JPS5859934A - Preparation of methacrolein - Google Patents
Preparation of methacroleinInfo
- Publication number
- JPS5859934A JPS5859934A JP57136270A JP13627082A JPS5859934A JP S5859934 A JPS5859934 A JP S5859934A JP 57136270 A JP57136270 A JP 57136270A JP 13627082 A JP13627082 A JP 13627082A JP S5859934 A JPS5859934 A JP S5859934A
- Authority
- JP
- Japan
- Prior art keywords
- methacrolein
- nitrate
- catalyst
- molecular oxygen
- mixture
- 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
- STNJBCKSHOAVAJ-UHFFFAOYSA-N Methacrolein Chemical compound CC(=C)C=O STNJBCKSHOAVAJ-UHFFFAOYSA-N 0.000 title claims abstract description 16
- 239000003054 catalyst Substances 0.000 claims abstract description 19
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000000203 mixture Substances 0.000 claims abstract description 15
- 239000007789 gas Substances 0.000 claims abstract description 11
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910001882 dioxygen Inorganic materials 0.000 claims abstract description 7
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 5
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 5
- 229910052701 rubidium Inorganic materials 0.000 claims abstract description 5
- 229910052718 tin Inorganic materials 0.000 claims abstract description 5
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 4
- 229910052785 arsenic Inorganic materials 0.000 claims abstract description 3
- 229910052796 boron Inorganic materials 0.000 claims abstract description 3
- 229910052792 caesium Inorganic materials 0.000 claims abstract description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical group [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- 229910017052 cobalt Inorganic materials 0.000 claims description 6
- 239000010941 cobalt Substances 0.000 claims description 6
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical group [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 6
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical group [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims description 4
- 229910052804 chromium Inorganic materials 0.000 claims description 4
- 239000011651 chromium Substances 0.000 claims description 4
- 239000011777 magnesium Substances 0.000 claims description 4
- 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 4
- 239000011591 potassium Substances 0.000 claims description 4
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 claims description 4
- 239000010936 titanium Substances 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- 239000011133 lead Substances 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 239000011701 zinc Substances 0.000 claims description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 2
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims description 2
- 230000001590 oxidative effect Effects 0.000 claims description 2
- 239000011574 phosphorus Substances 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 239000010937 tungsten Substances 0.000 claims description 2
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 abstract description 6
- 150000001875 compounds Chemical class 0.000 abstract description 5
- 238000007254 oxidation reaction Methods 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 3
- 239000003440 toxic substance Substances 0.000 abstract description 3
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- 230000003647 oxidation Effects 0.000 abstract description 2
- 231100000167 toxic agent Toxicity 0.000 abstract description 2
- 239000012808 vapor phase Substances 0.000 abstract 2
- 229910052745 lead Inorganic materials 0.000 abstract 1
- 125000004430 oxygen atom Chemical group O* 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 17
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- NLSCHDZTHVNDCP-UHFFFAOYSA-N caesium nitrate Chemical compound [Cs+].[O-][N+]([O-])=O NLSCHDZTHVNDCP-UHFFFAOYSA-N 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 4
- 239000000741 silica gel Substances 0.000 description 4
- 229910002027 silica gel Inorganic materials 0.000 description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- RTHYXYOJKHGZJT-UHFFFAOYSA-N rubidium nitrate Inorganic materials [Rb+].[O-][N+]([O-])=O RTHYXYOJKHGZJT-UHFFFAOYSA-N 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- 229910052716 thallium Inorganic materials 0.000 description 3
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 description 3
- 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 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 2
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 2
