CN102020535A - Method for producing phenol by oxidizing benzene through nitrous oxide - Google Patents
Method for producing phenol by oxidizing benzene through nitrous oxide Download PDFInfo
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- CN102020535A CN102020535A CN2009100925181A CN200910092518A CN102020535A CN 102020535 A CN102020535 A CN 102020535A CN 2009100925181 A CN2009100925181 A CN 2009100925181A CN 200910092518 A CN200910092518 A CN 200910092518A CN 102020535 A CN102020535 A CN 102020535A
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Abstract
The invention relates to a process method for producing phenol by selectively oxidizing benzene through nitrous oxide, comprising the following steps of: placing a Fe-ZSM-5 molecular sieve catalyst on a distribution plate inside a fixed fluidized bed reactor; firstly activating the Fe-ZSM-5 molecular sieve catalyst by using helium at 400-600 DEG C; then introducing a gas containing the nitrous oxide and the benzene from the lower end inside the fixed fluidized bed reactor at normal pressure; controlling the reaction gas velocity of the gas between 0.040m/s and 0.072m/s through the gas distribution plate so that catalyst granules contact with the gas in a suspended state in the fixed fluidized bed reactor to carry out continuous reaction at the temperature between 300 DEG C and 500 DEG C and the normal pressure, wherein the mol ratio of the raw material benzene/N2O is between 4 and 16; and condensing and separating reaction products to obtain the phenol. The invention enables the Fe-ZSM-5 molecular sieve catalyst to contact with reaction fluids in the suspended state by utilizing the fixed fluidized bed reactor, therefore sliding velocity higher than terminal granule velocity exists between the gas and a solid; and in addition, the invention not only has very high contact efficiency, but also is beneficial to carrying out mass transfer between the gas and the solid and desorbing a product, i.e. the phenol, thereby alleviating the coking deactivation of the Fe-ZSM-5 molecular sieve catalyst.
Description
Technical field
The present invention relates to a kind ofly effectively utilize method with what nitrous oxide was made oxygenant.Be specifically related to nitrous oxide selective oxidation benzene and produce the method for phenol.
Background technology
Nitrous oxide, chemical formula N
2O is commonly called as laughing gas, and can not only be serious damage the ozone layer and has powerful Greenhouse effect, and elimination of nitrous oxide is significant to environment protection.The method of elimination of nitrous oxide can be divided into high-temperature decomposition, catalytic decomposition method and recycling method at present.If adopt simple method of decomposing to handle nitrous oxide, not only expensive power consumption is huge, and has wasted the nitrous oxide resource.Therefore recycle around nitrous oxide both at home and abroad in recent years and launched big quantity research, wherein nitrous oxide is used as oxygenant and is significant, particularly utilizing nitrous oxide oxidation step benzene to produce phenol is a kind of method of effective recycling nitrous oxide, generally be to select suitable catalyzer, utilize fixed-bed reactor, use the nitrous oxide Oxybenzene, as: at US.No.5,672,777 and 5, disclose in 110,995, carried out on the pentasil type zeolite catalyst of modification experimental result at the small amounts of iron additive with the nitrous oxide Oxybenzene.The fixed bed reaction temperature is 275-450 ℃, and be 2-4 second duration of contact, and the liquid phase space velocity of benzene is 0.4h
-1, benzene/N
2The mol ratio of O is 1: 4, and the phenol selectivity reaches 90-97%, and phenol yield generally only reaches 20-30%.The shortcoming of these catalyzer is that heat-flash is put in reaction, cause the catalyst overheating sintering easily, and reactor throughput is low, the transformation efficiency of excessive nitrous oxide is low, and easily produce the deep oxidation by product, and oxidized byproduct is the carbon deposit precursor that causes catalyst deactivation.The method of another kind of nitrous oxide Oxybenzene has been proposed in people's such as Panov G.I. patent (PCT W095/27691).In the method, it is excessive benzene that use is equivalent to nitrous oxide, benzene/N
2The mol ratio of O is up to 9: 1, thereby improved the selectivity that nitrous oxide is converted into phenol, and the liquid phase air speed of benzene is increased to about 2-2.5h
-1, but phenol yield nearly all fails to surpass 20%.Because use substantially exceeds the needed benzene of optimum response selectivity, certainly will cause the load of downstream separation and recirculation benzene workshop section to increase greatly simultaneously.Even the ratio of benzene is only high to non-flammable mixture only is provided in the reactor, but, just might in exporting the logistics device, stay inflammable or explosive benzene and nitrous oxide mixture as long as nitrous oxide transforms fully in the reaction.
