting of magnesium, zinc, manganese, tin and lead, and Y is phosphorus, boron, sulfur, tellurium, silicon, germanium, cerium, niobium, titanium, zirconium, tungsten and antimony. At least one element selected from the group consisting of Z, Z represents at least one element selected from the group consisting of sodium, potassium, rubidium, cesium and thallium. However, a, b, c, d, e, f, g and h represent the atomic ratio of each element, and when a = 12, 0.1 ≦
b ≦ 5, 0.1 ≦ c ≦ 5, 1 ≦ d ≦ 12, 0 ≦ e ≦ 1
0, 0 ≦ f ≦ 10, 0.01 ≦ g ≦ 3, and h is the number of oxygen atoms required to satisfy the atomic ratio of each component. The present invention has surprisingly detailed the reason for the method of preparing a catalyst for the synthesis of methacrolein and methacrylic acid by the present inventors as a result of various structural analyzes of the catalyst precursor in the preparation process. Although it is not certain, the catalyst precursor calcined in the temperature range of 200 to 400 ° C. had a peak intensity of 2θ = about 26.4 ° in X-ray diffraction (anti-cathode Cu—Kα) of 2θ = about 9.5 °. It can be said that a catalyst having a K value defined by a ratio to a peak intensity of a certain value or less can be a constantly stable and reproducible catalyst different from the conventionally proposed catalysts for methacrolein and methacrylic acid synthesis. It arrived based on knowledge.
【０００８】本発明において、触媒前駆体を構成する触
媒成分は上述したように一般式（Ｉ）で表されるもので
あり、Ｍｏ、Ｂｉ、Ｆｅを必須成分とするものであり、
それ以外のＡ成分、Ｘ成分、Ｙ成分、Ｚ成分については
上記の各元素成分から任意に選択することができる。In the present invention, the catalyst component constituting the catalyst precursor is represented by the general formula (I) as described above, and contains Mo, Bi and Fe as essential components,
The other components A, X, Y, and Z can be arbitrarily selected from the above elemental components.
【０００９】本発明においては、触媒成分を構成する元
素の原料としては特に限定されず、酸化物又は強加熱す
ることにより酸化物になり得る塩化物、水酸化物、硫酸
塩、硝酸塩、炭酸塩、アンモニウム塩又はそれらの混合
物が適宜用いられる。In the present invention, the raw materials for the elements constituting the catalyst component are not particularly limited, and they are oxides, or chlorides, hydroxides, sulfates, nitrates, carbonates which can be transformed into oxides by strong heating. , Ammonium salts or mixtures thereof are used as appropriate.
【００１０】本発明の触媒前駆体は、触媒成分を構成す
る元素の化合物を含有する混合溶液又は水性スラリーを
乾燥し、しかる後得られる乾燥物を熱処理する、いわゆ
る仮焼成処理してなるものである。そして前記混合溶液
又は水性スラリーを乾燥する方法としては特に限定はな
く、汎用の箱形乾燥機、ドラムドライヤー、スラリード
ライヤー等を適宜用いることができる。The catalyst precursor of the present invention is obtained by drying a mixed solution or an aqueous slurry containing a compound of an element constituting a catalyst component and then heat-treating the dried product, so-called calcination treatment. is there. The method for drying the mixed solution or the aqueous slurry is not particularly limited, and a general-purpose box dryer, drum dryer, slurry dryer or the like can be appropriately used.
【００１１】なお、本発明を実施するに際して上記混合
溶液又は水性スラリーの乾燥とは上記混合溶液又は水性
スラリーからある程度の水分を除去することにより、実
質的に固形状物にすることであり、乾燥後の含水量等に
関しては特に限定はない。また、乾燥物の形状について
も特に限定はなく、粉体状でもブロック状でもよい。In carrying out the present invention, drying the mixed solution or aqueous slurry means removing a certain amount of water from the mixed solution or aqueous slurry to form a substantially solid substance, and drying There is no particular limitation on the subsequent water content and the like. The shape of the dried product is not particularly limited, and may be powder or block.
【００１２】本発明の触媒前駆体はかかる乾燥物を仮焼
成処理してなるものであるが、処理温度としては２００
〜４００℃の温度範囲が好ましく、２３０〜３６０℃の
温度範囲が特に好ましい。特に硝酸塩、アンモニウム塩
等を用いた場合には、かかる熱処理による仮焼成処理に
よって硝酸根やアンモニウム根をある程度除去すること
が好ましく、そのためにも一般に２００℃以上の温度で
熱処理することが好ましい。The catalyst precursor of the present invention is obtained by subjecting such a dried product to a calcination process.
