CN1049162C - Catalyst for preparing methacrylic acid by two-step oxidation of isobutene or tertiary butanol - Google Patents
Catalyst for preparing methacrylic acid by two-step oxidation of isobutene or tertiary butanol Download PDFInfo
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- CN1049162C CN1049162C CN94110762A CN94110762A CN1049162C CN 1049162 C CN1049162 C CN 1049162C CN 94110762 A CN94110762 A CN 94110762A CN 94110762 A CN94110762 A CN 94110762A CN 1049162 C CN1049162 C CN 1049162C
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- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 title claims abstract description 27
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 239000003054 catalyst Substances 0.000 title claims abstract description 13
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 title claims abstract description 10
- 230000003647 oxidation Effects 0.000 title claims description 11
- 238000007254 oxidation reaction Methods 0.000 title claims description 11
- 238000000034 method Methods 0.000 claims abstract description 19
- 239000002994 raw material Substances 0.000 claims abstract description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 23
- 238000002360 preparation method Methods 0.000 claims description 11
- 150000001875 compounds Chemical class 0.000 claims description 10
- 150000003839 salts Chemical class 0.000 claims description 9
- 229910002651 NO3 Inorganic materials 0.000 claims description 8
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- PPNKDDZCLDMRHS-UHFFFAOYSA-N dinitrooxybismuthanyl nitrate Chemical compound [Bi+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PPNKDDZCLDMRHS-UHFFFAOYSA-N 0.000 claims description 7
- 229910052742 iron Inorganic materials 0.000 claims description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 229910052728 basic metal Inorganic materials 0.000 claims description 5
- 150000003818 basic metals Chemical class 0.000 claims description 5
- 238000000465 moulding Methods 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims description 4
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- DJHGAFSJWGLOIV-UHFFFAOYSA-N Arsenic acid Chemical compound O[As](O)(O)=O DJHGAFSJWGLOIV-UHFFFAOYSA-N 0.000 claims description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 3
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 3
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- 229910052785 arsenic Inorganic materials 0.000 claims description 3
- 229940000488 arsenic acid Drugs 0.000 claims description 3
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims description 3
- 229910052797 bismuth Inorganic materials 0.000 claims description 3
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 3
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 3
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 3
- 229910052720 vanadium Inorganic materials 0.000 claims description 3
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- 239000006004 Quartz sand Substances 0.000 claims description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052787 antimony Inorganic materials 0.000 claims description 2
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(III) oxide Inorganic materials O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 239000011733 molybdenum Substances 0.000 claims description 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical group O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 239000011574 phosphorus Substances 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- -1 amine molybdate Chemical class 0.000 claims 2
- 239000007809 chemical reaction catalyst Substances 0.000 claims 2
- 239000012254 powdered material Substances 0.000 claims 2
- 238000001354 calcination Methods 0.000 claims 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical class [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 claims 1
- 229910052748 manganese Inorganic materials 0.000 claims 1
- 229910052719 titanium Inorganic materials 0.000 claims 1
- STNJBCKSHOAVAJ-UHFFFAOYSA-N Methacrolein Chemical compound CC(=C)C=O STNJBCKSHOAVAJ-UHFFFAOYSA-N 0.000 abstract description 14
- 238000006243 chemical reaction Methods 0.000 abstract description 6
- 239000000203 mixture Substances 0.000 abstract description 3
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 230000009466 transformation Effects 0.000 description 5
- 235000018660 ammonium molybdate Nutrition 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 230000033001 locomotion Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000010970 precious metal Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- MWFMGBPGAXYFAR-UHFFFAOYSA-N 2-hydroxy-2-methylpropanenitrile Chemical compound CC(C)(O)C#N MWFMGBPGAXYFAR-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- 206010013786 Dry skin Diseases 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 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
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000006392 deoxygenation reaction Methods 0.000 description 2
- 229910001882 dioxygen Inorganic materials 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 235000010333 potassium nitrate Nutrition 0.000 description 2
- 239000004323 potassium nitrate Substances 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- FAPDDOBMIUGHIN-UHFFFAOYSA-K antimony trichloride Chemical compound Cl[Sb](Cl)Cl FAPDDOBMIUGHIN-UHFFFAOYSA-K 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000011777 magnesium Substances 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
- 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 description 1
- 230000035800 maturation Effects 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910052714 tellurium Inorganic materials 0.000 description 1
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 1
- 229910052716 thallium Inorganic materials 0.000 description 1
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A catalyst for preparing methacrylic acid by two-step method using isobutene or tert-butanol as raw material and its preparing process, the composition general formula of the first-stage catalyst is Mo10The composition general formula of the BiaFebXcYdZeOf two-stage catalyst is Mo12Pa1Asb1Vc1Ad1De1Of1The reaction for preparing methacrylic acid by using the catalyst can reach the conversion rate of isobutene or tert-butyl alcohol of 100 percent, the once-through yield of methacrylic acid of more than 60 percent (mol) and the once-through yield of methacrolein of about 10 percent (mol).
