JPH0213652B2 - - Google Patents
Info
- Publication number
- JPH0213652B2 JPH0213652B2 JP56193948A JP19394881A JPH0213652B2 JP H0213652 B2 JPH0213652 B2 JP H0213652B2 JP 56193948 A JP56193948 A JP 56193948A JP 19394881 A JP19394881 A JP 19394881A JP H0213652 B2 JPH0213652 B2 JP H0213652B2
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- methacrolein
- acid
- methacrylic acid
- selectivity
- 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.)
- Expired - Lifetime
Links
- 239000003054 catalyst Substances 0.000 claims description 45
- STNJBCKSHOAVAJ-UHFFFAOYSA-N Methacrolein Chemical compound CC(=C)C=O STNJBCKSHOAVAJ-UHFFFAOYSA-N 0.000 claims description 30
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 25
- 239000000203 mixture Substances 0.000 claims description 19
- 239000007789 gas Substances 0.000 claims description 17
- 239000002253 acid Substances 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 11
- 239000010949 copper Substances 0.000 claims description 10
- 239000011964 heteropoly acid Substances 0.000 claims description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 6
- 229910052720 vanadium Inorganic materials 0.000 claims description 6
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 5
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- 229910052802 copper Inorganic materials 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 230000003647 oxidation Effects 0.000 claims description 5
- 238000007254 oxidation reaction Methods 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- 229910052698 phosphorus Inorganic materials 0.000 claims description 5
- 239000011574 phosphorus Substances 0.000 claims description 5
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 4
- 229910052796 boron Inorganic materials 0.000 claims description 4
- 229910001882 dioxygen Inorganic materials 0.000 claims description 4
- 229910052750 molybdenum Inorganic materials 0.000 claims description 4
- 239000011733 molybdenum Substances 0.000 claims description 4
- 229910001413 alkali metal ion Inorganic materials 0.000 claims description 3
- 230000003197 catalytic effect Effects 0.000 claims description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 45
- 238000006243 chemical reaction Methods 0.000 description 31
- 230000000694 effects Effects 0.000 description 14
- 239000002994 raw material Substances 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 10
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- DHRLEVQXOMLTIM-UHFFFAOYSA-N phosphoric acid;trioxomolybdenum Chemical compound O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.OP(O)(O)=O DHRLEVQXOMLTIM-UHFFFAOYSA-N 0.000 description 6
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 5
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 5
- 239000004327 boric acid Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 229910052783 alkali metal Inorganic materials 0.000 description 4
- 229960004643 cupric oxide Drugs 0.000 description 4
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 4
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 150000007513 acids Chemical class 0.000 description 3
- 150000001340 alkali metals Chemical class 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 229910000431 copper oxide Inorganic materials 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000004576 sand Substances 0.000 description 3