U.S. Solutia (first promise) company and Russian Boreskov (Bo Lisikefu) catalyst research institute (BIC) develop nitrous oxide in the hexanodioic acid tail gas is produced phenol as oxygenant oxidation step benzene AlphOx technology jointly, this technology is catalyzer with the acid ZSM-5 and the ZSM-11 zeolite molecular sieve of iron modification, with the nitrous oxide is that oxygenant and benzene carry out redox reaction, is reflected in the atmospheric fixed bed adiabatic reactor to carry out.Product can obtain the phenol of higher degree after simple separation and rectifying.The distinguishing feature of this technology be catalyzer initial activity and phenol selectivity height, flow process is simple and direct, product purity is high, and the waste that is produced is no more than 2% of benzene feedstock amount, and can effectively phenol production device and adipic acid plant be integrated.But the shortcoming that this technology exists is the catalyst activity less stable.Because product phenol, is not easy that desorption gets off on the active sites of catalyst surface in the strong adsorption of catalyst surface, the deep oxidation reaction further takes place form carbon deposit, makes the catalyzer rapid deactivation, has restricted the industrial applications of this Technology.
The common issue with that the nitrous oxide oxidation step benzene of above-mentioned bibliographical information is produced the phenol process existence is: catalyst system therefor all faces the problem of rapid deactivation, mainly be since catalyst surface active position or acidic site to generating strong absorption such as product phenol, cause the further deep oxidation of phenol to form carbon deposit and cause catalyst deactivation at catalyst surface, and in this field, present research generally is to start with from Preparation of Catalyst and modification aspect with solving this problem, but does not all have unusual effect.
Summary of the invention
The present invention overcomes nitrous oxide selective oxidation benzene to produce the problems such as catalyst carbon deposit inactivation that exist in the phenol, a kind of fixed fluidized bed processing method that nitrous oxide selective oxidation benzene is produced phenol of carrying out of utilizing is provided, make catalyzer both keep initial activity and higher selectivity preferably, the inactivation of catalyzer be can slow down again, and the regeneration and the cycling and reutilization of convenient catalyst made.
Nitrous oxide selective oxidation benzene provided by the invention is produced the phenol process method: adopt fixed fluidized-bed reactor, with the Fe-ZSM-5 molecular sieve catalyst, pack on the fixed fluidized-bed reactor grid distributor, use the helium deactivated catalyst down at 400-600 ℃ earlier, then under normal pressure, feed the gas of nitrous oxide and benzene from the inside reactor lower end, gas is by the gas distribution grid of horizontal fixed, red-tape operati air speed scope, granules of catalyst is contacted with reactant gases with suspended state in fixed fluidized-bed reactor, form the uniform catalyst dense-phase bed, control reaction temperature is between 300-500 ℃, reaction pressure is a normal pressure, benzene feedstock/N
2O mole proportioning is between 4-16, and reaction gas speed is carried out successive reaction between 0.040-0.072m/s, and reacted product obtains phenol through condensation separation.
In the processing method of the present invention, the Fe-ZSM-5 molecular sieve catalyst that is adopted prepares by general method, preferred Fe content 0.5-1.5wt%, and Si/Al is than 25-80, so that catalyzer has better activity.
In the processing method of the present invention, reaction gas speed, temperature of reaction and benzene feedstock/N
2O mole proportioning influences phenol selectivity, the N in the reaction of nitrous oxide selective oxidation benzene
2O transformation efficiency and catalyst carbon deposition deactivation rate.The three must regulate in suitable scope, wherein:
Described reaction gas speed control system scope is preferably 0.048-0.056m/s.The present invention is different fully with the production of nitrous oxide selective oxidation benzene in fixed-bed reactor phenol reactant situation, in fixed-bed reactor, reaction gas speed increases makes the residence time of reaction mass in reactor shorten, played the generation that stops the reaction of consecutive deep oxidation on the macroscopic view, thereby the phenol selectivity increases with the increase of reaction gas speed, but the duration of contact of raw material and catalyzer is short, causes more raw materials to have little time to participate in reaction just apace by beds, so N
2The O transformation efficiency reduces with the increase of reaction gas speed.The present invention finishes reaction process in fixed fluidized-bed reactor, granules of catalyst contacts with reactant gases with suspended state in fixed fluidized-bed reactor, reaction gas speed is big more, reaction mass back-mixing degree is just big more, target product phenol can not in time be taken out of reactor, returns and continues to participate in the deep oxidation reaction, the phenol selectivity is increased with gas speed reduce, and because the material back-mixing continues to participate in oxidizing reaction, N
2The O transformation efficiency can considerable change, generally remains on about 95% after measured, so phenol yield is than the height in the fixed-bed reactor.Therefore the present invention is directed to the reaction process of fixed fluidized-bed reactor, propose suitable reaction gas speed scope, when improving the gas-solid contact efficiency, by the variation of control reaction liquid form, the speed of slowing down the catalyst carbon deposit inactivation.
