CN103922882A - Method for improving selectivity of propylene in reaction of MTP (Methanol To Propylene) - Google Patents
Method for improving selectivity of propylene in reaction of MTP (Methanol To Propylene) Download PDFInfo
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- CN103922882A CN103922882A CN201410131794.5A CN201410131794A CN103922882A CN 103922882 A CN103922882 A CN 103922882A CN 201410131794 A CN201410131794 A CN 201410131794A CN 103922882 A CN103922882 A CN 103922882A
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- propylene
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- 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
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- 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
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
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- 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
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/40—Ethylene production
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Abstract
The invention discloses a method for improving selectivity of propylene in a reaction of MTP (Methanol To Propylene). According to the method, one or multiple additives in a certain proportion are added into the methanol taken as a reaction raw material, wherein the molar ratio of one or multiple additives and the methanol is 1:(1-10):1, so that the purposes of diluting, inducing and activating the methanol are realized; the carbon deposition of a catalyst is effectively reduced. Thus, the activity and stability of the catalyst as well as the selectivity of the catalyst to a target product are improved. The method comprises the following steps: carrying out the reaction in a fixed bed microreactor with the volume of 10ml under conditions that the reaction temperature is within 460 DEG C to 520 DEG C, the system pressure is within 0.1MPa to 1MPa and the weight hourly space velocity is within 1.0h<-1> to 2.0h<-1>; feeding materials by using a micro plunger pump; analyzing a reaction product via an Agilent gas chromatography.
Description
Technical field
The invention belongs to chemical field, be specifically related to the method for Propylene Selectivity in a kind of MTP of raising reaction.
Background technology
Propylene (propylene, CH
2=CHCH
3) be colourless, odorless, slightly sweetish gas under normal temperature.Inflammable, limits of explosion 2%-11%, water insoluble, be dissolved in organic solvent.Propylene is the basic raw material of three large synthetic materialss, mainly for the production of vinyl cyanide, polypropylene, second propylene, acetone and propylene oxide etc.
The existing method by preparing propylene from methanol in the world mainly contains MTP (preparing propylene from methanol) and MTO (methanol-to-olefins).In recent years, the preparing propylene from methanol project development of China was rapid, and the Dalian Chemistry and Physics Institute of the Chinese Academy of Sciences, Tsing-Hua University, Fudan University, Ningxia Shenhua etc. have all carried out the exploitation of project.On l0 9th, 2009, " fluidized-bed preparing propylene from methanol (FMTP) industrial technology development project " commerical test device is driven successfully at Huainan, Anhui, device is through 470h operation continuously at full capacity, obtain expected result, and in the assessment of result of having passed through the l1 month 27 by CNPC and Society of Chemical Industry's tissue.This technology has complete independent intellectual property right, and its Coal Chemical Industry gordian technique reaches world-class levels.But, in MTP reaction, still have so far that Propylene Selectivity is low, catalyst life is short, be not suitable for the defects such as long-term operation.Based on this, invent a kind of optionally method that can effectively improve propylene in MTP reaction and be necessary.
Summary of the invention
The object of the invention is for the low deficiency of Propylene Selectivity in current MTP reaction, a kind of method that can effectively improve Propylene Selectivity of proposition.
In order to realize such object, concrete scheme of the present invention is: a kind of method that improves Propylene Selectivity in MTP reaction, to fill in fixed-bed micro-reactor as the molecular sieve of catalyzer, pass into nitrogen, when question response actuator temperature reaches 460～520 DEG C, stop passing into nitrogen, start charging, non-water additive and methanol aqueous solution are according to the mixed in molar ratio of 1:1～1:10, mixture is dropped into after reactor, and system pressure remains on 0.1～1Mpa, and mass space velocity remains on 1.0～2.0h-1, after reaction 1h, obtain the mix products that contains propylene;
Described non-water additive be in dme, ethene, propylene, butylene any one or any two kinds with
On combination;
Described methanol aqueous solution is the mixing solutions that the mol ratio of methyl alcohol and water is 1: 5.
Improve a method for Propylene Selectivity in MTP reaction, reaction product through and the joining Agilent gas chromatographic analysis of system, draw the content of propylene.
A method that improves Propylene Selectivity in MTP reaction, is characterized in that, the catalyzer in fixed-bed micro-reactor is H-ZSM-5 molecular sieve, and Si/Al is than being 16-80, and the specific surface area of catalyst molecule sieve is 360-500m
2/ g.
Why the temperature of reactor is set in 460～520 DEG C, is mainly that methanol conversion is not high because temperature is too low; Temperature is high, and reaction Propylene Selectivity can reduce, and energy consumption also can increase a lot.
System pressure remains on 0.1～1Mpa, is mainly because pressure raises, and to reacting unfavorable, from molecular balance angle, this reaction is the reaction that volume increases, and high pressure can make reaction carry out to contrary direction, and low pressure is conducive to reaction.
Methanol aqueous solution be the mol ratio of methyl alcohol and water for being defined as 1: 5(be mainly because water alcohol such as fruit is low, Propylene Selectivity is just low, the alkene of high-carbon and aromaticity content can increase a lot; If water alcohol is than too high, the output of propylene is very low again, can waste a large amount of man power and materials.