The temperature range of to 400 ° C is preferable, and the temperature range of 230 to 360 ° C is particularly preferable. In particular, when nitrates, ammonium salts, etc. are used, it is preferable to remove the nitrate radicals and ammonium radicals to some extent by the calcination treatment by such heat treatment, and for that purpose, it is generally preferable to perform the heat treatment at a temperature of 200 ° C. or higher.
【００１３】本発明の触媒前駆体は、かかる仮焼成処理
されたものであり、触媒活性点の発現はむしろ抑制され
ているものである。このような触媒前駆体を４５０〜６
００℃の温度範囲で焼成処理してやることにより触媒の
活性点が一挙に発現するという特徴を有する。なお前記
仮焼成処理時の処理時間としては１０分〜５時間の範囲
が好ましい。The catalyst precursor of the present invention has been subjected to such a calcination treatment, and the expression of catalytically active sites is rather suppressed. 450 to 6 such a catalyst precursor
It has a feature that the active sites of the catalyst are developed all at once by performing the calcination treatment in the temperature range of 00 ° C. The processing time during the calcination is preferably 10 minutes to 5 hours.
【００１４】本発明において触媒前駆体のＸ線回折にお
ける２θ＝約９．５°のピーク強度の２θ＝約２６．４
°のピーク強度に対する比で定義されるＫ値が１．２以
下の範囲である場合に、この触媒前駆体を４５０〜６０
０℃の温度範囲で焼成すると、焼成段階において触媒活
性点形成反応が十分に進行し、良好な触媒が得られる。
一方、触媒前駆体のＫ値が１．２を超えるものでは、焼
成段階における触媒活性点形成反応が十分に進行せず、
結果として触媒活性の低い触媒が得られることが多い。In the present invention, 2θ = about 26.4 with a peak intensity of 2θ = about 9.5 ° in X-ray diffraction of the catalyst precursor.
When the K value, which is defined as the ratio of the peak intensity to the peak intensity, is in the range of 1.2 or less, the catalyst precursor is added in an amount of 450 to 60.
When calcined in the temperature range of 0 ° C., the catalytic active site forming reaction sufficiently proceeds in the calcining stage, and a good catalyst is obtained.
On the other hand, if the K value of the catalyst precursor exceeds 1.2, the catalyst active site forming reaction in the calcination stage does not proceed sufficiently,
As a result, a catalyst having low catalytic activity is often obtained.
【００１５】本発明者らの検討によると、Ｘ線回折にお
いて２θ＝約９．５°に特徴的なピークを有する物質は
モリブデンを主成分とした酸化物であり、かかる酸化物
の存在が、焼成段階における活性点形成反応を阻害する
ものと推定される。なお、Ｘ線回折における２θ＝約２
６．４°に特徴的なピークを有する物質は本触媒の基本
骨格であるモリブデン酸コバルトまたはその同型置換体
である。According to a study by the present inventors, a substance having a characteristic peak at 2θ = about 9.5 ° in X-ray diffraction is an oxide containing molybdenum as a main component, and the presence of such oxide is It is presumed that it inhibits the active site formation reaction in the firing stage. Note that 2θ in X-ray diffraction is about 2
The substance having a characteristic peak at 6.4 ° is cobalt molybdate, which is the basic skeleton of the present catalyst, or its homomorphic substitution product.
【００１６】本発明者らの検討によると、Ｘ線回折にお
いて２θ＝９．５°に特徴的なピークを有する化合物の
形成を制御するには、触媒前駆体を得るに先立ち、触媒
成分を構成する元素の化合物を含有する混合溶液又は水
性スラリーを得る際に、まず、触媒成分を構成する元素
の化合物を二種類以上に分割し、その内少なくとも二種
類を溶液又は分散液とした後、一方の溶液又は分散液に
もう一方の溶液又は分散液を攪拌しながら投入混合し、
混合溶液又はスラリー状物を得る過程において、該溶液
又は分散液の投入混合に費やす時間を調節することによ
りＸ線回折において２θ＝約９．５°に特徴的なピーク
を有する化合物の形成を制御できることがわかった。具
体的には、上述した投入混合に費やす時間を長くとるほ
ど２θ＝約９．５°に特徴的なピークを有するかかる化
合物の形成を抑制できることがわかった。According to the studies by the present inventors, in order to control the formation of a compound having a characteristic peak at 2θ = 9.5 ° in X-ray diffraction, the catalyst component is constituted prior to obtaining the catalyst precursor. When obtaining a mixed solution or an aqueous slurry containing a compound of an element, first, divide the compound of the element that constitutes the catalyst component into two or more kinds, and after at least two of them are made into a solution or a dispersion, The other solution or dispersion is added to the solution or dispersion while mixing with stirring,
In the process of obtaining a mixed solution or slurry, the formation of a compound having a characteristic peak at 2θ = about 9.5 ° in X-ray diffraction is controlled by adjusting the time spent for adding and mixing the solution or dispersion. I knew I could do it. Specifically, it has been found that the longer the time spent in the above-mentioned mixing for mixing is, the more the formation of such a compound having a characteristic peak at 2θ = about 9.5 ° can be suppressed.