- 239000011609 ammonium molybdate Substances 0.000 description 2
- 229940010552 ammonium molybdate Drugs 0.000 description 2
- 235000018660 ammonium molybdate Nutrition 0.000 description 2
- 229910052797 bismuth Inorganic materials 0.000 description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 2
- 239000012876 carrier material Substances 0.000 description 2
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-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
- 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
- 229910052742 iron Inorganic materials 0.000 description 2
- 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 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
- 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
- WKMKTIVRRLOHAJ-UHFFFAOYSA-N oxygen(2-);thallium(1+) Chemical compound [O-2].[Tl+].[Tl+] WKMKTIVRRLOHAJ-UHFFFAOYSA-N 0.000 description 2
- 239000004323 potassium nitrate Substances 0.000 description 2
- 235000010333 potassium nitrate Nutrition 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 229910003438 thallium oxide Inorganic materials 0.000 description 2
- QDZRBIRIPNZRSG-UHFFFAOYSA-N titanium nitrate Chemical compound [O-][N+](=O)O[Ti](O[N+]([O-])=O)(O[N+]([O-])=O)O[N+]([O-])=O QDZRBIRIPNZRSG-UHFFFAOYSA-N 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
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- DJHGAFSJWGLOIV-UHFFFAOYSA-N Arsenic acid Chemical compound O[As](O)(O)=O DJHGAFSJWGLOIV-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 239000004859 Copal Substances 0.000 description 1
- 241000782205 Guibourtia conjugata Species 0.000 description 1
- 241000556720 Manga Species 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 235000019892 Stellar Nutrition 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229940000488 arsenic acid Drugs 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 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
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 description 1
- 150000002816 nickel compounds Chemical class 0.000 description 1
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 208000020016 psychiatric disease Diseases 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- YQMWDQQWGKVOSQ-UHFFFAOYSA-N trinitrooxystannyl nitrate Chemical compound [Sn+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YQMWDQQWGKVOSQ-UHFFFAOYSA-N 0.000 description 1
- 150000003658 tungsten compounds Chemical class 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
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
【発明の詳細な説明】
本発明はターシャリ−ブチルアルコールとインブチレン
の混合物を分子状酸素又は分子状酸素含有ガスにより気
相で酸化してメタクロレインｔｌ−製造する際に一般組
成が
ＡａＦｅｂＢｌ。ＬｄＱｏＭｏｆｘｇＯｈ（式中Ａはコ
バルト又はコバルト及びニッケルを表わし、Ｌはリン、
ヒ素及びホウ素から選ばれた少なくとも一種の元素を表
わし、Ｑはカリウム、ルビジウム及びセシウムから選ば
れた少なくとも一種の元素を表わし％Ｘはチタン、錫、
鉛、マグネシウム、クロム、 亜鉛、マンガン、タング
ステンより選ばれた少なくとも一種の元素を表わし、ａ
＊ ｂ＋ Ｑｓ ６＋ ｅｐ ｆ＋ ｇ及びｈ
はそれぞれＡ。DETAILED DESCRIPTION OF THE INVENTION The present invention involves the production of methacrolein tl-, which has a general composition of AaFebBl, by oxidizing a mixture of tertiary-butyl alcohol and imbutylene in the gas phase with molecular oxygen or a molecular oxygen-containing gas. LdQoMofxgOh (in the formula, A represents cobalt or cobalt and nickel, L is phosphorus,
represents at least one element selected from arsenic and boron; Q represents at least one element selected from potassium, rubidium and cesium; %X represents titanium, tin,
Represents at least one element selected from lead, magnesium, chromium, zinc, manganese, and tungsten, and a
* b+ Qs 6+ ep f+ g and h
are each A.
Ｆｅ 、 Ｂｉ 、 Ｌ’へ嘔ｏ、！及び０の原子数を
示す。ｆを１２とした場合ａは２〜１５．１）は０．５
〜７．Ｃは０．１〜４．（ｌはＯ−４，ｅはｏ、ｏ １
−１．ｏ、 ｇは０〜３の値をとる。ｈは他の元素の原
子価により自然に決まる値である。）で示される触媒を
使用することを特徴とするメタクロレインの製造方法に
関する。Fe, Bi, L'! and the number of atoms of 0. If f is 12, a is 2 to 15.1) is 0.5
~7. C is 0.1-4. (l is O-4, e is o, o 1
-1. o and g take values from 0 to 3. h is a value naturally determined by the valences of other elements. ) The present invention relates to a method for producing methacrolein, which is characterized by using the catalyst shown in (1).
従来より気相接触酸化反応によってメタクロレインを製
造する方法は数多く提案されている。しかしながらそれ
らの方法は殆ど出発原料としてイソブチレンを使用して
いるものである。Many methods for producing methacrolein by gas phase catalytic oxidation reactions have been proposed. However, most of these methods use isobutylene as a starting material.
ターシャリ−ブチルアルコールｃ以下ＴＥＡと称す。）
を出発原料として気相酸化によりメタクロレインを得る
方法は特開昭４８−３２８１４号に記載されている。Tertiary-butyl alcohol c is hereinafter referred to as TEA. )
A method for obtaining methacrolein by gas phase oxidation using as a starting material is described in JP-A-48-32814.