Described temperature of reaction should be controlled at certain limit, and on the one hand, temperature of reaction raises, and helps N
2O is in the absorption of dissociating on Fe-ZSM-5 molecular sieve surface, thereby promotion N
2The increase of O transformation efficiency; On the other hand, temperature of reaction raises, and makes product phenol that deep oxidation further take place, and forms carbon deposit, causes the phenol selectivity to descend.So the present invention is at N
2In the O oxidation step benzene system phenol reactant, should consider that to the selection of temperature of reaction temperature of reaction is to N
2The favourable influence of O transformation efficiency take into account optionally negative impact of Pyrogentisinic Acid again.The preferable reaction temperature scope is 400-450 ℃.
Described benzene feedstock/N
2O mole proportion optimization is 7-10.N
2O transformation efficiency and phenol selectivity are all with benzene/N in the raw material
2The increase of O mol ratio and increasing, but N
2The increase of O transformation efficiency is not obvious relatively.Because the relative N of benzene in reaction process
2O is excessive all the time, increases benzene/N
2The O mol ratio is to N
2The influence of O transformation efficiency is not remarkable; But along with benzene/N
2The increase of O mol ratio, N
2The possibility of O deep oxidation benzene or phenol is more and more littler, thereby generates the selectivity increase of purpose product phenol.But too high benzene/N
2The O mol ratio is unfavorable to improving the phenol space-time yield.So benzene feedstock/N
2O mole proportioning must be controlled at certain limit.
In the processing method of the present invention, the fixed fluidized bed reaction unit that is adopted has known structure, comprises that gas imports, delivery line, reaction tubes, gas distribution grid is arranged in the reaction tubes, and gasket and strainer, wherein gas distribution grid is the multi-deck screen plate structure, total thickness is 1-5mm, average pore is 88-125 μ m, can improve the catalyst fluidization state, in the fluidized-bed reaction section, form the uniform catalyst dense-phase bed, reduce channel.
Effect of the present invention: the present invention proposes to utilize fixed fluidized-bed reactor to carry out the processing method that nitrous oxide selective oxidation benzene is produced phenol, propose first to overcome this reacting middle catalyst inactivation problem from the liquid form that changes reaction, catalyzer is contacted with reacting fluid with suspended state in fixed fluidized-bed reactor, not only the phase contact area of fluid and catalyst solid is very big, simultaneously by the control appropriate processing condition, make and exist the landing speed that is higher than the terminal particle speed between the gas-solid, help the carrying out of mass transfer between the gas-solid and the desorption of product phenol, contact efficiency is very high, thereby slowed down the coking deactivation of catalyzer, recording the product phenol yield can be up to 50-85%, and successive reaction after 275 minutes phenol yield still maintain more than 50%, and phenol yield is up to 30-40% in fixed bed, and catalyst deactivation is very fast, successive reaction after 275 minutes phenol yield only maintain about 10%; Granules of catalyst violent mixing owing to be subjected to the fluid effect simultaneously can realize the consistent of temperature and concentration in reactor, help the carrying out of this strong exothermal reaction, has avoided the thermal sintering of crossing of catalyzer; Because the variation of voidage can cause the wide variation of granules of catalyst drag coefficient in the gas-solid system, therefore fixed fluidized bed operational condition can in very large range be adjusted, thereby can satisfy industrial needs.
The present invention forms the uniform catalyst dense-phase bed in conversion zone, can make granules of catalyst present fluidization preferably, reduces channel, improves the stability of catalyzer.
Description of drawings
Fig. 1 is a fixed fluidized bed reaction unit synoptic diagram of the present invention
Embodiment
The present invention is described further by following embodiment, yet protection scope of the present invention should not be subjected to the restriction of this embodiment.Also should comprise, under the premise of without departing from the spirit of the present invention, the various conspicuous change that those skilled in the art carry out.
