CN103204792A - Preparation method of tert-butyl hydroperoxide - Google Patents
Preparation method of tert-butyl hydroperoxide Download PDFInfo
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Abstract
本发明公开了一种叔丁基过氧化氢的制备方法，在氧化反应条件下，将叔丁醇、氧化剂、溶剂和催化剂混合接触，其特征在于所述的催化剂为以可溶性锌盐改性的杂原子分子筛。The invention discloses a preparation method of tert-butyl hydroperoxide. Under oxidation reaction conditions, tert-butanol, an oxidant, a solvent and a catalyst are mixed and contacted, and the catalyst is characterized in that the catalyst is modified with a soluble zinc salt. Heteroatom Molecular Sieves.
Description
Technical field
The invention relates to a kind of method for preparing tertbutyl peroxide, further saying so prepares the method for tertbutyl peroxide about a kind of catalyzed oxidation trimethyl carbinol.
Background technology
Tertbutyl peroxide is water white transparency or yellow liquid, can with immiscible organic solvents such as ethanol, ether.Stable below 75 ℃, lose oxygen at 90～100 ℃, then explode in the time of 250 ℃.Tertbutyl peroxide mainly as the catalyzer of polyreaction, is used as the introducing agent of peroxidation group in the substitution reaction, be used for fiber and coloration of textile materials and stamps such as cotton, viscose glue, silk, continuous synthetic fibre, also is used for washing/gluing blended fabric dyeing.Tertbutyl peroxide also can be used as siccative, polymerization starter, the organic synthesis intermediate of unsaturated melamine resin coating.Existing preparation method mainly contains: the one, after p-Nitroaniline ortho-sulfonic acid diazotization, with sour coupling, then the nitroreduction in the conjugates is become amino, again with the phosgene condensation, finally by saltouing, filter and dry and make.The 2nd, the trimethyl carbinol and sulfuric acid reaction generate the hydrogen sulfate tert-butyl ester, get with hydroperoxidation again.In addition the trimethyl carbinol is added reactor, in 35 ℃ of adding hydrogen peroxide, be warming up to 50 ℃ then under stirring, drip 70% sulfuric acid, add afterreaction 5h, temperature remains on 55～60 ℃, standing demix, get top oil reservoir anhydrous sodium sulfate drying, filter, get tertbutyl peroxide.As can be seen, existing technology exists equipment corrosion and hazardous emission, and the utmost point does not meet eco-friendly developing direction, and the by product of by-product cheapness, deficiency in economic performance.Disclose a kind of method for preparing tertbutyl peroxide among the CN1699339A, this method is catalyzer with the HTS merely, is oxygenant with the hydrogen peroxide, the trimethyl carbinol transformation efficiency leeway that still is greatly improved.
Summary of the invention
Therefore, the objective of the invention is the deficiency at existing technology, provide a kind of environmentally friendly and technology is simple, is the method that the oxidizer catalytic oxidation trimethyl carbinol prepares tertbutyl peroxide with the hydrogen peroxide.
The method for preparing tertbutyl peroxide provided by the invention, it is characterized in that the hetero-atom molecular-sieve with the soluble zinc salt modification is catalyzer, being 20～180 ℃ in temperature is under the condition of 0.1～3.0MPa with pressure, with the trimethyl carbinol, oxygenant, solvent contacts with catalyst mix, wherein the mol ratio of the trimethyl carbinol and oxygenant is 1: 1～10, the mass ratio of solvent and catalyzer is 0～200: 1, in the hetero-atom molecular-sieve of described soluble zinc salt modification, hetero-atom molecular-sieve (in heteroatoms) is 0.05～10: 1 with the mol ratio of soluble zinc salt (in zinc).
Method provided by the invention with respect to traditional method, has overcome problems such as traditional processing technology complexity, equipment corrosion and noxious emission, in raw material, need not to add any inhibitor or initiator, production process is simple, is green synthesis process, and tertbutyl peroxide yield height.