しかしながらこの方法は触媒成分のひとつとしてタリウ
ム酸化物を使用しており、タリウムを含有することを主
たる特徴とするものである。However, this method uses thallium oxide as one of the catalyst components, and its main feature is that it contains thallium.
タリウム酸化物は周知のように還元雰囲気中で′は容易
に還元を受けて低次の酸化物又は金属タリウムとなって
揮散するおそれがある。As is well known, thallium oxide may easily undergo reduction in a reducing atmosphere and become a lower-order oxide or metal thallium and volatilize.
タリウムは吸入、耐着等によって人体に吸収されると精
神障害等の原因となる有毒物質であり、このような物質
を工業的に触媒成分として使用することは極めて大きな
問題となる可能性がある。Thallium is a toxic substance that can cause mental disorders when absorbed into the human body through inhalation, adhesion, etc., and the industrial use of such a substance as a catalyst component may pose an extremely serious problem. .
本発明者らは、このような有毒物質を使用しない触媒系
について鋭意検討した結果、前記組成を有する触媒を使
用すると、ＴＥＡとイソブチレンとの混合物から極めて
高収率でメタクロレインを製造することが出来ることを
見出し、本発明を完成した。The present inventors have conducted extensive studies on catalyst systems that do not use such toxic substances, and have found that methacrolein can be produced in extremely high yield from a mixture of TEA and isobutylene when a catalyst having the above composition is used. They discovered what could be done and completed the present invention.
本発明においては、ＴＥＡの反応率は１００チに達する
。In the present invention, the reaction rate of TEA reaches 100%.
本発明で使用する触媒は例えば次のようにして製造する
ことが出来る。The catalyst used in the present invention can be produced, for example, as follows.
適当なモリブデン酸塩例えばモリブデン酸アンモニウム
の水溶液に水溶性の鉄、ビスマス、コバルトの化合物、
必要があればニッケルの化合物、カリウム（および／又
はルビジウム、セシウム）の化合物及び必要があれば、
燐酸、ヒ酸またはホウ酸から選ばれた少なくとも一種の
化合物、更に必要があれば、水溶性のチタン、錫、鉛、
マグネシウム、クロム、亜鉛、マンガン、タングステン
化合物のなかから選ばれた少なくとも一種の化合物を水
溶液の形で加える。生じた泥状懸濁液をそのまま、又は
適当な担体物質を加えて蒸発乾固しこれを空気又は酸素
の存在下に高温例えば４００〜８００℃で４時間以上焼
成する。suitable molybdates, e.g. compounds of iron, bismuth, cobalt soluble in aqueous solutions of ammonium molybdate;
If necessary, nickel compounds, potassium (and/or rubidium, cesium) compounds, and if necessary,
At least one compound selected from phosphoric acid, arsenic acid, or boric acid, and if necessary, water-soluble titanium, tin, lead,
At least one compound selected from magnesium, chromium, zinc, manganese, and tungsten compounds is added in the form of an aqueous solution. The resulting slurry suspension is evaporated to dryness as it is or with the addition of a suitable carrier material, and then calcined in the presence of air or oxygen at a high temperature, e.g., 400 to 800 DEG C., for 4 hours or more.
モリブデンの出発原料としてはモリブデン酸アンモニウ
ムの他にモリブデン酸又は三酸化モリブデン等が使用で
きる。水溶性の鉄、ビスマス、コバルト、ニッケル、カ
リウム、ルビジウム、セシウムの化合物としては、例え
ば、硝酸ニッケル。As a starting material for molybdenum, in addition to ammonium molybdate, molybdic acid or molybdenum trioxide can be used. Examples of water-soluble iron, bismuth, cobalt, nickel, potassium, rubidium, and cesium compounds include nickel nitrate.
硝酸コバルト、硝酸第二鉄、硝酸カリウム、硝酸ルビジ
ウム、硝酸セシウム、硝酸ビスマス等が使用できる。Cobalt nitrate, ferric nitrate, potassium nitrate, rubidium nitrate, cesium nitrate, bismuth nitrate, etc. can be used.