【００１７】また、触媒前駆体を得るに先立ち、触媒成
分を構成する元素の化合物を含有する混合溶液又は水性
スラリーを得る際に、まず、触媒成分を構成する元素の
化合物を二種類以上に分割し、その内少なくとも二種類
を溶液又は分散液とした後、一方の溶液又は分散液にも
う一方の溶液又は分散液を攪拌しながら投入混合し、混
合溶液又はスラリー状物を得る過程において、該溶液又
は分散液を投入混合する際の攪拌状態を調節することに
よってもＸ線回折において２θ＝９．５°に特徴的なピ
ークを有する化合物の形成を制御できることがわかっ
た。具体的には、上述した攪拌状態を激しくするほどか
かる２θ＝９．５°に特徴的なピークを有する化合物の
形成を抑制できることがわかった。Prior to obtaining the catalyst precursor, when obtaining a mixed solution or an aqueous slurry containing the compound of the element constituting the catalyst component, first, the compound of the element constituting the catalyst component is divided into two or more kinds. In the process of obtaining a mixed solution or slurry, at least two of them are made into solutions or dispersions, and then one solution or dispersion is charged and mixed with the other solution or dispersion while stirring to obtain a mixed solution or slurry. It was found that the formation of the compound having a characteristic peak at 2θ = 9.5 ° in X-ray diffraction can be controlled also by adjusting the stirring state when the solution or the dispersion is charged and mixed. Specifically, it was found that the formation of a compound having a characteristic peak at 2θ = 9.5 °, which is caused by increasing the agitation state described above, can be suppressed.
【００１８】上記方法によりかかる２θ＝９．５°に特
徴的なピークを有する化合物形成量を制御する際の具体
的かつ適切な時間及び攪拌状態については、上述した投
入混合過程で用いる容器、攪拌翼の形状及び規模などに
より異なるので、それらの装置に応じて検討し、最適化
しなければならない。なお、このような方法を実施する
に際しては、少なくともモリブデン化合物を含む溶液を
第一の溶液とし、少なくともビスマスを含む溶液を第二
の溶液として、第一の溶液に第二の溶液を投入混合する
方法が特に好ましい。Regarding the specific and appropriate time and stirring state when controlling the amount of the compound having a characteristic peak at 2θ = 9.5 ° by the above method, the container used in the above-mentioned mixing process and the stirring Since it depends on the shape and scale of the blade, etc., it must be examined and optimized according to those devices. In carrying out such a method, a solution containing at least a molybdenum compound is used as a first solution, a solution containing at least bismuth is used as a second solution, and the second solution is added to the first solution and mixed. The method is particularly preferred.
【００１９】本発明において、得られた触媒前駆体から
最終的な実用触媒を得る方法としては特に限定はない
が、必要に応じて成形するか、あるいは不活性担体に担
持し、その後４００〜６５０℃の範囲で１〜２０時間程
度焼成する方法が用いられる。In the present invention, the method for obtaining the final practical catalyst from the obtained catalyst precursor is not particularly limited, but it may be molded or supported on an inert carrier if necessary, and then 400 to 650. A method of firing in the temperature range of 1 to 20 hours is used.
【００２０】本発明の触媒前駆体を用いて得られた触媒
は成形体又は担持体として固定床で使用することが好ま
しいが、粒状として流動床で使用しても良い。The catalyst obtained by using the catalyst precursor of the present invention is preferably used as a molded body or a carrier in a fixed bed, but may be used in the form of particles in a fluidized bed.