Embodiment
The catalyzed oxidation trimethyl carbinol provided by the invention prepares in the method for tertbutyl peroxide, and described catalyzer is the hetero-atom molecular-sieve of soluble zinc salt modification.Hetero-atom molecular-sieve is one or more the molecular sieve that contains in the framework of molecular sieve structure in the heteroatomss such as being selected from titanium, vanadium, iron, cobalt, tin, cerium, as HTS, V-Si molecular sieve, iron si molecular sieves, cobalt si molecular sieves, tin si molecular sieves, cerium si molecular sieves etc., preferred HTS wherein.Described HTS is one or more among TS-1, TS-2, Ti-MCM-22, Ti-MCM-41, Ti-SBA-15, the Ti-ZSM-48, and preferred hetero-atom molecular-sieve is titanium-silicon molecular sieve TS-1.Most preferred hetero-atom molecular-sieve is the HTS of the MFI structure of hollow structure crystal grain, and the radical length of the cavity part of its hollow structure is 5～300 nanometers, and described HTS is at 25 ℃, P/P
0=0.10, adsorption time is that the benzene adsorptive capacity that records under 1 hour the condition is at least 70 milligrams/gram, has hysteresis loop between the adsorption isothermal line of the cryogenic nitrogen absorption of this HTS and the desorption isotherm.
Method provided by the invention, described catalyzer is in the hetero-atom molecular-sieve of soluble zinc salt modification, and soluble zinc salt is selected from one or more in zinc phosphate, zinc nitrate, zinc chloride, zinc sulfate, Zinc Gluconate, zinc acetate, zinc bromide, zinc fluoride or the zinc hydrogen phosphate.
In the hetero-atom molecular-sieve of described soluble zinc salt modification, hetero-atom molecular-sieve (in heteroatoms) is 0.05～10: 1 with the mol ratio of soluble zinc salt (in zinc), preferred 0.1～5: 1.The hetero-atom molecular-sieve of soluble zinc salt modification, be by soluble Zn salt brine solution and hetero-atom molecular-sieve mix that the back is dry, roasting and getting, wherein dry, roasting condition is well known to those skilled in the art, at this and have no special requirements, drying generally is in air atmosphere, handles 1～8h in ℃ scope of room temperature～200; Usually, the temperature of described roasting can be 200～800 ℃, and the time can be 1～12 hour.Described roasting can be carried out under air or oxygen atmosphere.
In the method provided by the invention, described oxygenant is hydrogen peroxide, can be pure product, but considers the preferably aqueous solution of hydrogen peroxide from angle economic and safety, and the quality percentage composition of hydrogen peroxide is selected from 5%～90%, preferred 20%～70%.
In preparation method provided by the invention, can realize under condition of no solvent that the inventor finds, can improve reactivity worth in implementation process when introducing certain solvent.So, in preparation method provided by the invention, also can introduce solvent as required, preferably introduce the situation of solvent.Described solvent is selected from nitrile or their mixing such as ketones such as methyl alcohol, ethanol or acetone, butanone or acetonitrile, propionitrile, benzyl cyanide, is preferably acetonitrile, acetone, methyl alcohol or their mixing, more preferably acetone, methyl alcohol and/or acetonitrile.
In the method provided by the invention, the raw material optimum ratio is as follows: the mol ratio of the trimethyl carbinol and oxygenant is preferably 1: 1～and 5, the mass ratio of solvent and catalyzer is preferably 0～150: 1.Amount between the raw material trimethyl carbinol and the catalyzer does not have clear and definite restriction, can realize that the present invention gets final product, and the mass ratio of the general trimethyl carbinol and catalyzer is 0.5～100: 1.
In method provided by the invention, temperature of reaction is preferably 40～120 ℃, and reaction pressure is preferably 0.1～2.5MPa.
In preparation method provided by the invention, reinforced order does not have special requirement yet, can add the trimethyl carbinol earlier, can add oxygenant or solvent earlier yet.
The invention will be further described below by embodiment, but therefore do not limit content of the present invention.
In embodiment and the Comparative Examples, agents useful for same is commercially available chemically pure reagent, and wherein hydrogen peroxide is that mass concentration is 30% the aqueous solution.Used HTS is the method preparation by prior art (Zeolites, the 943rd～950 page of 1992, Vol.12).Used hollow HTS is the HTS Industrial products of the described embodiment 6 of Chinese patent CN1301599A, this HTS is the MFI structure, have hysteresis loop between the adsorption isothermal line of the cryogenic nitrogen absorption of this HTS and the desorption isotherm, crystal grain is that the radical length of hollow crystal grain and cavity part is 15～180 nanometers; This HTS sample is at 25 ℃, P/P
0=0.10, the benzene adsorptive capacity that records under 1 hour the condition of adsorption time is 78 milligrams/gram)
Its preparation process of HTS of catalyzer soluble zinc salt modification among the embodiment is, at normal temperatures and pressures, as required a certain amount of soluble Zn salt brine solution and HTS are mixed, then under air atmosphere, change 120 ℃ of dry 5h in the baking oven over to, at last at 550 ℃ of roasting 5h of retort furnace.The mol ratio of HTS in the catalyst preparation process (in titanium) and soluble zinc salt (in zinc) sees the explanation among each embodiment for details.