水溶性のチタン、錫、鉛、マグネシウム、クロム、ｌ［
Ｌ、マンガ、ノー１−タング、ステラ化合物としては例
えば、塩化チタン、硝酸チタン、酸化チタン、塩化スズ
、硝酸スズ、硝酸鉛、硝酸マグネシウム、炭酸マグネシ
ウム、硝酸クロム、無水クロム酸、硝酸亜鉛、硝酸マン
ガン、タングステン酸アンモン等が使用できる。Water-soluble titanium, tin, lead, magnesium, chromium,
Examples of L, Manga, No 1-Tung, and Stellar compounds include titanium chloride, titanium nitrate, titanium oxide, tin chloride, tin nitrate, lead nitrate, magnesium nitrate, magnesium carbonate, chromium nitrate, chromic anhydride, zinc nitrate, and nitric acid. Manganese, ammonium tungstate, etc. can be used.
担体物質としてはシリカゲル、シリカゾル、ケイソウ士
、アルミナ、カーポランダム等が用いられる。As the carrier material, silica gel, silica sol, diatomaceous material, alumina, carporundum, etc. are used.
触媒は一般に粒状又は錠剤として固定床に用いられるが
移動床或いは流動床にも使用出来る。Catalysts are generally used as granules or tablets in fixed beds, but can also be used in moving or fluidized beds.
分子状酸素としては通常空気が使用されるが純酸素を使
用してもよい。又、酸素を窒素、炭酸ガス等の不活性ガ
スで希釈して使用してもよい。Air is usually used as molecular oxygen, but pure oxygen may also be used. Further, oxygen may be diluted with an inert gas such as nitrogen or carbon dioxide.
又希釈剤として水蒸気を使用することが好ましい。It is also preferred to use water vapor as a diluent.
本発明の反応は通常２５０〜４５０℃の温度で、常圧な
いし１０気圧のもとで行なわれる。The reaction of the present invention is usually carried out at a temperature of 250 to 450°C and under normal pressure to 10 atm.
本発明において例えば空気及び水蒸気を用いる場合、混
合原料ガスの接触時間は反応温度、反応圧力基準で０・
１〜１０秒である。In the present invention, for example, when air and steam are used, the contact time of the mixed raw material gas is 0.
It is 1 to 10 seconds.
触媒上を通過させる混合ガスに含まれるＴＥＡとインブ
チレン、酸素及び水蒸気の割合はＴＥＡとインブチレン
の合計モル数１モルに対して酸素１〜５モル、水蒸気１
〜２０モルの割合が適当である。The ratio of TEA, imbutylene, oxygen and water vapor contained in the mixed gas passed over the catalyst is 1 to 5 mol of oxygen and 1 mol of water vapor per 1 mol of total moles of TEA and imbutylene.
A proportion of ˜20 mol is suitable.
以下実施例をあげて本発明をさらに詳細に説明する。The present invention will be explained in more detail below with reference to Examples.
実施例及び参考例中の反応率、選択率、単流収率は次の
定義に従うものとする。The reaction rate, selectivity, and single flow yield in Examples and Reference Examples shall comply with the following definitions.
供給したＴＢＡ又はＴＢＡおよびインフ゛テレンのモル
数反応したＴＢＡ又はＴＢＡおよびインフヂレンのモル
数参考例１
パラモリブデン酸アンモン４２．４Ｆを蒸留水に溶解し
、硝酸力Ｉ７０．２８ｆを加え溶解する。この溶液を攪
拌しながら硝酸コバルト４０・２ｆを含む水溶液、硝酸
鉄８．１ｆを含む水溶液及び硝酸ビスマス９．７ｆを含
む希硝酸溶液を加える。生じた泥状懸濁液に微粉状シリ
カゲル１！５．１ｆを加え充分攪拌しながら蒸発乾固さ
せる。更に３００℃で３〜４時間加熱し冷却後粉砕する
。Number of moles of supplied TBA or TBA and inphelene Number of moles of reacted TBA or TBA and inphelene Reference example 1 Ammonium paramolybdate 42.4F is dissolved in distilled water, nitric acid strength I70.28f is added and dissolved. While stirring this solution, an aqueous solution containing 40.2 f of cobalt nitrate, an aqueous solution containing 8.1 f of iron nitrate, and a dilute nitric acid solution containing 9.7 f of bismuth nitrate are added. 1.5.1 f of finely powdered silica gel is added to the resulting muddy suspension and evaporated to dryness with thorough stirring. The mixture is further heated at 300°C for 3 to 4 hours, cooled, and then pulverized.