【００２１】本発明の触媒前駆体を用いて得られた触媒
を用いて、イソブチレン又は三級ブタノールを分子状酸
素により気相接触酸化して、メタクロレイン及びメタク
リル酸を製造するに際しては、イソブチレン又は三級ブ
タノール対酸素のモル比は１：０．５〜３が好ましい。
原料のイソブチレン又は三級ブタノールは不活性ガスで
希釈して用いることが好ましい。酸化に用いられる分子
状酸素は純酸素ガスでも良いが、工業的には空気が有利
である。反応圧力は常圧ないし数気圧まで用いられる。
反応温度は３００〜４５０℃の範囲が好ましい。In the case of producing methacrolein and methacrylic acid by gas phase catalytic oxidation of isobutylene or tertiary butanol with molecular oxygen using the catalyst obtained by using the catalyst precursor of the present invention, isobutylene or The molar ratio of tertiary butanol to oxygen is preferably 1: 0.5 to 3.
The raw material isobutylene or tertiary butanol is preferably diluted with an inert gas before use. The molecular oxygen used for the oxidation may be pure oxygen gas, but industrially air is advantageous. The reaction pressure is from normal pressure to several atmospheres.
The reaction temperature is preferably in the range of 300 to 450 ° C.
【００２２】[0022]
【実施例】以下に本発明を実施例により示す。なお、反
応用原料としてのイソブチレン又は三級ブタノールの反
応率、生成されるメタクロレイン及びメタクリル酸の選
択率は以下のように定義される。EXAMPLES The present invention will be described below with reference to examples. The reaction rate of isobutylene or tertiary butanol as a reaction raw material and the selectivity of methacrolein and methacrylic acid produced are defined as follows.
【００２３】反応用原料の反応率（％）＝｛（反応した
原料のモル数）／（供給した原料のモル数）｝×１００ メタクロレインの選択率（％）＝｛（生成したメタクロ
レインのモル数）／（反応した原料のモル数）｝×１０
０ メタクリル酸の選択率（％）＝｛（生成したメタクリル
酸のモル数）／（反応した原料のモル数）｝×１００ また、Ｘ線回折は、粉末反射法により測定した。装置は
株式会社リガク製ＲＵ−２００、Ｘ線源としてはＣｕ−
Ｋα、Ｎｉフィルターを使用した。Reaction rate (%) of raw material for reaction = {(mol number of reacted raw material) / (mol number of supplied raw material)} × 100 Methacrolein selectivity (%) = {(of generated methacrolein Number of moles) / (number of moles of reacted raw material)} × 10
0 Methacrylic acid selectivity (%) = {(number of moles of methacrylic acid produced) / (number of moles of reacted raw material)} × 100 Further, X-ray diffraction was measured by a powder reflection method. The equipment is RU-200 manufactured by Rigaku Corporation, and Cu- as the X-ray source.
Kα and Ni filters were used.
【００２４】実施例１ 幅２０ｍｍ、長さ９０ｍｍの羽根を４枚備えたフラット
パドル型回転式攪拌翼及び幅２０ｍｍ、長さ３００ｍｍ
の邪魔板を４枚有する内径３４０ｍｍ、高さ４００ｍｍ
の丸底ステンレス製容器に水６０００ｇを投入し、加熱
した後、パラモリブデン酸アンモニウム３０００ｇを溶
解し、続いて三酸化アンチモン８２．６ｇを分散させ、
回転数１８０ｒｐｍで攪拌しＡ液とした。これとは別に
水５５００ｇに６０％硝酸水溶液１００ｇ、硝酸ビスマ
ス８２４．２ｇ、硝酸第二鉄１１４４．１ｇ、硝酸ニッ
ケル１６４６．７ｇ、硝酸コバルト４１２．０ｇ、硝酸
鉛４６９．０ｇ、硝酸マグネシウム７２６．２ｇ、硝酸
セリウム６１．５ｇ及び硝酸セシウム１１０．４ｇを順
次加え溶解したＢ液とした。１８０ｒｐｍで攪拌した状
態で、Ａ液にＢ液を２００秒の時間を費やしてほぼ一定
の流速で投入混合し、スラリー状物を得た。Example 1 A flat paddle type rotary stirring blade equipped with four blades having a width of 20 mm and a length of 90 mm and a width of 20 mm and a length of 300 mm
With 4 baffles, inner diameter 340mm, height 400mm
6000 g of water was put into a round bottom stainless steel container and heated, and then 3000 g of ammonium paramolybdate was dissolved, followed by dispersing 82.6 g of antimony trioxide,
Liquid A was stirred at a rotation speed of 180 rpm. Separately from this, 100 g of 60% nitric acid aqueous solution, 824.2 g of bismuth nitrate, 1144.1 g of ferric nitrate, 1646.7 g of nickel nitrate, 412.0 g of cobalt nitrate, 469.0 g of lead nitrate and 726.2 g of magnesium nitrate are separately added to 5500 g of water. , 61.5 g of cerium nitrate and 110.4 g of cesium nitrate were sequentially added to prepare a dissolved solution B. While stirring at 180 rpm, the liquid B was added to the liquid A for 200 seconds at a substantially constant flow rate and mixed to obtain a slurry.