The fixed fluidized bed reaction unit that processing method of the present invention adopts comprises: gas eduction tube 1, gasket 2 as shown in Figure 1, strainer 3, reaction pipeline section 4, gas distribution grid 5, gas introduction tube 6, wherein: gas distribution grid is the multi-deck screen plate structure, and lower floor's plate hole is counted few greatly, and porosity is 125 μ m, start to control the effect of falling of neutralizing, more up each layer hole count is the more and little, and the superiors' porosity is 88 μ m, is convenient to even gas distribution.Most preferably adopt the multilayer Stainless Steel Cloth to be overrided to form, its thickness is 1-3mm, can form the uniform catalyst dense-phase bed in fixed fluidized bed conversion zone, reduces channel.The reaction tubes size requires design according to the gentle speed of different output, and the thick more gas flow that just requires of reaction tubes is big more under same gas speed, and suitable pipe range is in order to guarantee that catalyzer can have suitable fluidisation space, and preferred reaction tubes aspect ratio is 15-30: 1.The outlet of reactor top is equipped with strainer interception catalyst dust, and reactor head is used gasket and thread seal.
The concrete enforcement of processing method of the present invention: with the Fe-ZSM-5 molecular sieve catalyst, on the interior gas distribution grid of the fixed fluidized-bed reactor of packing into, under 400-600 ℃, activate 4-6 hour earlier with helium, then in temperature of reaction, normal pressure (0.1Mpa) feeds nitrous oxide and benzene down and begins reaction, reactant gases is by the gas distribution grid of horizontal fixed, pass through bed with bubble form, be scattered in the reactant gases in operation air speed scope catalyst particles, in fixed fluidized-bed reactor, contact with reactant gases with suspended state, form the uniform catalyst dense-phase bed, control reaction temperature is between 300-500 ℃ in the reaction process, preferred 400-450 ℃, reaction pressure is 0.1Mpa, benzene feedstock/N
2O mole proportioning is between 4-16, preferred 7-10, reaction gas speed is between 0.040-0.072m/s, preferred 0.048-0.056m/s, carry out successive reaction, reacted product is through condenser and gas-liquid separator condensation separation, and non-condensable gases enters gas chromatographic analysis after metering, the condensation liquid product is then put into receiving flask and is measured, the timing sampling analysis.The gas-liquid facies analysis is all finished on the GC4000A type gas chromatograph that thing Electronics Co., Ltd. in Beijing produces.Record the product phenol yield and can reach 50-85%, and successive reaction after 275 minutes phenol yield still maintain more than 50%.
In the processing method of the present invention, used Fe-ZSM-5 molecular sieve catalyst makes by the following method: at first take by weighing a certain amount of Fe (NO
3)
39H
2O is configured to solution, this solution is poured in the there-necked flask that certain amount of H-ZSM-5 is housed, reflux down at 100 ℃ then and stirred 3 hours, filter with deionized water wash again, drying is 12 hours under 110 ℃, 540 ℃ of roastings 4 hours, after the cooling catalyzer compressing tablet is ground to form the particle of 125-450 μ m.In fixed-bed reactor, introduce water vapor then and under 550-750 ℃, catalyzer is carried out hydrothermal treatment consists, obtain the Fe-ZSM-5 molecular sieve catalyst after the cooling, Fe content 0.5-1.5wt%, Si/Al compares 25-80.
Describe the present invention in detail below in conjunction with specific embodiment, thereby will help to understand the present invention, but be not limited to these embodiment.
Embodiment 1: select Si/Al than H-ZSM-5 molecular sieve 20 grams that are 25, put into there-necked flask as carrier.Take by weighing 1.448 gram Fe (NO
3)
39H
2O, add 300 ml distilled waters and be mixed with solution, this solution is poured in the there-necked flask that 20 gram H-ZSM-5 are housed, 100 ℃ of stirrings 3 hours that reflux down, filter 3 times with deionized water wash again, drying is 12 hours under 110 ℃, 540 ℃ of roastings 4 hours, after the cooling catalyzer compressing tablet is ground to form the particle of 180-300 μ m.In fixed-bed reactor, introduce water vapor then and under 650 ℃, catalyzer is carried out hydrothermal treatment consists, obtain the Fe-ZSM-5 molecular sieve catalyst after the cooling.