In Comparative Examples and embodiment:
Comparative Examples 1
This Comparative Examples illustrates under the situation that does not have catalyzer to exist, the reaction conditions of the trimethyl carbinol and hydrogen peroxide and result.
Be 1: 2 with the trimethyl carbinol, hydrogen peroxide and solvent according to the mol ratio of the trimethyl carbinol and hydrogen peroxide, wherein the solvent methanol quality is 20g, is that 60 ℃ of pressure are to react under the 1.5MPa in temperature.React after 2 hours, the transformation efficiency of the trimethyl carbinol and tertbutyl peroxide selectivity are 0%.
Comparative Examples 2
This Comparative Examples illustrates under the situation of catalyst Ti-si molecular sieves Individual existence, the reaction conditions of the trimethyl carbinol and hydrogen peroxide and result.
Be 2: 7 with the trimethyl carbinol, hydrogen peroxide, solvent and catalyst Ti-si molecular sieves according to the mol ratio of the trimethyl carbinol and hydrogen peroxide, the mass ratio of solvent methanol and catalyzer is 20: 1, the mass ratio of the trimethyl carbinol and catalyzer is 10: 1, is that 80 ℃ of pressure are to react under the 1.5MPa in temperature.The result who reacts 2 hours is as follows: trimethyl carbinol transformation efficiency is 26%; The tertbutyl peroxide selectivity is 88%.
Comparative Examples 3
This Comparative Examples illustrates under the situation of catalyzer soluble zinc salt (zinc phosphate) Individual existence, the reaction conditions of the trimethyl carbinol and hydrogen peroxide and result.
Be 1: 4 with the trimethyl carbinol, hydrogen peroxide, solvent and catalyzer (zinc phosphate) according to the mol ratio of the trimethyl carbinol and hydrogen peroxide, the mass ratio of solvent acetone and catalyzer is 40: 1, the mass ratio of the trimethyl carbinol and catalyzer is 10: 1, is that 60 ℃ of pressure are to react under the 2.5MPa in temperature.The result who reacts 2 hours is as follows: trimethyl carbinol transformation efficiency is 3%; The tertbutyl peroxide selectivity is 6%.
Embodiment 1
Be 1: 2 with the trimethyl carbinol, hydrogen peroxide, solvent and catalyzer (mol ratio of HTS and zinc nitrate 0.2: 1) according to the mol ratio of the trimethyl carbinol and hydrogen peroxide, the mass ratio of solvent acetonitrile and catalyzer is 20: 1, the mass ratio of the trimethyl carbinol and catalyzer is 10: 1, is that 50 ℃ of pressure are to react under the 1.5MPa in temperature.The result who reacts 2 hours is as follows: trimethyl carbinol transformation efficiency is 34%; The tertbutyl peroxide selectivity is 94%.
Embodiment 2
Be 1: 3 with the trimethyl carbinol, hydrogen peroxide, solvent and catalyzer (mol ratio of HTS and zinc phosphate 1: 1) according to the mol ratio of the trimethyl carbinol and hydrogen peroxide, the mass ratio of solvent acetone and catalyzer is 50: 1, the mass ratio of the trimethyl carbinol and catalyzer is 20: 1, is that 60 ℃ of pressure are to react under the 2.5MPa in temperature.The result who reacts 2 hours is as follows: trimethyl carbinol transformation efficiency is 45%; The tertbutyl peroxide selectivity is 96%.
Embodiment 3
Be 2: 9 with the trimethyl carbinol, hydrogen peroxide, solvent and catalyzer (mol ratio of HTS and zinc sulfate 0.1: 1) according to the mol ratio of the trimethyl carbinol and hydrogen peroxide, the mass ratio of solvent acetic acid and catalyzer is 60: 1, the mass ratio of the trimethyl carbinol and catalyzer is 1: 1, is that 100 ℃ of pressure are to react under the 0.5MPa in temperature.The result who reacts 2 hours is as follows: trimethyl carbinol transformation efficiency is 73%; The tertbutyl peroxide selectivity is 92%.