Description
The present invention is an application number 90105311.2, applying date 90.6.9, denomination of invention " iso-butylene or trimethyl carbinol two-step oxidation system methacrylic acid ' divide an application.
The present invention relates to produce employed catalyzer of methacrylic acid and preparation method.
Methacrylic acid (MAA) and ester class thereof are epochmaking Chemicals.Wherein methymethacrylate (MMA) is a monomer of producing synthetic glass, and methacrylic acid and ester class thereof also are widely used in and make coating, binding agent and be used as plastic modifier in addition.MMA only produced with the acetone cyanohydrin method in the past.This method operational path maturation, raw material is also cheap and easy to get, but propyl alcohol cyanalcohol method has unsurmountable shortcoming, shows that mainly toxicity is big, equipment corrosion serious and pay produce big and difficult etc.In order to overcome the shortcoming of acetone cyanohydrin method, people have proposed many new MMA and have produced routes, and these new routes all are with the product of large-scale petroleum chemical industry such as ethene, propylene, iso-butylene (i-C
4 =) or the trimethyl carbinol (TBA) be main raw material, wherein with i-C
4 =Or TBA is raw material production MAA, and to produce the route of MMA be economical favourable in esterification then.
With i-C
4 =Or the process that TBA produces MAA for the raw material two-step oxidation is: the first step, i-C
4 =Or TBA catalytic gas phase oxidation in the presence of molecular oxygen becomes Methylacrylaldehyde (MAL): in second step, MAL catalytic gas phase oxidation in the presence of molecular oxygen becomes MAA.Relevant i-C
4 =Or the TBA catalytic gas phase oxidation becomes MAL, and the MAL two-step oxidation catalyzer that is oxidized to MAA has many motions then.Used tellurium (Te), thallium elements such as (Tl) key component as catalyzer in U.S4250339, these motions of day public property special permission 57-72937 as catalyzer.The loss yet these materials are easy to disperse in the long-term operation process of catalyzer, thus the performance degradation of catalyzer caused, and the precious metal element usage quantity in these motions is big on the other hand, and the manufacturing cost of catalyzer is improved.This is uneconomic from industrial angle.
The object of the present invention is to provide that stable performance, cost are low, the catalyzer of high produced in yields MAA.
In order to achieve the above object, research by experiment, the present invention is with consisting of Mo
10The catalyzer of BiaFebXcY-dZeOF is as i-C
4 =Or TBA is oxidized to the catalyzer of Methylacrylaldehyde (MAL), usefulness composition Mo
12Pa
1Asb
1Vc
1Ad
1De
1Of
1Catalyzer, be oxidized to second section catalyzer of MAA as MAL.Here Mo represents molybdenum element, Bi represents bismuth element, Fe represents ferro element, X is at least a element of selecting from cobalt and nickel, and Y is from manganese, magnesium, zinc, iron, at least a element of selecting in the vanadium, Z are at least a elements of selecting from basic metal, Q represents oxygen element, P represents phosphoric, and As represents arsenic element, and V represents v element, A is from copper, antimony, cobalt, iron, zinc, at least a element of selecting in the silver, D is at least a element of selecting from basic metal and alkaline-earth metal, preferably uses potassium, wherein a, b, c, d, e, f and a1, b1, C1, d1, e1, f1 represents the molar ratio of each element, they get positive numerical value: a=0 respectively, .01～5, b=0.1～10, c=2～15, d=0～5, e=0.001～0.5, f is determined by other each atoms of elements valency and atomic ratio: a1=5～3, b1=0.01～2, C1=0.01～5, d1=0.01～5, e1=0.01～3, f1 is by other each atoms of elements valency and atomic ratio decision.