- 239000000741 silica gel Substances 0.000 description 3
- 229910002027 silica gel Inorganic materials 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- 239000005751 Copper oxide Substances 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
- RAOSIAYCXKBGFE-UHFFFAOYSA-K [Cu+3].[O-]P([O-])([O-])=O Chemical compound [Cu+3].[O-]P([O-])([O-])=O RAOSIAYCXKBGFE-UHFFFAOYSA-K 0.000 description 2
- GLMOMDXKLRBTDY-UHFFFAOYSA-A [V+5].[V+5].[V+5].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O Chemical compound [V+5].[V+5].[V+5].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O GLMOMDXKLRBTDY-UHFFFAOYSA-A 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 229910052785 arsenic Inorganic materials 0.000 description 2
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 229910052716 thallium Inorganic materials 0.000 description 2
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 description 2
- 239000012002 vanadium phosphate Substances 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- -1 Alkali metal salts Chemical class 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- QUEDYRXQWSDKKG-UHFFFAOYSA-M [O-2].[O-2].[V+5].[OH-] Chemical compound [O-2].[O-2].[V+5].[OH-] QUEDYRXQWSDKKG-UHFFFAOYSA-M 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052810 boron oxide Inorganic materials 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229940116318 copper carbonate Drugs 0.000 description 1
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 1
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 1
- GEZOTWYUIKXWOA-UHFFFAOYSA-L copper;carbonate Chemical compound [Cu+2].[O-]C([O-])=O GEZOTWYUIKXWOA-UHFFFAOYSA-L 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 1
- 229940112669 cuprous oxide Drugs 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 1
- 238000007865 diluting Methods 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
- YWEUIGNSBFLMFL-UHFFFAOYSA-N diphosphonate Chemical compound O=P(=O)OP(=O)=O YWEUIGNSBFLMFL-UHFFFAOYSA-N 0.000 description 1
- 230000005183 environmental health Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- OGUCKKLSDGRKSH-UHFFFAOYSA-N oxalic acid oxovanadium Chemical compound [V].[O].C(C(=O)O)(=O)O OGUCKKLSDGRKSH-UHFFFAOYSA-N 0.000 description 1
- QLOKAVKWGPPUCM-UHFFFAOYSA-N oxovanadium;dihydrochloride Chemical compound Cl.Cl.[V]=O QLOKAVKWGPPUCM-UHFFFAOYSA-N 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- DLYUQMMRRRQYAE-UHFFFAOYSA-N phosphorus pentoxide Inorganic materials O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000008262 pumice Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 description 1
- UUUGYDOQQLOJQA-UHFFFAOYSA-L vanadyl sulfate Chemical compound [V+2]=O.[O-]S([O-])(=O)=O UUUGYDOQQLOJQA-UHFFFAOYSA-L 0.000 description 1
- 229940041260 vanadyl sulfate Drugs 0.000 description 1
- 229910000352 vanadyl sulfate Inorganic materials 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
本発明はメタクロレインを高温気相下に分子状
酸素または分子状酸素含有ガスにより接触酸化し
て収率よく、メタクリル酸を製造する方法に関す
るものである。
メタクロレインを高温気相下に接触酸化してメ
タクリル酸を製造する方法に関しては、従来から
既に燃モリブデン酸またはその塩からなる触媒を
用いる数多くの方法が提案されているが、未だ工
業化されるには至つていない。
この理由はひとつにはメタクロレインからメタ
クリル酸を製造する際の収率が低いことにある。
同じような反応でアクロレインからアクリル酸を
製造する場合の収率が著しく高い水準にあり、既
に工業化されているのと好対称である。