【００２５】混合完了後、攪拌回転数を１００ｒｐｍに
減速した後、得られたスラリー状物を９０℃に加熱し、
１００ｒｐｍで攪拌した状態で１００分間熟成処理し、
続いて、噴霧乾燥した。After the mixing was completed, the stirring speed was reduced to 100 rpm, and the resulting slurry was heated to 90 ° C.
Aged for 100 minutes while stirring at 100 rpm,
Subsequently, it was spray dried.
【００２６】得られた乾燥物を３００℃で１時間仮焼成
し、触媒前駆体を得た。この触媒前駆体のＸ線回折測定
を行ったところ２θ＝約９．６°のピーク強度の２θ＝
約２６．４°のピーク強度に対する比で表されるＫ値は
０．１２であった。The obtained dried product was calcined at 300 ° C. for 1 hour to obtain a catalyst precursor. When X-ray diffraction measurement of this catalyst precursor was performed, 2θ = 2θ = about 9.6 ° peak intensity = 2θ =
The K value, expressed as a ratio to the peak intensity of about 26.4 °, was 0.12.
【００２７】続いて、得られた触媒前駆体を直径及び高
さが共に３ｍｍの円柱状に成型し、５１０℃で３時間焼
成した。Subsequently, the obtained catalyst precursor was molded into a cylindrical shape having a diameter and a height of 3 mm, and was fired at 510 ° C. for 3 hours.
【００２８】得られた触媒の組成は次式で示される。The composition of the obtained catalyst is shown by the following formula.
【００２９】Ｍｏ12Ｂｉ1.2Ｆｅ2Ｎｉ4Ｃｏ1Ｐｂ1Ｍｇ2
Ｓｂ0.4Ｃｅ0.1Ｃｓ0.4Ｏx （式中、Ｍｏ、Ｂｉ、Ｆｅ、Ｎｉ、Ｃｏ、Ｐｂ、Ｍｇ、
Ｓｂ、Ｃｅ、Ｃｓ及びＯはそれぞれモリブデン、ビスマ
ス、鉄、ニッケル、コバルト、鉛、マグネシウム、アン
チモン、セリウム、セシウム及び酸素を表す。また、元
素記号右下の添字数字は各元素の原子比であり、ｘは前
記各成分の原子価を満足するのに必要な酸素原子数であ
る。） こうして得られた触媒をステンレス製反応管に充填し、
イソブチレン５％、酸素１２％、水蒸気１０％及び窒素
７３％の原料混合ガスを接触時間４．５秒で触媒層を通
過させ、３５０℃で反応させた。その結果、イソブチレ
ンの反応率９７．４％、メタクロレインの選択率８８．
２％、メタクリル酸の選択率５．４％であった。Mo 12 Bi 1.2 Fe 2 Ni 4 Co 1 Pb 1 Mg 2
Sb 0.4 Ce 0.1 Cs 0.4 O x (in the formula, Mo, Bi, Fe, Ni, Co, Pb, Mg,
Sb, Ce, Cs and O represent molybdenum, bismuth, iron, nickel, cobalt, lead, magnesium, antimony, cerium, cesium and oxygen, respectively. The subscript number in the lower right of the element symbol is the atomic ratio of each element, and x is the number of oxygen atoms required to satisfy the valence of each component. ) The catalyst thus obtained is filled in a stainless reaction tube,
A raw material mixed gas containing 5% of isobutylene, 12% of oxygen, 10% of steam and 73% of nitrogen was passed through the catalyst layer at a contact time of 4.5 seconds and reacted at 350 ° C. As a result, the conversion of isobutylene was 97.4% and the selectivity of methacrolein was 88.
The selectivity was 2% and methacrylic acid was 5.4%.
【００３０】実施例２ 実施例１において、投入混合過程における攪拌回転数を
１３０ｒｐｍに変更する以外は実施例１と同じ条件によ
り触媒前駆体を得た。実施例１と同様にこの触媒前駆体
についてＸ線回折測定を行ったところ、Ｋ値は０．３４
であった。Example 2 A catalyst precursor was obtained under the same conditions as in Example 1 except that the stirring rotation number in the charging and mixing process was changed to 130 rpm. When X-ray diffraction measurement was performed on this catalyst precursor in the same manner as in Example 1, the K value was 0.34.
Met.