Prepare this two catalyzer, used raw material can be oxide compound, acid or the salt that contains above various elements.Can be with molybdic oxide or ammonium molybdate as molybdenum; Bismuth can be used bismuthous oxide bismuth trioxide, Bismuth trinitrate etc.: iron can use iron nitrate, iron(ic) chloride, ferric oxide: X can use nitrate, the muriate of respective element: nitrate, oxide compound or other the salt that can use respective element.Phosphorus can be with phosphoric acid or other salt, and arsenic can be with arsenic acid etc., and vanadium can be used ammonium vanadate, Vanadium Pentoxide in FLAKES etc.; A can be with the oxide compound of respective element or nitrate etc.; D can use nitrate, oxyhydroxide or the muriate etc. of respective element.
The all cpds that will contain above element during the preparation catalyzer dissolves in water, mixes, and 50～90 ℃ of stirrings, adds ammoniacal liquor and is neutralized to pH=4～8.Evaporate to dryness moisture content then, the material that obtains after 100～150 ℃ of oven dry, carries out preroasting again, makes it to decompose, and removes the part volatile matter.Can straight forming to first section catalyzer, can add 10～50% (silicon carbide of wt% or Al to second section catalyzer
2O
3, quartz sand is as the carrier moulding, or no carrier added(NCA) straight forming.Granules of catalyst roasting in air of moulding can be obtained required catalyzer.For first section oxide catalyst, the condition of preroasting is 150～400 ℃, 1～50 hour, is more preferably 5～20 hours.The condition of roasting is 500～800 ℃, 1～30 hour, is more preferably 210 hours.For second section oxide catalyst, the condition of preroasting is 150～320 ℃, 0.5～20 hour, is more preferably 1～10 hour.The condition of roasting is 300～450 ℃, 0.5～30 hour, is more preferably 2～10 hours.
Can obtain aforesaid catalyzer of the present invention by aforesaid method.
Purpose of the present invention reaches, and the cost of catalyzer can reduce, owing to there is not the oxidation wastage problem, the stability of catalyzer and selectivity is improved again.
Use catalyzer of the present invention, by i-C
4 =Or TBA produces MAA, i-C
4 =Or the transformation efficiency of TBA is that the single receipts of 100%MAA can be stabilized in more than 60% (mol), and single receipts of MAL is 10% (mol).The MAA total recovery is more than 65% (mol).
Because the consumption without precious metal Cs, Te, Tl or precious metal among the present invention is very low, and still can obtain higher MAA yield, thereby can reduce the Preparation of catalysts cost, and therefore the MAA production cost is also reduced.
Embodiment
Example 1: 88.3 gram ammonium molybdates are dissolved in 100ml, 50 ℃ the deionized water.24.3 gram Bismuth trinitrates are dissolved in weight concentration 15%, in rare nitric acid of 40ml.40.4 the gram iron nitrate is dissolved in the 10ml deionized water.87.3 the gram Xiao Suangu is dissolved in the 200ml deionized water.2.8 gram saltpetre is dissolved in the 20ml deionized water.The aqueous solution that will contain Bismuth trinitrate, iron nitrate, Xiao Suangu and saltpetre is constantly adding respectively in the ammonium molybdate solution under the condition of stirring, adds 50% manganese nitrate aqueous solution, 17.9 grams at last again, obtains a pulpous state liquid.With this pulpous state liquid evaporate to dryness in water-bath, obtained a solid matter in 24 hours 110 ℃ of dryings then.With the roasting 10 hours in 250 ℃ air of this solid, obtain powdery substance.This powder compacting is made 10～20 purpose particles, roasting 5 hours in 500 ℃ airflow then.The Mo that consists of that is not promptly comprised oxygen
10Bi
1Fe
2Co
6Mn
1K
0.1First section catalyzer.