メタクリル酸の収率が低いことは、メタクロレ
インがアクロレインに較べて酸化されやすく部分
酸化に比して完全酸化（一酸化炭素、二酸化炭素
の生成）が起こりやすいという事実に起因するも
のと考えられる。
更に未だ工業化されるに至らないもうひとつの
理由としては、この目的に用いようとする触媒の
寿命が短いために実用的な工業触媒として採用し
得ないことがあげられる。
燐モリブデン酸またはその塩からなる触媒は耐
熱性に難点があり、熱分解や焼結等の現象により
活性が低下する。
メタクロレインからメタクリル酸を生成する選
択性は低温程高いこともあつて、燐モリブデン酸
またはその塩からなる触媒は可能な限り低温で使
用することが望まれている。とは言え活性は低温
程低下するため、反応器の大きさおよび充填する
触媒量が膨大なものとなり、経済的に成立しにく
い。
メタクロレインのワンパス反応率を抑えて高い
メタクリル酸の選択率を得ようとする多段酸化や
リサイクル法においては、より一層高い活性の触
媒が要請されている。
反応器に充填する形状に成型された触媒で
600hr-1以上、１〜２mmに破砕された状態で
1500-1以上の空間速度で十分に反応しうる触媒で
なければならない。こうした点で従来知られてい
る触媒は活性が不十分であり、選択性も満足でき
ないものである。
最近メタクリル酸の収率を高める工夫として
は、モリブデン、燐、バナジウム、銅を主成分と
する燐モリブデン酸系触媒にカリウム、ルビジウ
ムあるいはセシウム等のアルカリ金属やタリウム
を加えて、それらの塩とすることとか砒素を加え
ることが提案されている。
しかしながら、これらの成分を加えることは一
見ワンパス収率を高めているようであるが、活性
を低下させるという不利を生じている。又砒素は
代表的な毒物であり、特定化学物質に指定されて
いる物質の中でも特に取扱いおよび管理が問題と
されている。触媒の製造、運搬、反応器での充
填、抜出作業あるいは廃棄等、労働衛生および環
境衛生上極めて困難な問題をかかえている。
本願発明者らはこうした問題に鑑み、鋭意高い
活性、特に低温において高い活性と高い選択性を
有し、安全で取扱い易い触媒の探索を進めた結
果、本発明に至つたものである。
本発明はモリブデン、燐、バナジウム、銅およ
び硼素からなる触媒を使用することにより、メタ
クリル酸を高選択率、高収率で製造するものであ
り、特にその極めて高い活性、特に低温における
高い活性から触媒寿命も極めて長く、十分に工業
的に成立する方法を提供するものである。
触媒は一般組成が
MoaPbVcCudBeOf
（ここにおいてａ、ｂ、ｃ、ｄ、ｅおよびｆはそ
れぞれモリブデン、燐、バナジウム、銅、硼素お
よび酸素の原子数の比である。そしてａ＝12とす
るとｂ＝0.1〜６、ｃ＝0.1〜６、ｄ＝0.01〜６、
ｅ＝0.01〜６、特に好ましくはｂ＝0.5〜３、ｃ
＝0.3〜３、ｄ＝0.1〜３、ｅ＝0.1〜３であり、ｆ
＝各原子の原子価とａ〜ｅの値により自然に決ま
る数で表わされる。）
で示される実質的にアンモニウムまたはアルカリ
金属イオンを含まない遊離酸型ヘテロポリ酸触媒
である。
ここで実質的にアンモニウムまたはアルカリ金
属イオンを含まない遊離酸型ヘテロポリ酸とは、
150℃にて乾燥した後のＸ線回折スペクトルにお
いて主要面間隔が13.8、11.2、10.0、9.60、4.98、
4.78、3.49、3.42、3.21、3.14、2.99および2.81Å
からなる三斜晶型および9.93、4.90、4.44、4.33、
3.92、3.30、3.25、3.07および2.07Åからなる正方
晶型と思われるものの混合物であり、室温におい
て飽和蒸気圧下においては13.6、8.18、5.82、
5.33、4.44、4.11、3.91、3.53、3.35、3.02、2.90
および2.67Åのピークからなるダイアモンド型の
立方晶をとり、実質的にアルカリ金属やタリウム
あるいはアンモニウムを含まない組成物を意味す
る。
遊離酸型ヘテロポリ酸は、その構造中に含む結
晶水の量により上記のようなＸ線回折スペクトル
の変化を与えるが、又反応雰囲気に接触させる
と、還元型の遊離酸型ヘテロポリ酸となり、主要
面間隔8.50、4.98、4.79、4.69、4.35、4.27、4.19、
3.59、3.48、3.42、3.28および3.23ÅのＸ線回折ピ
ークを与える。
本発明方法に用いられる触媒の製造にあたつて
は、遊離の燐モリブデン酸の調製方法が一般的に
使用される。
触媒を製造する際に用いられる出発原料として
は、モリブデンは酸化モリブデン、モリブデン
酸、燐モリブデン酸、燐バナドモリブデン酸が、
燐原料としては燐酸、亜燐酸、五酸化燐、燐モリ
ブデン酸、燐バナドモリブデン酸、燐酸バナジウ
ム、燐酸銅等が、バナジウム原料としては五酸化
バナジウム、四二酸化バナジウム、三酸化バナジ
ウム、蓚酸バナジル、硫酸バナジル、二塩化バナ
ジル、燐酸バナジウム、燐バナドモリブデン酸等
が、銅原料としては酸化第一銅、酸化第二銅、塩
基性炭酸銅、燐酸銅等が、そして硼酸原料として
は酸化硼素、硼酸等が使用される。
モリブデン酸、燐酸、バナジン酸、硼酸等のア
ルカリ金属塩やアンモニウム塩も使用できなくは
ないが、鉱酸等で遊離酸に変換したり、エーテル
で遊離酸を抽出したりあるいは塩酸を加えてアン
モニウム根を塩化アンモニウムとして揮散させる
操作が必要となる。又残留するアルカリ金属やア
ンモニウムにより、活性が低下するので、好まし
い方法とは言えない。
先に挙げた原料化合物に水を加えて高温で煮
沸、還流し、ヘテロポリ酸の水溶液とする。
この水溶液を砂浴上で100〜150℃で蒸発乾固し
て固形物を得る。この固形物を粉砕して、更に打
錠してタブレツトにするか、担体にまぶしつけて
粒状の触媒とする。又触媒を蒸発乾固する過程に
おいて、水溶液を粒状多孔質無機担体に含浸し
て、これを乾燥する方法も使用することができ
る。
担体としては、シリカゲル、アルミナ、アルミ
ノシリケート、シリコンカーバイド、軽石、硅藻
土、チタン等の成型物あるいはこれらの粉末やシ
リカゲル等のコロイドが使用される。
本発明において使用されるメタクロレイン原料
としては、純粋なメタクロレインである必要はな
く、イソブチレンを空気で触媒上で酸化して得ら
れたメタクロレイン、未反応イソブチレン、一酸
化炭素、炭酸ガス、室素ガス、水蒸気等を含んだ
混合ガスでもよい。
使用する酸素原料も同様に、純粋な酸素でもよ
いが、一般には空気が使用される。また酸素を二
酸化炭素あるいは窒素のような不活性ガスで希釈
したガスを使用してもよい。
本発明の触媒による反応条件として適当な反応
温度は、触媒および原料ガス組成、空間速度等に
よつて異なるが、この種の反応に通常用いられて
いる温度、すなわち200〜450℃、好ましくは250
〜400℃である。
また、本発明は加圧下、減圧下のいずれでも行
いうるが、常圧下で行うのが便利である。
空間速度は200〜12000hr-1、好ましくは500〜
6000hr-1である。
原料ガス組成はメタクロレイン0.1〜10モル％、
酸素は0.1〜20モル％、水蒸気は０〜90モル％、
好ましくは10〜80モル％である。
原料混合ガス中に水蒸気を共存させることは目
的物であるメタクリル酸の収率上著しく有利であ
る。
本発明触媒は一般には固定床で用いられるが、
流動床でも使用することができる。
以下に実施例をあげて本発明を具体的に説明す
るが、本発明はこれら実施例によつて限定される
ものではない。
なお、本発明明細書におけるメタクロレイン反
応率、メタクリル酸選択率および酢酸選択率は次