The catalyzer that makes is packed in the fixed fluidized-bed reactor of the present invention on the gas distribution grid, earlier under 500 ℃ with helium activation 5 hours, under normal pressure, feed nitrous oxide, benzene and diluent gas helium then.Temperature of reaction is 400 ℃, benzene feedstock/N
2O mole proportioning is 10, and reaction gas speed is 0.040m/s, and the reaction times is 155 minutes.Phenol yield can reach 75.48%, and successive reaction after 155 minutes yield still maintain more than 67%.
Embodiment 2: catalyst preparation process is with embodiment 1.Temperature of reaction is 500 ℃, and other reaction conditions is constant.Phenol yield can reach 68.51%, and successive reaction after 155 minutes yield still maintain more than 61%.
Embodiment 3: catalyst preparation process is with embodiment 1.Benzene feedstock/N
2O mole proportioning is 13, and other reaction conditions is constant.Phenol yield can reach 83.18%, and successive reaction after 155 minutes yield still maintain more than 74%.
Embodiment 4: catalyst preparation process is with embodiment 1.Reaction gas speed is 0.064m/s, and other reaction conditions is constant.Phenol yield can reach 59.38%, and successive reaction after 155 minutes yield still maintain more than 43%.
Claims (6)
1. a nitrous oxide selective oxidation benzene is produced the processing method of phenol, it is characterized in that, adopt fixed fluidized-bed reactor, the Fe-ZSM-5 molecular sieve catalyst is packed on the fixed fluidized-bed reactor grid distributor, use the helium deactivated catalyst down at 400-600 ℃ earlier, then under normal pressure, feed the gas of nitrous oxide and benzene from the inside reactor lower end, gas passes through gas distribution grid, control reaction gas speed makes granules of catalyst contact successive reaction with suspended state with gas in fixed fluidized-bed reactor at 0.040-0.072m/s, and temperature of reaction is between 300-500 ℃, reaction pressure is a normal pressure, benzene feedstock/N
2O mole proportioning is between 4-16, and reacted product obtains phenol through condensation separation.
2. according to the processing method of claim 1, it is characterized in that, described Fe-ZSM-5 molecular sieve catalyst, Fe content 0.5-1.5wt%, Si/Al compares 25-80.
3. according to the processing method of claim 1, it is characterized in that described reaction gas speed control system scope is 0.048-0.056m/s.
4. according to the processing method of claim 1, it is characterized in that described temperature of reaction is 400-450 ℃.
5. according to the processing method of claim 1, it is characterized in that described benzene feedstock/N
2O mole proportioning is 7-10.
6. according to the processing method of claim 1, it is characterized in that gas distribution grid is the multi-deck screen plate structure in the described fixed fluidized-bed reactor, total thickness is 1-5mm, and average pore is 88-125 μ m.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910092518.1A CN102020535B (en) | 2009-09-17 | 2009-09-17 | Method for producing phenol by oxidizing benzene through nitrous oxide |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910092518.1A CN102020535B (en) | 2009-09-17 | 2009-09-17 | Method for producing phenol by oxidizing benzene through nitrous oxide |
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| Publication Number | Publication Date |
|---|---|
| CN102020535A true CN102020535A (en) | 2011-04-20 |
| CN102020535B CN102020535B (en) | 2014-04-02 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107140675A (en) * | 2017-07-06 | 2017-09-08 | 华南理工大学 | A kind of energy-saving copper sludge recycling prepares the device of copper sulphate |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1148844A (en) * | 1994-04-12 | 1997-04-30 | 波列斯科夫催化学会 | Method for production of phenol and its derivatives |
-
2009
- 2009-09-17 CN CN200910092518.1A patent/CN102020535B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1148844A (en) * | 1994-04-12 | 1997-04-30 | 波列斯科夫催化学会 | Method for production of phenol and its derivatives |
Non-Patent Citations (2)
| Title |
|---|
| E.J.M. HENSEN 等: "Effect of high-temperature treatment on Fe/ZSM-5 prepared by chemical", 《JOURNAL OF CATALYSIS》 * |
| R. LEANZA 等: "Study of Fe-silicalite catalyst for the N2O oxidation of", 《APPLIED CATALYSIS A: GENERAL》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107140675A (en) * | 2017-07-06 | 2017-09-08 | 华南理工大学 | A kind of energy-saving copper sludge recycling prepares the device of copper sulphate |
| CN107140675B (en) * | 2017-07-06 | 2019-05-14 | 华南理工大学 | A kind of energy-saving copper sludge recycling prepares the device of copper sulphate |
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| CN102020535B (en) | 2014-04-02 |
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