【００３１】続いて、得られた触媒前駆体を用いて実施
例１と同じ方法により触媒を得た。Then, a catalyst was obtained by the same method as in Example 1 using the obtained catalyst precursor.
【００３２】こうして得られた触媒を用いて、実施例１
と同様にして反応を行った。結果を表１に示す。得られ
た触媒の性能は実施例１と同等であった。Using the catalyst thus obtained, Example 1
The reaction was carried out in the same manner as in. Table 1 shows the results. The performance of the obtained catalyst was equivalent to that of Example 1.
【００３３】比較例１ 実施例１において、投入混合過程における攪拌回転数を
５０ｒｐｍとする以外は実施例１と同じ条件により触媒
前駆体を得た。実施例１と同様にこの触媒前駆体につい
てＸ線回折測定を行ったところ、Ｋ値は１．９２であっ
た。Comparative Example 1 A catalyst precursor was obtained under the same conditions as in Example 1 except that the stirring speed in the charging and mixing process was 50 rpm. When the X-ray diffraction measurement was performed on this catalyst precursor in the same manner as in Example 1, the K value was 1.92.
【００３４】続いて、得られた触媒前駆体を用いて実施
例１と同じ方法により触媒を得た。Then, using the obtained catalyst precursor, a catalyst was obtained in the same manner as in Example 1.
【００３５】こうして得られた触媒を用いて、実施例１
と同様にして反応を行った。結果を表１に示す。得られ
た触媒の性能は実施例１と比べ劣るものであった。Using the catalyst thus obtained, Example 1
The reaction was carried out in the same manner as in. Table 1 shows the results. The performance of the obtained catalyst was inferior to that of Example 1.
【００３６】実施例３ 実施例１と同様の攪拌翼及び邪魔板を有する同様の容器
内に、水６０００ｇを投入し、加熱した後、パラモリブ
デン酸アンモニウム３０００ｇを溶解し、続いて二酸化
テルル２２．６ｇを分散させ、回転数２００ｒｐｍで攪
拌しＣ液とした。これとは別に水５５００ｇに６０％硝
酸水溶液１００ｇ、８５％リン酸水溶液３２．６ｇ、硝
酸ビスマス１０３０．３ｇ、硝酸第二鉄１０２９．７
ｇ、硝酸ニッケル８２３．３ｇ、硝酸コバルト１２３
５．９ｇ、硝酸亜鉛８４２．４ｇ、硝酸マンガン８１．
３ｇ、硝酸ルビジウム８３．５ｇを順次加え溶解したＤ
液とした。２００ｒｐｍで攪拌した状態で、Ｃ液にＤ液
を２００秒の時間を費やしてほぼ一定の流速で投入混合
し、スラリー状物を得た。Example 3 In a similar container having the same stirring blades and baffles as in Example 1, 6000 g of water was charged and heated, and then 3000 g of ammonium paramolybdate was dissolved, and subsequently tellurium dioxide 22. 6 g was dispersed and stirred at a rotation speed of 200 rpm to prepare a C liquid. Separately, water 5500 g, 60% nitric acid aqueous solution 100 g, 85% phosphoric acid aqueous solution 32.6 g, bismuth nitrate 1030.3 g, ferric nitrate 1029.7
g, nickel nitrate 823.3 g, cobalt nitrate 123
5.9 g, zinc nitrate 842.4 g, manganese nitrate 81.
3 g and 83.5 g of rubidium nitrate were sequentially added and dissolved D
Liquid. While stirring at 200 rpm, liquid D was added to liquid C for 200 seconds at a substantially constant flow rate, and mixed to obtain a slurry.
【００３７】混合完了後、攪拌回転数を８０ｒｐｍに減
速した後、得られたスラリー状物を１００℃に加熱し、
８０ｒｐｍで攪拌した状態で６０分間熟成処理し、続い
て、噴霧乾燥した。After the completion of mixing, the stirring speed was reduced to 80 rpm, and the obtained slurry was heated to 100 ° C.
The mixture was aged for 60 minutes while being stirred at 80 rpm, and then spray-dried.
【００３８】得られた乾燥物を３００℃で１時間仮焼成
し、触媒前駆体を得た。得られた触媒前駆体について、
実施例１と同様にＸ線回折測定を行ったところ、Ｋ値は
０．２２であった。The obtained dried product was calcined at 300 ° C. for 1 hour to obtain a catalyst precursor. Regarding the obtained catalyst precursor,
When X-ray diffraction measurement was performed in the same manner as in Example 1, the K value was 0.22.