のように定義する。
メタクロレイン反応率＝消費メタクロ
レインのモル数／供給メタクロレインのモル数×100（
％）
メタクリル酸選択率＝生成メタクリル
酸のモル数／消費メタクロレインのモル数×100（％）
酢酸選択率＝生成酢酸のモル数／消費
メタクロレインのモル数×100×1/2（％）
なお、分析はガスクロマトグラフイーによつ
た。
実施例 １
酸化モリブデン86.4ｇ、五酸化バナジウム4.55
ｇ、酸化第二銅0.80ｇおよび硼酸1.24ｇを水600
mlに懸濁させ、85％燐酸6.34ｇを更にその液に加
えた。
この懸濁液を10時間煮沸、還流すると赤色の透
明な液となつた。次いてこの液を砂浴上で蒸発乾
固し、更に乾燥器で150℃で５時間乾燥した。
得られた固形物のＸ線回折スペクトルは、主要
面間隔13.8、11.2、10.0、9.93、9.60、4.98、4.90、
4.78、4.44、4.33、3.42、3.30、3.25および3.21Å
のピーク群からなり、遊離酸型ヘテロポリ酸であ
ることを示している。
触媒の組成はMo12P1.1V1Cu0.2B0.4O42.1であつ
た。
触媒固形物を粉砕した後圧縮成型し、これを再
び粗く砕いて10〜16メツシユに篩別した。この触
媒２mlを内径12mmのガラス製反応管に充填し、メ
タクロレイン3.9モル％、酸素7.2モル％、窒素
74.6モル％、水蒸気14.2モル％の組成の原料ガス
を触媒に対する空間速度2800hr-1にて供給した。
反応温度300℃においてはメタクロレイン反応
率72.5％、メタクリル酸選択率87.5％、酢酸選択
率4.6％であつた。
また、反応温度320℃ではメタクロレイン反応
率87.9％、メタクリル酸選択率83.7％、酢酸選択
率6.2％であつた。
実施例 ２
実施例１の触媒を用い、メタクロレイン3.9モ
ル％、酢酸7.2モル％、窒素60.4モル％、水蒸気
28.4モル％の水蒸気の含まれる濃度を高めた組成
の原料ガスを空間速度2800hr-1で供給した。
反応温度300℃においてはメタクロレイン反応
率80.6％、メタクリル酸選択率89.2％、酢酸選択
率5.4％であつた。
また反応温度320℃ではメタクロレイン反応率
95.4％、メタクリル酸選択率85.4％、酢酸選択率
4.1％であつた。
実施例 ３
実施例１の触媒を用い、実施例２と同じ組成の
ガスで空間速度1600hr-1の比較的緩やかな条件で
反応を行つた。
反応温度280℃においてはメタクロレイン反応
率80.1％、メタクリル酸選択率88.5％、酢酸選択
率2.9％であつた。
反応温度300℃ではメタクロレイン反応率95.8
％、メタクリル酸選択率85.5％、酢酸選択率4.6
％であつた。
実施例 ４〜９
実施例１と同様にして製作された種々の組成の
触媒について実施例１と同じ反応条件で活性試験
を行つた。
触媒組成と活性試験結果を第１表に示す。
The present invention relates to a method for producing methacrylic acid in high yield by catalytically oxidizing methacrolein with molecular oxygen or a molecular oxygen-containing gas in a high-temperature gas phase. Regarding the production of methacrylic acid by catalytic oxidation of methacrolein in a high-temperature gas phase, many methods using catalysts made of molybdic acid or its salts have been proposed, but these methods have yet to be industrialized. has not been reached yet. One reason for this is that the yield when producing methacrylic acid from methacrolein is low.
When acrylic acid is produced from acrolein using a similar reaction, the yield is at an extremely high level, which is in good contrast to what has already been industrialized. The low yield of methacrylic acid may be due to the fact that methacrolein is more easily oxidized than acrolein, and complete oxidation (formation of carbon monoxide and carbon dioxide) is more likely to occur than partial oxidation. . Another reason why it has not yet been industrialized is that the catalyst used for this purpose has a short lifespan and cannot be used as a practical industrial catalyst. Catalysts made of phosphomolybdic acid or its salts have difficulty in heat resistance, and their activity decreases due to phenomena such as thermal decomposition and sintering. Since the selectivity for producing methacrylic acid from methacrolein is higher at lower temperatures, it is desirable to use a catalyst made of phosphomolybdic acid or a salt thereof at as low a temperature as possible. However, since the activity decreases as the temperature decreases, the size of the reactor and the amount of catalyst charged become enormous, making it difficult to achieve economically. Catalysts with even higher activity are required in multi-stage oxidation and recycling methods in which the one-pass reaction rate of methacrolein is suppressed to obtain a high selectivity of methacrylic acid. A catalyst molded into a shape to be filled into a reactor.