Example 2: 63.6 gram ammonium molybdates are dissolved in 100ml, 50 ℃ the deionized water.Add the phosphoric acid of 3.45 grams 86% and the arsenic acid of 0.5 gram 85% then.Add the 6N hydrochloric acid 6ml that is dissolved with 3.42 gram butter of antimony more successively, be dissolved with the aqueous solution 50ml of 1.76 gram ammonium vanadate, be dissolved with the aqueous solution 30ml of 3.36 gram potassium hydroxide, obtain a pulpous state solution.Stir ageing 2 hours 70～90 ℃ of temperature, cooling adds the ammoniacal liquor neutralization below 35 ℃ to make pH be 5～7.This solution was obtained a solid matter in 24 hours in 110 ℃ of dryings behind evaporate to dryness in the water-bath.The roasting in 250 ℃ airflow of this solid was obtained powdery substance in 3 hours.This powder compacting is made 10～20 purpose particles, roasting 6 hours in 380 ℃ air then.The Mo that consists of that is not promptly comprised oxygen
12P
1As
0.1V
0.5Sn
0.5Second section catalyzer of K2.0.
Example 3. is each 12ml of catalyzer of example 1 and example 2, after the silicon carbide dilution with the identical order number of 12ml, is respectively charged into flow reactor of fixed bed, at TBA: HO: air=1: 4: 10, air speed 3000h
-1(standard state) answers device by first section under the condition of normal pressure and temperature of reaction 395 ℃ (focuses).First section reaction product directly introduced second section reactor, adds each 5000ml/hr of oxygen and nitrogen simultaneously
-1, be under the condition of 320 ℃ (focuses) in the temperature of second section reactor, reaction result is a trimethyl carbinol transformation efficiency 100%, methacrylic acid yield 64.4%, Methylacrylaldehyde yield 10.5%.
First section catalyzer of method preparation that example 4. usefulness and example 1 are identical consists of Mo beyond the deoxygenation
10Bi
1Fe3Ni6Mg
1Cs
0.005With methods preparation second section catalyzer identical, consist of Mo beyond the deoxygenation with example 2
10P
1As
0.1V
0.5Cu
0.5Sb
0.1K
1.0, with estimating with example 3 identical methods, the result is a trimethyl carbinol transformation efficiency 100% with these two catalyzer, and the methacrylic acid yield is 63.5%, and the Methylacrylaldehyde yield is 11.2%.
Example 5. makes two catalyzer of use-case 1 and example 2, and with estimating with example 3 identical methods, the result who turned round 1000 hours is a trimethyl carbinol transformation efficiency 100%, methacrylic acid yield 64.2%, Methylacrylaldehyde yield 10.1%.
Example 6～example 12: use method preparation first section catalyzer identical with specification sheets example 1, method preparation second section catalyzer identical with example 2 uses the method identical with example 3 to implement the reaction of TBA oxidation system MAA, and reaction result is as shown in table 1.