【００３９】続いて、得られた触媒前駆体を直径及び高
さが共に３ｍｍの円柱状に成型し、５１０℃で３時間焼
成した。Subsequently, the obtained catalyst precursor was molded into a columnar shape having a diameter and a height of 3 mm and calcined at 510 ° C. for 3 hours.
【００４０】得られた触媒の組成は次式で示される。The composition of the obtained catalyst is shown by the following formula.
【００４１】Ｍｏ12Ｂｉ1.5Ｆｅ1.8Ｎｉ2Ｃｏ3Ｚｎ2Ｍ
ｎ0.2Ｐ0.2Ｔｅ0.1Ｒｂ0.4Ｏｘ （式中、Ｍｏ、Ｂｉ、Ｆｅ、Ｎｉ、Ｃｏ、Ｚｎ、Ｍｎ、
Ｐ、Ｔｅ、Ｒｂ及びＯはそれぞれモリブデン、ビスマ
ス、鉄、ニッケル、コバルト、亜鉛、マンガン、リン、
テルル、ルビジウム及び酸素を表す。また、元素記号右
下の添字数字は各元素の原子比であり、ｘは前記各成分
の原子価を満足するのに必要な酸素原子数である。） こうして得られた触媒を用いて、実施例１と同様にして
反応を行った。結果を表１に示す。Mo 12 Bi 1.5 Fe 1.8 Ni 2 Co 3 Zn 2 M
n 0.2 P 0.2 Te 0.1 Rb 0.4 Ox (in the formula, Mo, Bi, Fe, Ni, Co, Zn, Mn,
P, Te, Rb and O are molybdenum, bismuth, iron, nickel, cobalt, zinc, manganese, phosphorus,
Represents tellurium, rubidium and oxygen. The subscript number in the lower right of the element symbol is the atomic ratio of each element, and x is the number of oxygen atoms required to satisfy the valence of each component. ) A reaction was carried out in the same manner as in Example 1 using the catalyst thus obtained. Table 1 shows the results.
【００４２】実施例４ 実施例３において、投入混合に費やす時間を１５０秒に
変更する以外は実施例３と同じ条件により触媒前駆体を
得た。実施例１と同様にこの触媒前駆体についてＸ線回
折測定を行ったところ、Ｋ値は０．４２であった。Example 4 A catalyst precursor was obtained under the same conditions as in Example 3 except that the time spent for charging and mixing in Example 3 was changed to 150 seconds. When X-ray diffraction measurement was performed on this catalyst precursor in the same manner as in Example 1, the K value was 0.42.
【００４３】こうして得られた触媒を用いて、実施例３
と同様にして反応を行った。結果を表１に示す。得られ
た触媒の性能は実施例３と同等であった。Using the catalyst thus obtained, Example 3
The reaction was carried out in the same manner as in. Table 1 shows the results. The performance of the obtained catalyst was equivalent to that of Example 3.
【００４４】比較例２ 実施例３において、投入混合に費やす時間を５０秒に変
更する以外は実施例３と同じ条件により触媒前駆体を得
た。実施例１と同様にこの触媒前駆体についてＸ線回折
測定を行ったところ、Ｋ値は１．６８であった。Comparative Example 2 A catalyst precursor was obtained under the same conditions as in Example 3 except that the time spent for mixing and charging in Example 3 was changed to 50 seconds. When the X-ray diffraction measurement was performed on this catalyst precursor in the same manner as in Example 1, the K value was 1.68.
【００４５】こうして得られた触媒を用いて、実施例３
と同様にして反応を行った。結果を表１に示す。得られ
た触媒の性能は実施例３及び４と比べ劣るものであっ
た。Example 3 was carried out using the catalyst thus obtained.
The reaction was carried out in the same manner as in. Table 1 shows the results. The performance of the obtained catalyst was inferior to that of Examples 3 and 4.