600hr -1 or more, crushed to 1-2mm
The catalyst must be able to react sufficiently at a space velocity of 1500 -1 or higher. In this respect, conventionally known catalysts have insufficient activity and unsatisfactory selectivity. Recently, a method to increase the yield of methacrylic acid has been to add alkali metals such as potassium, rubidium, or cesium, or thallium to a phosphomolybdic acid catalyst whose main components are molybdenum, phosphorus, vanadium, and copper to form a salt thereof. It has been proposed to add koto or arsenic. However, although the addition of these components appears to increase the one-pass yield, it has the disadvantage of decreasing activity. Furthermore, arsenic is a typical poisonous substance, and its handling and management are particularly problematic among substances designated as specific chemical substances. Catalyst production, transportation, filling in reactors, extraction work, and disposal pose extremely difficult problems in terms of occupational and environmental health. In view of these problems, the inventors of the present application have earnestly searched for a catalyst that has high activity, particularly high activity and high selectivity at low temperatures, and is safe and easy to handle, and as a result, the present invention has been achieved. The present invention uses a catalyst consisting of molybdenum, phosphorus, vanadium, copper, and boron to produce methacrylic acid with high selectivity and high yield, and particularly because of its extremely high activity, especially at low temperatures. The catalyst has an extremely long life and provides a method that is fully commercially viable. The general composition of the catalyst is Mo a P b V c Cu d B e Of (where a, b, c, d, e and f are the ratios of the numbers of molybdenum, phosphorus, vanadium, copper, boron and oxygen atoms, respectively If a=12, b=0.1~6, c=0.1~6, d=0.01~6,
e=0.01-6, particularly preferably b=0.5-3, c
=0.3~3, d=0.1~3, e=0.1~3, and f
= Represented by a number naturally determined by the valence of each atom and the values of a to e. ) is a free acid type heteropolyacid catalyst substantially free of ammonium or alkali metal ions. Here, the free acid type heteropolyacid that does not substantially contain ammonium or alkali metal ions is
The main spacings in the X-ray diffraction spectrum after drying at 150°C are 13.8, 11.2, 10.0, 9.60, 4.98,
4.78, 3.49, 3.42, 3.21, 3.14, 2.99 and 2.81Å
Triclinic type consisting of and 9.93, 4.90, 4.44, 4.33,
It is a mixture of what appears to be a tetragonal crystal type consisting of 3.92, 3.30, 3.25, 3.07 and 2.07 Å, and at room temperature and under saturated vapor pressure it is 13.6, 8.18, 5.82,
5.33, 4.44, 4.11, 3.91, 3.53, 3.35, 3.02, 2.90
It means a composition that has a diamond-shaped cubic crystal structure with a peak of 2.67 Å and does not substantially contain alkali metals, thallium, or ammonium. A free acid type heteropolyacid changes its X-ray diffraction spectrum as described above depending on the amount of crystallization water contained in its structure, but when it comes into contact with a reaction atmosphere, it becomes a reduced free acid type heteropolyacid, and the main Surface spacing 8.50, 4.98, 4.79, 4.69, 4.35, 4.27, 4.19,
It gives X-ray diffraction peaks at 3.59, 3.48, 3.42, 3.28 and 3.23 Å. In producing the catalyst used in the process of the present invention, a method for preparing free phosphomolybdic acid is generally used. The starting materials used in the production of catalysts include molybdenum oxide, molybdic acid, phosphomolybdic acid, phosphovanadomolybdic acid,
Phosphorus raw materials include phosphoric acid, phosphorous acid, phosphorus pentoxide, phosphomolybdic acid, phosphovanadomolybdic acid, vanadium phosphate, copper phosphate, etc. Vanadium raw materials include vanadium pentoxide, vanadium tetroxide, vanadium trioxide, vanadyl oxalate, etc. Vanadyl sulfate, vanadyl dichloride, vanadium phosphate, phosphovanadomolybdic acid, etc. are used as copper raw materials, cuprous oxide, cupric oxide, basic copper carbonate, copper phosphate, etc. are used as raw materials for copper, and boron oxide, Boric acid etc. are used. Alkali metal salts and ammonium salts such as molybdic acid, phosphoric acid, vanadate acid, and boric acid can also be used, but ammonium salts can be obtained by converting them to free acids with mineral acids, extracting the free acids with ether, or adding hydrochloric acid. It is necessary to volatilize the roots as ammonium chloride. Furthermore, the remaining alkali metals and ammonium reduce the activity, so it cannot be said to be a preferable method. Water is added to the above-mentioned raw material compound, and the mixture is boiled and refluxed at a high temperature to form an aqueous solution of heteropolyacid. This aqueous solution is evaporated to dryness on a sand bath at 100-150°C to obtain a solid. This solid substance is pulverized and further compressed into tablets, or sprinkled on a carrier to form a granular catalyst. Further, in the process of evaporating the catalyst to dryness, a method of impregnating a granular porous inorganic carrier with an aqueous solution and drying the carrier can also be used. As the carrier, molded products such as silica gel, alumina, aluminosilicate, silicon carbide, pumice, diatomaceous earth, titanium, etc., or powders thereof, and colloids such as silica gel are used. The methacrolein raw material used in the present invention does not need to be pure methacrolein, but includes methacrolein obtained by oxidizing isobutylene with air over a catalyst, unreacted isobutylene, carbon monoxide, carbon dioxide gas, A mixed gas containing raw gas, water vapor, etc. may be used. Similarly, the oxygen source used may be pure oxygen, but air is generally used. Alternatively, a gas obtained by diluting oxygen with an inert gas such as carbon dioxide or nitrogen may be used. The reaction temperature suitable for the reaction conditions using the catalyst of the present invention varies depending on the catalyst, raw material gas composition, space velocity, etc., but is the temperature normally used for this type of reaction, that is, 200 to 450°C, preferably 250°C.