| Example | One section catalyzer | Two sections catalyzer | TBA transformation efficiency (mol%) | MAA yield (mol%) | MAL yield (mol%) |
| 6 7 8 9 10 11 12 | Mo 10Bi 1Fe 2Co 6Zn 2Cs 0.01Mo 10Bi 1Fe 2Co 8Ti 0.5Cs 0.01Mo 10Bi 1.5Fe 3Co 7V 0.1Cs 0.01Mo 10Bi 1.5Fe 3Co 7V 0.1Rb 0.03Mo 10Bi 1Fe 2Co 8Ti 0.5Cs 0.005Mo 10Bi 1Fe 2Co 8Ti 0.5Cs 0.005Mo 10Bi 1Fe 2Co 8Ti 0.5Cs 0.01 | Mo 12P 1As 0.1V 0.5Sb 0.5K 2.0 Mo 12P 1.13As 0.2V 0.5Sb 0.2K 1.5 Mo 12P 1.13As 0.2V 0.5Sb 0.2K 2.0 Mo 12P 1.13As 0.2V 0.2Sb 0.2K 2.0 Mo 12P 1.13As 0.2V 0.2Co 0.1Fe 0.1K 1.70 Mo 12P 1.13As 0.2V 0.2Zn 0.2K 1.5 Mo 12P 1.13As 0.2V 0.2Ag 0.3K 1.50 | 100 100 100 100 100 100 100 | 64.2 64.1 63.5 63.8 63.3 63.6 64.0 | 10.5 10.3 11.2 10.2 10.7 10.2 10.5 |
Claims (5)
1, a kind of is the catalyzer that the raw material two-step oxidation is produced methacrylic acid with the iso-butylene or the trimethyl carbinol, it is characterized in that: the general formula of first section reaction catalyst system therefor is: Mo
10BiaFebXcYdZeOf, in the formula:
At least a element that the X representative is selected from Co and Ni;
Y represents at least a element of selecting among Mn, Mg, Zn, Ti and the V;
The Z representative is selected from least a element in the basic metal;
A～f represents the molar ratio of each element, a=0.01～5, and b=0.1～10, c=2～15, d=0～5, e=0.001～0.5,
F is by other each atoms of elements valency and atomic ratio decision;
The general formula of second section reaction catalyst system therefor is: Mo
12Pa
1Asb
1Vc
1Ad
1De
1Of
1, in the formula:
At least a element that the A representative is selected from Cu, Sb, Co, Fe, Zn and Ag;
At least a element that the D representative is selected from basic metal and alkaline-earth metal;
a
1～f
1Represent the molar ratio of each element, a
1=0.5～3, b
1=0.01～2, c
1=0.01～5, d
1=0.01～5,
e
1=0.01～3, f
1By other each atoms of elements valency and atomic ratio decision;
2, by the described catalyzer of claim 1, it is characterized in that described basic metal or alkaline-earth metal D are potassium.
3, the Preparation of catalysts method of claim 1 is characterized in that: (1) first section catalysts
The preparation method is:
A) raw material be contain with one section catalyzer in oxide compound, acid or the salt of elements corresponding;
B) oxide compound, acid or the salt that will contain each respective element is dissolved in water or the acid, makes solution respectively, and these solution are mixed, and stirs down at 50～90 ℃, obtains a pulpous state liquid;
C) moisture content in the evaporate to dryness pulpous state liquid, the material that obtains are again 100 ℃～150 ℃ oven dry down;
D) the powdered material of preroasting in air, condition is:
Pre-150～400 ℃ of 1～50 hour times of roast temperature;
E) moulding: the powder straight forming is made 10～20 purpose particles;
F) roasting in air, condition is:
500～800 ℃ of 1～30 hour times of maturing temperature, promptly obtain one section catalyzer.
The preparation method of (2) second sections catalysts is:
A) raw material be contain with two sections catalyzer in oxide compound, acid or the salt of elements corresponding;
B) oxide compound, acid or the salt that will contain each respective element is dissolved in water or the acid, makes solution respectively, and these solution are mixed, and stirs down at 50～90 ℃, obtains a pulpous state liquid, is neutralized to PH=4～8 again;
C) moisture content in the evaporate to dryness pulpous state liquid, the material that obtains are again 100 ℃～150 ℃ oven dry down;
D) the powdered material of preroasting in air, condition is:
150～320 ℃ of 0.5～20 hour times of pre-calcination temperature;
E) moulding: both can no carrier added(NCA) with the powder straight forming, also can add the silicon carbide or the Al of 10～50% (Wt%)
2O
3, quartz sand is as the carrier moulding, makes 10～20 purpose particles;
F) roasting in air, condition is:
300～450 ℃ of 0.5～30 hour times of maturing temperature, promptly obtain two sections catalyzer.