Embodiment 4
Be 1: 4 with the trimethyl carbinol, hydrogen peroxide, solvent and catalyzer (mol ratio of HTS and zinc hydrogen phosphate 2: 1) according to the mol ratio of the trimethyl carbinol and hydrogen peroxide, the mass ratio of solvent methanol and catalyzer is 35: 1, the mass ratio of the trimethyl carbinol and catalyzer is 50: 1, is that 40 ℃ of pressure are to react under the 0.5MPa in temperature.The result who reacts 2 hours is as follows: trimethyl carbinol transformation efficiency is 71%; The tertbutyl peroxide selectivity is 96%.
Embodiment 5
Be 1: 2 with the trimethyl carbinol, hydrogen peroxide, solvent and catalyzer (mol ratio of HTS and zinc chloride 5: 1) according to the mol ratio of the trimethyl carbinol and hydrogen peroxide, the mass ratio of solvent acetonitrile and catalyzer is 5: 1, the mass ratio of the trimethyl carbinol and catalyzer is 70: 1, is that 80 ℃ of pressure are to react under the 0.5MPa in temperature.The result who reacts 2 hours is as follows: trimethyl carbinol transformation efficiency is 82%; The tertbutyl peroxide selectivity is 94%.
Embodiment 6
Be 3: 8 with the trimethyl carbinol, hydrogen peroxide, solvent and catalyzer (mol ratio of HTS and zinc acetate 0.2: 1) according to the mol ratio of the trimethyl carbinol and hydrogen peroxide, the mass ratio of solvent benzol acetonitrile and catalyzer is 120: 1, the mass ratio of the trimethyl carbinol and catalyzer is 100: 1, is that 90 ℃ of pressure are to react under the 1.5MPa in temperature.The result who reacts 2 hours is as follows: trimethyl carbinol transformation efficiency is 79%; The tertbutyl peroxide selectivity is 95%.
Embodiment 7
Be 1: 5 with the trimethyl carbinol, hydrogen peroxide, solvent and catalyzer (mol ratio of HTS and zinc bromide 0.3: 1) according to the mol ratio of the trimethyl carbinol and hydrogen peroxide, solvent (equal-volume is than acetonitrile and acetone) is 200: 1 with the mass ratio of catalyzer, the mass ratio of the trimethyl carbinol and catalyzer is 0.5: 1, is that 60 ℃ of pressure are to react under the 0.5MPa in temperature.The result who reacts 2 hours is as follows: trimethyl carbinol transformation efficiency is 65%; The tertbutyl peroxide selectivity is 91%.
Embodiment 8
Be 1: 2 with the trimethyl carbinol, hydrogen peroxide, solvent and catalyzer (mol ratio of HTS and Zinc Gluconate 0.5: 1) according to the mol ratio of the trimethyl carbinol and hydrogen peroxide, the mass ratio of solvent propionitrile and catalyzer is 10: 1, the mass ratio of the trimethyl carbinol and catalyzer is 30: 1, is that 70 ℃ of pressure are to react under the 1.5MPa in temperature.The result who reacts 2 hours is as follows: trimethyl carbinol transformation efficiency is 84%; The tertbutyl peroxide selectivity is 93%.
Embodiment 9
Be 1: 4 with the trimethyl carbinol, hydrogen peroxide, solvent and catalyzer (mol ratio of HTS and zinc fluoride 0.8: 1) according to the mol ratio of the trimethyl carbinol and hydrogen peroxide, the mass ratio of solvent acetonitrile and catalyzer is 80: 1, the mass ratio of the trimethyl carbinol and catalyzer is 90: 1, is that 120 ℃ of pressure are to react under the 0.1MPa in temperature.The result who reacts 1 hour is as follows: trimethyl carbinol transformation efficiency is 91%; The tertbutyl peroxide selectivity is 93%.
Embodiment 10
The method oxidation trimethyl carbinol according to embodiment 1 prepares tertbutyl peroxide.Different is that the trimethyl carbinol and hydrogen peroxide mol ratio become 1: 1.Behind the reaction 2h, trimethyl carbinol transformation efficiency is 12%; The tertbutyl peroxide selectivity is 79%.