~400℃. Further, although the present invention can be carried out either under increased pressure or reduced pressure, it is convenient to carry out under normal pressure. Space velocity is 200~12000hr -1 , preferably 500~
6000hr -1 . Raw material gas composition is methacrolein 0.1 to 10 mol%,
Oxygen is 0.1 to 20 mol%, water vapor is 0 to 90 mol%,
Preferably it is 10 to 80 mol%. The coexistence of water vapor in the raw material mixed gas is extremely advantageous in terms of the yield of methacrylic acid, which is the target product. The catalyst of the present invention is generally used in a fixed bed, but
Fluidized beds can also be used. The present invention will be specifically explained below with reference to Examples, but the present invention is not limited to these Examples. In addition, the methacrolein reaction rate, methacrylic acid selectivity, and acetic acid selectivity in the present specification are defined as follows. Methacrolein reaction rate = Number of moles of methacrolein consumed / Number of moles of methacrolein supplied × 100 (
%) Methacrylic acid selectivity = Number of moles of methacrylic acid produced/Number of moles of methacrolein consumed x 100 (%) Acetic acid selectivity = Number of moles of acetic acid produced/Number of moles of methacrolein consumed x 100 x 1/2 (%) The analysis was conducted using gas chromatography. Example 1 Molybdenum oxide 86.4g, vanadium pentoxide 4.55g
g, 0.80 g of cupric oxide and 1.24 g of boric acid to 600 g of water
ml and further added 6.34 g of 85% phosphoric acid to the solution. When this suspension was boiled and refluxed for 10 hours, it became a red transparent liquid. Next, this liquid was evaporated to dryness on a sand bath and further dried in a drier at 150°C for 5 hours. The X-ray diffraction spectrum of the obtained solid has major spacings of 13.8, 11.2, 10.0, 9.93, 9.60, 4.98, 4.90,
4.78, 4.44, 4.33, 3.42, 3.30, 3.25 and 3.21Å
It consists of a group of peaks, indicating that it is a free acid type heteropolyacid. The composition of the catalyst was Mo 12 P 1.1 V 1 Cu 0.2 B 0.4 O 42.1 . The catalyst solid was crushed and compression molded, and then coarsely crushed again and sieved into 10 to 16 meshes. 2 ml of this catalyst was packed into a glass reaction tube with an inner diameter of 12 mm, and 3.9 mol% of methacrolein, 7.2 mol% of oxygen, and nitrogen
A raw material gas having a composition of 74.6 mol% and water vapor of 14.2 mol% was supplied at a space velocity of 2800 hr -1 relative to the catalyst. At a reaction temperature of 300°C, the methacrolein reaction rate was 72.5%, the methacrylic acid selectivity was 87.5%, and the acetic acid selectivity was 4.6%. Furthermore, at a reaction temperature of 320°C, the methacrolein reaction rate was 87.9%, the methacrylic acid selectivity was 83.7%, and the acetic acid selectivity was 6.2%. Example 2 Using the catalyst of Example 1, methacrolein 3.9 mol%, acetic acid 7.2 mol%, nitrogen 60.4 mol%, water vapor
A raw material gas having a composition with an increased concentration of 28.4 mol % water vapor was supplied at a space velocity of 2800 hr -1 . At a reaction temperature of 300°C, the methacrolein reaction rate was 80.6%, the methacrylic acid selectivity was 89.2%, and the acetic acid selectivity was 5.4%. In addition, at the reaction temperature of 320℃, the methacrolein reaction rate
95.4%, methacrylic acid selectivity 85.4%, acetic acid selectivity
It was 4.1%. Example 3 Using the catalyst of Example 1 and a gas having the same composition as in Example 2, a reaction was carried out under relatively gentle conditions at a space velocity of 1600 hr -1 . At a reaction temperature of 280°C, the methacrolein reaction rate was 80.1%, the methacrylic acid selectivity was 88.5%, and the acetic acid selectivity was 2.9%. Methacrolein reaction rate 95.8 at reaction temperature 300℃
%, methacrylic acid selectivity 85.5%, acetic acid selectivity 4.6
It was %. Examples 4 to 9 Activity tests were conducted on catalysts of various compositions prepared in the same manner as in Example 1 under the same reaction conditions as in Example 1. The catalyst composition and activity test results are shown in Table 1.