かくして得られた粉末を成型したのち６５０℃で４時間
以上空気流通下で焼成する。この触媒を原子比で表わす
とＣＯ７Ｆ ８１Ｂ １１Ｋ ｏ、１ａ Ｍ Ｏ１２°
４９．５で示される。（以下酸素については、他の元素
の原子価により自然に決まる値であるので省略する。）
この触媒２０ｍ１を内径１８闘の反応管に充填し、これ
にＴＢＡ １モル、空気１２．４モル、水蒸気１０モル
よりなる混合ガスを空間速度１５０口ｔ−ｇａｓ ／
ｔ−ｃａｔ ／ ｈｒ で供給し３３０℃で反応させ
たところＴＥＡの反応率は１００％でア秒メタクロレイ
ン選択率は８０．３％でありメタクロレイン単流収率は
８０・３チであった。The powder thus obtained is molded and then calcined at 650° C. for 4 hours or more under air circulation. This catalyst is expressed in atomic ratio as CO7F 81B 11K o, 1a M O12°
49.5. (The value for oxygen is omitted below as it is a value naturally determined by the valence of other elements.)
20 ml of this catalyst was packed into a reaction tube with an inner diameter of 18 mm, and a mixed gas consisting of 1 mol of TBA, 12.4 mol of air, and 10 mol of water vapor was charged into the reaction tube at a space velocity of 150 t-gas/
When the reaction was carried out at 330°C by feeding at t-cat/hr, the TEA reaction rate was 100%, the second methacrolein selectivity was 80.3%, and the methacrolein single flow yield was 80.3%. .
参考例２
参考例１において硝酸コパル）４０．２Ｆに代えて硝酸
コバル）３４．９ｆ、硝酸ニッケル１１．６Ｆを、硝酸
カリ０・２８２に代えて硝酸ルビジウム０．４１２を、
微粉末シリカゲル１３．１ｆに代えて′微粉末シリカゲ
ル１５４１Ｆを用いた以外は参考例１と全く同様にして
触媒を調製すると次の組成の触媒が得られる。Reference Example 2 In Reference Example 1, cobal nitrate) 34.9f was substituted for copal nitrate) 40.2F, nickel nitrate 11.6F was substituted, rubidium nitrate 0.412 was substituted for potassium nitrate 0.282,
A catalyst was prepared in exactly the same manner as in Reference Example 1 except that fine powder silica gel 1541F was used in place of fine powder silica gel 13.1f to obtain a catalyst having the following composition.
Ｃ０６Ｎ１２ＦθＩ Ｂ１１Ｒｂ０．１４ Ｍ０１２参
考例１における反応条件と同様な条件で反応を行ったと
ころＴＥＡの反応率は１００チ、メタクロレインの選択
率は８２．１％であってメタクロレインの単流収率は８
２．１ ％であった。C06N12FθI B11Rb0.14 M012 When the reaction was carried out under the same conditions as in Reference Example 1, the reaction rate of TEA was 100%, the selectivity of methacrolein was 82.1%, and the single flow yield of methacrolein was 8
It was 2.1%.
参考例３
参考例２において硝酸ルビジウム０．４１９に代えて硝
酸セシウムを用いた以外は参考例２と同様にして調製し
た触媒（触媒組成： Ｃｏ６Ｎｉ２Ｆｅ、 Ｂｉ。Reference Example 3 A catalyst prepared in the same manner as in Reference Example 2 except that cesium nitrate was used in place of rubidium nitrate 0.419 in Reference Example 2 (catalyst composition: Co6Ni2Fe, Bi).
Ｃｓ。、、ａ ＭＯ１２）を用いて参考例１と同様な反
応条件で反応を行った。Cs. ,,a MO12) was used to carry out the reaction under the same reaction conditions as in Reference Example 1.
反応成績はＴＤＡの反応率１００％、メタクロレインの
選択率は８０．５％、単流収率は８０．５％であった。The reaction results were as follows: TDA reaction rate was 100%, methacrolein selectivity was 80.5%, and single flow yield was 80.5%.
参考例４〜１４
参考例１に準じて調製した表−１に示す組成を有する触
媒を用いて、参考例１と同様な反応条件下で反応を行っ
た。Reference Examples 4 to 14 Using catalysts prepared according to Reference Example 1 and having the compositions shown in Table 1, reactions were carried out under the same reaction conditions as in Reference Example 1.
その結果を表−１に示した。The results are shown in Table-1.