Embodiment 11
The method oxidation trimethyl carbinol according to embodiment 5 prepares tertbutyl peroxide.The mol ratio of HTS that different is in the catalyzer and zinc chloride becomes 12: 1.Behind the reaction 2h, trimethyl carbinol transformation efficiency is 76%; The tertbutyl peroxide selectivity is 76%.
Embodiment 12
The method oxidation trimethyl carbinol according to embodiment 6 prepares tertbutyl peroxide.Different is that zinc acetate is replaced by equimolar zinc chloride.Behind the reaction 2h, trimethyl carbinol transformation efficiency is 85%; The tertbutyl peroxide selectivity is 97%.
Embodiment 13
The method oxidation trimethyl carbinol according to embodiment 9 prepares tertbutyl peroxide.Different is that solvent acetonitrile is replaced by benzyl cyanide.Behind the reaction 2h, trimethyl carbinol transformation efficiency is 72%; The tertbutyl peroxide selectivity is 86%.
Embodiment 14
With the trimethyl carbinol, hydrogen peroxide, solvent and catalyzer (according to the mol ratio of the V-Si molecular sieve of the method preparation of describing among the Chinese patent CN1840477A embodiment 1 and zinc acetate 2: 1, wherein Si/ heteroatoms mol ratio is 80: 1 in the V-Si molecular sieve) be 2: 9 according to the mol ratio of the trimethyl carbinol and hydrogen peroxide, the mass ratio of solvent acetic acid and catalyzer is 60: 1, the mass ratio of the trimethyl carbinol and catalyzer is 10: 1, is that 100 ℃ of pressure are to react under the 0.5MPa in temperature.The result who reacts 2 hours is as follows: trimethyl carbinol transformation efficiency is 79%; The tertbutyl peroxide selectivity is 86%.
Embodiment 15
With the trimethyl carbinol, hydrogen peroxide, solvent and catalyzer (according to J.Mol.Catal.A:Chem., 1996, the tin si molecular sieves of the method preparation of describing in 105:149～158 and the mol ratio of zinc bromide 5: 1, wherein Si/ heteroatoms mol ratio is 60: 1 in the tin si molecular sieves) be 1: 4 according to the mol ratio of the trimethyl carbinol and hydrogen peroxide, the mass ratio of solvent methanol and catalyzer is 35: 1, the mass ratio of the trimethyl carbinol and catalyzer is 5: 1, is that 40 ℃ of pressure are to react under the 0.5MPa in temperature.The result who reacts 2 hours is as follows: trimethyl carbinol transformation efficiency is 67%; The tertbutyl peroxide selectivity is 97%.
Embodiment 16
With the trimethyl carbinol, hydrogen peroxide, solvent and catalyzer (according to J.Chem.Soc.Chem.Commun., 1997, the HTS Ti-Beta of the method preparation described in 677～678 and the mol ratio of Zinc Gluconate 0.2: 1, wherein Si/ heteroatoms mol ratio is 30: 1 in the HTS) be 1: 2 according to the mol ratio of the trimethyl carbinol and hydrogen peroxide, the mass ratio of solvent acetonitrile and catalyzer is 5: 1, the mass ratio of the trimethyl carbinol and catalyzer is 70: 1, is that 80 ℃ of pressure are to react under the 0.5MPa in temperature.The result who reacts 2 hours is as follows: trimethyl carbinol transformation efficiency is 78%; The tertbutyl peroxide selectivity is 85%.
Embodiment 17
With the trimethyl carbinol, hydrogen peroxide, solvent and catalyzer (zinc fluoride and according to Chem.Commun., 1994, the mol ratio of the HTS Ti-MCM-41 of the method preparation described in 147～148 0.2: 1, wherein Si/ heteroatoms mol ratio is 40: 1 in the HTS) be 3: 8 according to the mol ratio of the trimethyl carbinol and hydrogen peroxide, the mass ratio of solvent benzol acetonitrile and catalyzer is 20: 1, the mass ratio of the trimethyl carbinol and catalyzer is 10: 1, is that 90 ℃ of pressure are to react under the 1.5MPa in temperature.The result who reacts 2 hours is as follows: trimethyl carbinol transformation efficiency is 71%; The tertbutyl peroxide selectivity is 89%.
From embodiment 1～17 and Comparative Examples 1～3 as can be seen: under the suitable situation of selectivity, it is that the trimethyl carbinol transformation efficiency of catalyzer is apparently higher than comparative sample such as unmodified HTS that the present invention adopts the HTS of soluble zinc salt modification.