4, by the described method of claim 3, it is characterized in that the oxide compound of described various elements, acid or salt are: molybdenum is molybdic oxide or amine molybdate; Bismuth is bismuthous oxide bismuth trioxide or Bismuth trinitrate; Iron is ferric oxide, iron nitrate or iron(ic) chloride; X is the nitrate or the muriate of respective element; Y is nitrate, oxide compound or other the salt of respective element; Phosphorus is phosphoric acid or other phosphorous salt; Arsenic is arsenic acid; Vanadium is vanadic acid amine or Vanadium Pentoxide in FLAKES; A is the oxide compound or the nitrate of respective element; D is nitrate, oxyhydroxide or the muriate of respective element.
5, by the described method of claim 3, it is characterized in that the Preparation of Catalyst condition is:
One section catalyzer: pre-2～10 hours roast time of 5～20 hours roast time
Two sections catalyzer: pre-2～10 hours roast time of 1～10 hour roast time.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN94110762A CN1049162C (en) | 1994-06-09 | 1994-06-09 | Catalyst for preparing methacrylic acid by two-step oxidation of isobutene or tertiary butanol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN94110762A CN1049162C (en) | 1994-06-09 | 1994-06-09 | Catalyst for preparing methacrylic acid by two-step oxidation of isobutene or tertiary butanol |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 90105311 Division CN1028224C (en) | 1990-06-09 | 1990-06-09 | Two-step oxidation of isobutene or tert-butanol to produce methacrylic acid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1109383A CN1109383A (en) | 1995-10-04 |
| CN1049162C true CN1049162C (en) | 2000-02-09 |
Family
ID=5034694
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN94110762A Expired - Fee Related CN1049162C (en) | 1994-06-09 | 1994-06-09 | Catalyst for preparing methacrylic acid by two-step oxidation of isobutene or tertiary butanol |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1049162C (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101410360B (en) * | 2006-04-03 | 2012-05-16 | 日本化药株式会社 | Method for producing methacrolein and/or methacrylic acid |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114849740A (en) * | 2022-04-14 | 2022-08-05 | 大连理工大学 | Composite metal oxide catalyst for preparing methacrylic acid by oxidizing isobutene and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3576857A (en) * | 1967-11-16 | 1971-04-27 | Goodrich Co B F | Process of preparing unsaturated acids and aldehydes |
| DE2550394A1 (en) * | 1974-11-12 | 1976-05-13 | Montedison Spa | PROCESS FOR THE MANUFACTURING OF ACROLEIN AND ACRYLIC ACID OR METHACROLEIN AND METHACRYLIC ACID AND A CATALYST FOR CARRYING OUT THE SAME |
| US4742884A (en) * | 1985-07-30 | 1988-05-10 | Honda Giken Kogyo Kabushiki Kaisha | Brake device for a motorcycle |
| CN87103192A (en) * | 1986-03-24 | 1988-06-08 | 三菱油化株式会社 | The production of composite oxide catalysts |
-
1994
- 1994-06-09 CN CN94110762A patent/CN1049162C/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3576857A (en) * | 1967-11-16 | 1971-04-27 | Goodrich Co B F | Process of preparing unsaturated acids and aldehydes |
| DE2550394A1 (en) * | 1974-11-12 | 1976-05-13 | Montedison Spa | PROCESS FOR THE MANUFACTURING OF ACROLEIN AND ACRYLIC ACID OR METHACROLEIN AND METHACRYLIC ACID AND A CATALYST FOR CARRYING OUT THE SAME |
| US4742884A (en) * | 1985-07-30 | 1988-05-10 | Honda Giken Kogyo Kabushiki Kaisha | Brake device for a motorcycle |
| CN87103192A (en) * | 1986-03-24 | 1988-06-08 | 三菱油化株式会社 | The production of composite oxide catalysts |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101410360B (en) * | 2006-04-03 | 2012-05-16 | 日本化药株式会社 | Method for producing methacrolein and/or methacrylic acid |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1109383A (en) | 1995-10-04 |
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