【００４６】[0046]
【表１】 [Table 1]
【００４７】[0047]
【発明の効果】本発明で規定されるメタクロレイン及び
メタクリル酸合成用触媒前駆体をもとに触媒を製造法す
ると、触媒活性及び目的生成物選択性に優れた触媒を容
易に再現性よく得ることができる。EFFECTS OF THE INVENTION When a catalyst is produced based on the catalyst precursor for methacrolein and methacrylic acid synthesis specified in the present invention, a catalyst excellent in catalytic activity and target product selectivity can be easily and reproducibly obtained. be able to.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 ＦＩ 技術表示箇所 // Ｃ０７Ｂ 61/00 ３００ Ｃ０７Ｂ 61/00 ３００ ──────────────────────────────────────────────────続 き Continuation of the front page (51) Int.Cl. 6 Identification number Agency reference number FI Technical display location // C07B 61/00 300 C07B 61/00 300
Claims (1)
ら構成され、且つＸ線回折（対陰極Ｃｕ−Ｋα）におけ
る２θ＝約９．５°のピーク強度の２θ＝約２６．４°
のピーク強度に対する比で定義されるＫ値が１．２以下
であることを特徴とするメタクロレイン及びメタクリル
酸合成用触媒前駆体。 ＭｏaＢｉbＦｅcＡdＸeＹfＺgＯh （Ｉ） （式中、Ｍｏ、Ｂｉ、Ｆｅ及びＯはそれぞれモリブデ
ン、ビスマス、鉄及び酸素を表し、Ａはニッケル及びコ
バルトからなる群より選ばれた少なくとも１種の元素、
Ｘはマグネシウム、亜鉛、マンガン、スズ及び鉛からな
る群より選ばれた少なくとも１種の元素、Ｙはリン、ホ
ウ素、イオウ、テルル、ケイ素、ゲルマニウム、セリウ
ム、ニオブ、チタン、ジルコニウム、タングステン及び
アンチモンからなる群より選ばれた少なくとも１種の元
素、Ｚはナトリウム、カリウム、ルビジウム、セシウム
及びタリウムからなる群より選ばれた少なくとも１種の
元素を表す。ただし、ａ、ｂ、ｃ、ｄ、ｅ、ｆ、ｇ及び
ｈは各元素の原子比を表し、ａ＝１２のとき、０．１≦
ｂ≦５、０．１≦ｃ≦５、１≦ｄ≦１２、０≦ｅ≦１
０、０≦ｆ≦１０、０．０１≦ｇ≦３であり、ｈは前記
各成分の原子比を満足するのに必要な酸素原子数であ
る。）1. A compound having a catalyst component represented by the following general formula (I) and having a peak intensity of 2θ = about 9.5 ° in X-ray diffraction (anti-cathode Cu—Kα) = 2θ = about 26.4. °
K value defined by the ratio to the peak intensity is 1.2 or less, a catalyst precursor for methacrolein and methacrylic acid synthesis. Mo a Bi b Fe c A d X e Y f Z g O h (I) (wherein Mo, Bi, Fe and O represent molybdenum, bismuth, iron and oxygen, respectively, and A is a group consisting of nickel and cobalt. At least one element selected from
X is at least one element selected from the group consisting of magnesium, zinc, manganese, tin and lead, and Y is phosphorus, boron, sulfur, tellurium, silicon, germanium, cerium, niobium, titanium, zirconium, tungsten and antimony. At least one element selected from the group consisting of Z, Z represents at least one element selected from the group consisting of sodium, potassium, rubidium, cesium and thallium. However, a, b, c, d, e, f, g and h represent the atomic ratio of each element, and when a = 12, 0.1 ≦
b ≦ 5, 0.1 ≦ c ≦ 5, 1 ≦ d ≦ 12, 0 ≦ e ≦ 1
0, 0 ≦ f ≦ 10, 0.01 ≦ g ≦ 3, and h is the number of oxygen atoms required to satisfy the atomic ratio of each component. )
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7283925A JPH09122490A (en) | 1995-10-31 | 1995-10-31 | Catalyst precursor for synthesizing methacrolein and methacrylic acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7283925A JPH09122490A (en) | 1995-10-31 | 1995-10-31 | Catalyst precursor for synthesizing methacrolein and methacrylic acid |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH09122490A true JPH09122490A (en) | 1997-05-13 |
Family
ID=17671992
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP7283925A Pending JPH09122490A (en) | 1995-10-31 | 1995-10-31 | Catalyst precursor for synthesizing methacrolein and methacrylic acid |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH09122490A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009523609A (en) * | 2006-01-17 | 2009-06-25 | サウディ ベーシック インダストリーズ コーポレイション | Process for producing mixed metal oxide catalysts for producing unsaturated aldehydes from olefins |
| WO2012063771A1 (en) * | 2010-11-10 | 2012-05-18 | 日本化薬株式会社 | Catalyst for producing methacrolein and methacrylic acid, and process for production thereof |
-
1995
- 1995-10-31 JP JP7283925A patent/JPH09122490A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009523609A (en) * | 2006-01-17 | 2009-06-25 | サウディ ベーシック インダストリーズ コーポレイション | Process for producing mixed metal oxide catalysts for producing unsaturated aldehydes from olefins |
| WO2012063771A1 (en) * | 2010-11-10 | 2012-05-18 | 日本化薬株式会社 | Catalyst for producing methacrolein and methacrylic acid, and process for production thereof |
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