Claims (11)
1. the preparation method of a tertbutyl peroxide under oxidation reaction condition, contacts the trimethyl carbinol, oxygenant, solvent and catalyst mix, it is characterized in that described catalyzer is the hetero-atom molecular-sieve with the soluble zinc salt modification.
2. according to the method for claim 1, it is characterized in that this method is that 20～180 ℃ and pressure are to carry out under the condition of 0.1～3MPa in temperature, wherein, the mol ratio of the trimethyl carbinol and oxygenant is 1: 1～10, the mass ratio of solvent and catalyzer is 0～200: 1, and in the hetero-atom molecular-sieve of described soluble zinc salt modification, the mol ratio of hetero-atom molecular-sieve and soluble zinc salt is 0.05～10: 1, hetero-atom molecular-sieve is in heteroatoms, and soluble zinc salt is in zinc.
3. according to the process of claim 1 wherein, described hetero-atom molecular-sieve is selected from HTS, V-Si molecular sieve, iron si molecular sieves, tin si molecular sieves or cerium si molecular sieves.
4. according to the method for claim 3, wherein, described HTS is selected from one or more among TS-1, TS-2, Ti-MCM-22, Ti-MCM-41, Ti-SBA-15, the Ti-ZSM-48.
5. according to the process of claim 1 wherein, described hetero-atom molecular-sieve is the HTS of the MFI structure of hollow structure crystal grain, and the radical length of the cavity part of its hollow structure is 5～300 nanometers, and described HTS is at 25 ℃, P/P
0=0.10, adsorption time is that the benzene adsorptive capacity that records under 1 hour the condition is at least 70 milligrams/gram, has hysteresis loop between the adsorption isothermal line of the cryogenic nitrogen absorption of this HTS and the desorption isotherm.
6. according to the process of claim 1 wherein, described soluble zinc salt is selected from one or more in zinc phosphate, zinc nitrate, zinc chloride, zinc sulfate, Zinc Gluconate, zinc acetate, zinc bromide, zinc fluoride and the zinc hydrogen phosphate.
7. according to the process of claim 1 wherein, the trimethyl carbinol and oxygenant mol ratio are 1: 2～5, and solvent is 5～150: 1 with the catalyst quality ratio, and the trimethyl carbinol is 0.5～100: 1 with the catalyst quality ratio.
8. according to the method for claim 1, it is characterized in that the hetero-atom molecular-sieve with the soluble zinc salt modification is catalyzer, being 40～120 ℃ in temperature is under the condition of 0.1～2.5MPa with pressure, and the trimethyl carbinol, oxygenant, solvent and catalyst mix are contacted.
9. according to the process of claim 1 wherein, described catalyzer is the HTS of soluble zinc salt modification, and the mol ratio of HTS and soluble zinc salt is 0.1～5: 1, and HTS is in titanium, and soluble zinc salt is in zinc.
10. according to the process of claim 1 wherein, the hetero-atom molecular-sieve of soluble zinc salt modification, be by soluble Zn salt brine solution and hetero-atom molecular-sieve mix that the back is dry, roasting and getting.
11. according to claim 1,2,7, one of 8 method, wherein, described oxygenant is hydrogen peroxide.
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| CN110128313A (en) * | 2018-02-09 | 2019-08-16 | 中国石油化工股份有限公司 | The method for preparing tert-butyl hydroperoxide |
| CN111389457A (en) * | 2020-04-22 | 2020-07-10 | 陕西延长石油（集团）有限责任公司 | A kind of catalyst and method for preparing methacrylic acid and propylene oxide by co-oxidation of isobutane and propylene |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110128313A (en) * | 2018-02-09 | 2019-08-16 | 中国石油化工股份有限公司 | The method for preparing tert-butyl hydroperoxide |
| CN111389457A (en) * | 2020-04-22 | 2020-07-10 | 陕西延长石油（集团）有限责任公司 | A kind of catalyst and method for preparing methacrylic acid and propylene oxide by co-oxidation of isobutane and propylene |
| CN111389457B (en) * | 2020-04-22 | 2022-08-30 | 陕西延长石油（集团）有限责任公司 | Catalyst and method for preparing methacrylic acid and propylene oxide by co-oxidation of isobutane and propylene |
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