とイソブチレンの混合物の反応率は９８・０％であ抄メ
タクロレインの選択率はａｌ、１％であり、メタクロレ
イン単流収率は７９．５チであった。The reaction rate of the mixture of and isobutylene was 98.0%, the selectivity of methacrolein was 1%, and the single flow yield of methacrolein was 79.5%.
実施例２〜１４
参考例２〜１４で用いた触媒と、表−２に示した混合割
合のＴＢＡとイソブチレンの混合物を用い、実施例１と
同様にして反応を行なった。結果は表−２に示した。Examples 2 to 14 Reactions were carried out in the same manner as in Example 1 using the catalysts used in Reference Examples 2 to 14 and a mixture of TBA and isobutylene in the mixing ratio shown in Table 2. The results are shown in Table-2.
Claims (1)
を分子状酸素又は分子状酸素含有ガスにより気相で酸化
してメタクロレインを製造する際に一般組成が ＡａＦｅｂＢｌ。ＬｄＱｏＭＯｆＸｇＯｈｃ式中Ａはコ
バルト又はコバルト及びニッケルを表わし、Ｌはリン、
ヒ素及びホウ素から選ばれた少なくとも一種の元素を表
わし、Ｑはカリウム、ルビジウム及びセシウムから選ば
れた少なくとも一種の元素を表わし、Ｘはチタン、錫、
鉛、マグネシウム、クロム、亜鉛、マンガン、タングス
テンより選ばれた少なくとも一種の元素を表わし、ａ、
ｂ、ｃ、 ｄ、ｅ、ｆ、ｇ及びｈはそれぞれＡ。 ＩＦｅ 、 Ｂｉ 、 Ｌ 、 Ｃ１、Ｍｏ 、 Ｘ及
び０の原子数を示すＯｆを１２とした場合ａは２〜１５
．ｂは０．５〜７゜Ｃは０．１〜４．（ｉはＯ−４，ｅ
は０．０１−１．０ 。 ｇは０〜３の値をとる。ｈは他の元素の原子価により自
然に決まる値である。）で示される触媒を使用すること
を特徴とするメタクロレインの製造方法。[Claims] When methacrolein is produced by oxidizing a mixture of tertiary butyl alcohol and imbutylene in the gas phase with molecular oxygen or a molecular oxygen-containing gas, the general composition is AaFebBl. LdQoMOfXgOhc In the formula, A represents cobalt or cobalt and nickel, L is phosphorus,
represents at least one element selected from arsenic and boron; Q represents at least one element selected from potassium, rubidium, and cesium; X represents titanium, tin,
Represents at least one element selected from lead, magnesium, chromium, zinc, manganese, and tungsten, a,
b, c, d, e, f, g and h are each A. If Of, which indicates the number of atoms of IFe, Bi, L, C1, Mo, X, and 0, is 12, a is 2 to 15
．． b is 0.5-7°C is 0.1-4. (i is O-4, e
is 0.01-1.0. g takes a value of 0 to 3. h is a value naturally determined by the valences of other elements. ) A method for producing methacrolein, characterized by using the catalyst shown in (a).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57136270A JPS5859934A (en) | 1982-08-06 | 1982-08-06 | Preparation of methacrolein |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57136270A JPS5859934A (en) | 1982-08-06 | 1982-08-06 | Preparation of methacrolein |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP49011424A Division JPS5823370B2 (en) | 1974-01-29 | 1974-01-29 | Methacrolein |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS5859934A true JPS5859934A (en) | 1983-04-09 |
Family
ID=15171261
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP57136270A Pending JPS5859934A (en) | 1982-08-06 | 1982-08-06 | Preparation of methacrolein |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5859934A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6130539A (en) * | 1984-07-23 | 1986-02-12 | Mitsubishi Rayon Co Ltd | Production of methacrolein and methacrylic acid |
| JPS6133135A (en) * | 1984-07-24 | 1986-02-17 | Mitsubishi Rayon Co Ltd | Method for producing methacrolein and methacrylic acid |
-
1982
- 1982-08-06 JP JP57136270A patent/JPS5859934A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6130539A (en) * | 1984-07-23 | 1986-02-12 | Mitsubishi Rayon Co Ltd | Production of methacrolein and methacrylic acid |
| JPS6133135A (en) * | 1984-07-24 | 1986-02-17 | Mitsubishi Rayon Co Ltd | Method for producing methacrolein and methacrylic acid |
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