【表】
実施例 10
酸化モリブデン86.4ｇ、五酸化バナジウム4.55
ｇ、酸化銅1.60ｇおよび硼酸1.24ｇを水600mlに
懸濁させ、85％燐酸6.34ｇを更にその液に加え
た。
この懸濁液を10時間煮沸、還流して赤色の透明
液を得た。この液を更に煮沸し、200mlまで濃縮
した。
次いで液に直径５mmの球形多孔質アルフアアル
ミナ145.7ｇを投入し、なおも濃縮を続行し、蒸
発乾固させ、触媒成分を完全に担体に担持した。
こうして得られた触媒の活性成分の組成は
Mo12P1.1V1Cu0.4O42.3であり、触媒中の活性成分
量は約40重量％であつた。
この触媒を実施例１と同じ組成の原料ガスで空
間速度1600hr-1で活性試験を行つた。
その結果320℃においてはメタクロレイン反応
率77.6％、メタクリル酸選択率88.2％、酢酸選択
率3.8％であつた。
また、340℃ではメタクロレイン反応率93.6％、
メタクリル酸選択率83.0％、酢酸選択率6.3％で
あつた。
実施例 11
酸化モリブデン86.4ｇ、五酸化バナジウム4.55
ｇ、酸化銅1.60ｇおよび硼酸1.24ｇを水600mlに
懸濁させ、85％燐酸6.34ｇを更にその液に加え
た。
この懸濁液を10時間煮沸、還流して赤色の透明
液を得た。この液に担体として20重量％濃度のシ
リカゲル105ｇを加えた。次いでこの液を砂浴上
で蒸発乾固し、更に乾燥器で150℃で５時間乾燥
した。
得られた固形物を粉砕した後圧縮成型し、これ
を再び粗く砕いて10〜16メツシユに篩別した。
こうして得られた触媒の活性成分の組成は
Mo12P1.1V1Cu0.4B0.4O42.3であり、触媒中の活性
成分量は約82.2重量％であつた。
この触媒を用い実施例１と同じ組成の原料ガス
を空間速度2800hr-1にて供給した。
その結果反応速度300℃においてはメタクロレ
イン反応率70.4％、メタクリル酸選択率87.0％、
酢酸選択率4.9であつた。
また反応温度320℃ではメタクロレイン反応率
88.6％、メタクリル酸選択率82.3％、酢酸選択率
6.6％であつた。
実施例 12
実施例10の触媒を用い、実施例10の条件でただ
触媒層温度を350℃として熱的に過酷な条件で寿
命試験を行つた。活性測定はその都度触媒層温度
を320℃まで下げて行つた。第２表に活性の経時
的変化を示す。[Table] Example 10 Molybdenum oxide 86.4g, vanadium pentoxide 4.55
g, 1.60 g of copper oxide and 1.24 g of boric acid were suspended in 600 ml of water, and 6.34 g of 85% phosphoric acid was further added to the solution. This suspension was boiled and refluxed for 10 hours to obtain a red transparent liquid. This liquid was further boiled and concentrated to 200ml. Next, 145.7 g of spherical porous alpha alumina with a diameter of 5 mm was added to the solution, and concentration was continued to evaporate to dryness, so that the catalyst component was completely supported on the carrier. The composition of the active component of the catalyst thus obtained is
Mo 12 P1.1V 1 Cu 0.4 O 42.3 , and the amount of active component in the catalyst was about 40% by weight. This catalyst was subjected to an activity test using a raw material gas having the same composition as in Example 1 at a space velocity of 1600 hr -1 . As a result, at 320°C, the methacrolein reaction rate was 77.6%, the methacrylic acid selectivity was 88.2%, and the acetic acid selectivity was 3.8%. In addition, at 340℃, the methacrolein reaction rate was 93.6%,
The methacrylic acid selectivity was 83.0% and the acetic acid selectivity was 6.3%. Example 11 Molybdenum oxide 86.4g, vanadium pentoxide 4.55g
g, 1.60 g of copper oxide and 1.24 g of boric acid were suspended in 600 ml of water, and 6.34 g of 85% phosphoric acid was further added to the solution. This suspension was boiled and refluxed for 10 hours to obtain a red transparent liquid. To this solution was added 105 g of 20% by weight silica gel as a carrier. This liquid was then evaporated to dryness on a sand bath and further dried in a dryer at 150°C for 5 hours. The obtained solid was pulverized and compression molded, then coarsely crushed again and sieved into 10 to 16 meshes. The composition of the active component of the catalyst thus obtained is
The amount of active component in the catalyst was approximately 82.2 % by weight . Using this catalyst, a raw material gas having the same composition as in Example 1 was supplied at a space velocity of 2800 hr -1 . As a result, at a reaction rate of 300℃, the methacrolein reaction rate was 70.4%, the methacrylic acid selectivity was 87.0%,
The acetic acid selectivity was 4.9. In addition, at the reaction temperature of 320℃, the methacrolein reaction rate
88.6%, methacrylic acid selectivity 82.3%, acetic acid selectivity
It was 6.6%. Example 12 Using the catalyst of Example 10, a life test was conducted under the conditions of Example 10 but under thermally severe conditions with the catalyst layer temperature at 350°C. Each time the activity was measured, the temperature of the catalyst layer was lowered to 320°C. Table 2 shows changes in activity over time.
【表】
参考例 １
実施例１の触媒の組成から硼素を抜いた組成で
あるMo12V1P1.1Cu0.2O41.5を実施例１と同様に作
り同じ条件で活性試験を行つた。
反応温度300℃におけるメタクロレイン反応率
は53.7％、メタクリル酸選択率84.6％、酢酸選択
率6.9％であつた。[Table] Reference Example 1 Mo 12 V 1 P1.1Cu 0.2 O 41.5 , which had a composition in which boron was removed from the catalyst composition of Example 1, was prepared in the same manner as in Example 1, and an activity test was conducted under the same conditions. At a reaction temperature of 300°C, the methacrolein reaction rate was 53.7%, the methacrylic acid selectivity was 84.6%, and the acetic acid selectivity was 6.9%.
Claims (1)
素含有ガスにより気相接触酸化してメタクリル酸
を製造するにあたり、一般組成が MoaPbVcCudBeOf （ここにａ、ｂ、ｃ、ｄ、ｅおよびｆはそれぞれ
モリブデン、燐、バナジウム、銅、硼素および酸
素の原子数の比である。そしてａ＝12とすると、
ｂ＝0.1〜６、ｃ＝0.1〜６、ｄ＝0.01〜６、ｅ＝
0.01〜６、ｆ＝各原子の原子価とａ〜ｅの値によ
り自然に決まる数で表わされる。） で示される実質的にアンモニウムまたはアルカリ
金属イオンを含まない遊離酸型ヘテロポリ酸触媒
を使用することを特徴とするメタクリル酸の製造
方法。 ２ 触媒成分の原子数の比がａ＝12に固定した場
合、ｂ＝0.5〜３、ｃ＝0.3〜３、ｄ＝0.1〜３、ｅ
＝0.1〜３、ｆ＝各原子の原子価とａ〜ｅの値に
より自然に決まる数で表わされる特許請求の範囲
第１項記載の方法。[Claims] 1. In producing methacrylic acid by gas phase catalytic oxidation of methacrolein with molecular oxygen or molecular oxygen-containing gas, the general composition is Mo a P b V c Cu d B e Of (here where a, b, c, d, e and f are the ratios of the number of atoms of molybdenum, phosphorus, vanadium, copper, boron and oxygen, respectively.If a=12, then
b=0.1~6, c=0.1~6, d=0.01~6, e=
0.01 to 6, f = a number naturally determined by the valence of each atom and the values of a to e. ) A method for producing methacrylic acid, which comprises using a free acid type heteropolyacid catalyst substantially free of ammonium or alkali metal ions. 2 When the ratio of the number of atoms of the catalyst components is fixed at a = 12, b = 0.5 to 3, c = 0.3 to 3, d = 0.1 to 3, e
1. The method according to claim 1, wherein f=0.1 to 3, and f=a number naturally determined by the valence of each atom and the values of a to e.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP56193948A JPS5896041A (en) | 1981-12-01 | 1981-12-01 | Preparation of methacrylic acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP56193948A JPS5896041A (en) | 1981-12-01 | 1981-12-01 | Preparation of methacrylic acid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5896041A JPS5896041A (en) | 1983-06-07 |
| JPH0213652B2 true JPH0213652B2 (en) | 1990-04-04 |
Family
ID=16316415
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP56193948A Granted JPS5896041A (en) | 1981-12-01 | 1981-12-01 | Preparation of methacrylic acid |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5896041A (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60209258A (en) * | 1984-04-02 | 1985-10-21 | Nippon Shokubai Kagaku Kogyo Co Ltd | Oxidation catalyst and its manufacture |
| JP4745766B2 (en) * | 2004-09-07 | 2011-08-10 | 三菱レイヨン株式会社 | Catalyst for producing methacrylic acid, method for producing the same, and method for producing methacrylic acid |
| DE102012207811A1 (en) | 2012-05-10 | 2012-07-12 | Basf Se | Heterogeneously catalyzed gas phase partial oxidation of (meth)acrolein to (meth)acrylic acid using a catalytically active multimetal oxide mass |
| DE102013202048A1 (en) | 2013-02-07 | 2013-04-18 | Basf Se | Preparing catalytically active composition useful for preparing a catalyst, comprises e.g. thermally treating geometrical precursor bodies formed by a mixture obtained by uniformly mixing e.g. a spray-dried powder and molybdenum oxide |
| JP2023522261A (en) | 2020-04-21 | 2023-05-29 | ベーアーエスエフ・エスエー | Method for producing catalytically active multi-element oxides containing elements Mo, W, V and Cu |
| EP4237145A1 (en) | 2020-10-29 | 2023-09-06 | Basf Se | Method for producing a core-shell catalyst |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5466619A (en) * | 1977-10-31 | 1979-05-29 | Nippon Kayaku Co Ltd | Preparation of methacrylic acid and its catalyst |
| JPS5579341A (en) * | 1978-12-13 | 1980-06-14 | Nippon Kayaku Co Ltd | Preparation of methacrylic acid and catalyst |
-
1981
- 1981-12-01 JP JP56193948A patent/JPS5896041A/en active Granted
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5466619A (en) * | 1977-10-31 | 1979-05-29 | Nippon Kayaku Co Ltd | Preparation of methacrylic acid and its catalyst |
| JPS5579341A (en) * | 1978-12-13 | 1980-06-14 | Nippon Kayaku Co Ltd | Preparation of methacrylic acid and catalyst |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5896041A (en) | 1983-06-07 |
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