In MTP reaction, the first step, under the katalysis of catalyzer, methanol dehydration generates dme; Second step, dme generates low-carbon alkene; The 3rd step, low-carbon alkene forms higher olefins, long chain alkane, naphthenic hydrocarbon, aromatic hydrocarbon etc.In MTP reaction, how to make the reaction process of the first step and second step improve, and the reaction process of the 3rd step is reduced, be the key that improves Propylene Selectivity.
For these reasons, the present invention is by add different additives in reactant, and has different action effects, thereby improves the selectivity of propylene.1) additive is ethene, propylene, butylene, and based on present stage, by the indirect C-C carbon pond mechanism of extensive discussions, the alkene of interpolation forms methylbenzene active intermediate by oligomeric, condensation, alkylation, thereby accelerates MTP reaction process.2) additive is dme, Main Function is to accelerate reaction process, shorten the reaction of first stage, because MTP reaction is a strong exothermal reaction, if reaction heat can not be taken away in time, heat accumulation is at reactor catalyst bed, and coking that will accelerator activator has namely increased the formation of C5 and aromatic hydrocarbons and above higher carbon compounds.In the time adding certain dme as reactant, liberated heat while being equivalent to reduce first stage methanol dehydration formation dme, has also just effectively reduced the carbon distribution of catalyzer.
Distinguishing feature of the present invention is, as compared with additive, non-water additive of the present invention, can participate in reaction, improves the selectivity of propylene with water.By adding the additive of different sorts and different mixing proportion, can obviously improve the selectivity of propylene, effectively reduce the carbon distribution of catalyzer, improve the stability of catalyzer.Key of the present invention is, by the effect of additive, while making to form propylene, can pass through fast catalyzer duct, to be discharged in product system, reduces the conversion of propylene to higher olefins, improves Propylene Selectivity.The gas-phase olefin generating discharges in time from catalyzer duct, has effectively reduced catalyst carbon deposit, and the life-span of catalyzer is increased, and stability is improved.
Embodiment
The H-ZSM-5 using in the present invention is homemade molecular sieve catalyst, does not have any metal of load to carry out modifying and decorating, and catalyst S i/Al is than being 16-80, and the specific surface area of molecular sieve catalyst is 360-500m
2/ g.
From document, in MTP reaction, the mol ratio of methyl alcohol and water is selected 1: 5 conventionally.
Embodiment 1
In clean wide-mouth vial, configure methyl alcohol and water mixed liquid, the mol ratio of methyl alcohol and water is respectively 1: 5.
Get 8gSi/Al than 40 H) ZSM) 5 catalyzer, be loaded in the constant temperature zone of reaction tubes, the porcelain ball that particle diameter is 3mm is all equipped with in reaction tubes upper and lower, and reaction tubes is loaded in reactor, is fixedly connected with, and device is carried out to airtight leak test.
Set 500 DEG C of reaction conditionss, control 4 DEG C/min of temperature rise rate, mass space velocity 1.5h) 1, when temperature of reaction reaches set(ting)value, start charging, and pass into respectively ethene, propylene and butylene gas at reactor inlet, pressure is normal pressure, and flow is 18.67ml/min.Get product and carry out gas chromatographic analysis, result is as table 1.
The different gas-phase additive of table 1 optionally affect reaction result
Add ethene and propylene, reaction is had to certain promoter action, Propylene Selectivity improves, and adds aromaticity content showed increased after butylene.
Embodiment 2
In clean wide-mouth vial, configure methyl alcohol and water mixed liquid, the mol ratio of methyl alcohol and water is respectively 1: 5.
Get 8g Si/Al than 30 H) ZSM) 5 catalyzer, be loaded in the constant temperature zone of reaction tubes, the porcelain ball that particle diameter is 3mm is all equipped with in reaction tubes upper and lower, and reaction tubes is loaded in reactor, is fixedly connected with, and device is carried out to airtight leak test.
Set 520 DEG C of reaction conditionss, control 4 DEG C/min of temperature rise rate, mass space velocity 1.0h
-1, when temperature of reaction reaches set(ting)value, starting charging, and pass into gas of dimethyl ether at reactor inlet, pressure is normal pressure, flow is respectively 7.47ml/min, 18.67ml/min, 37.3ml/min, 56.0ml/min, 74.66ml/min.Get product and carry out gas chromatographic analysis, result is as table 2.
The affect situation of the dme of table 2 different flow on Propylene Selectivity
Compared with during with independent interpolation water, within the specific limits, along with the increase of dme intake, speed of response is accelerated, and product Propylene Selectivity obviously improves, and be conducive to reaction, and in this experiment, the dme content in product is little, has nearly all participated in reaction.Methanol conversion is greater than 99.5%.
Claims (3)
1. one kind is improved the method for Propylene Selectivity in MTP reaction, it is characterized in that, using filling in fixed-bed micro-reactor as the molecular sieve of catalyzer, pass into nitrogen, when question response actuator temperature reaches 460～520 DEG C, stop passing into nitrogen, start charging, non-water additive and methanol aqueous solution, according to the mixed in molar ratio of 1:1～1:10, drop into mixture after reactor, system pressure remains on 0.1～1Mpa, and mass space velocity remains on 1.0～2.0h
-1, after reaction 1h, obtain the mix products that contains propylene;
Described non-water additive is any one or any two or more combination in dme, ethene, propylene, butylene;
Described methanol aqueous solution is the mixing solutions that the mol ratio of methyl alcohol and water is 1: 5.
2. a kind of method that improves Propylene Selectivity in MTP reaction as claimed in claim 1, is characterized in that, reaction product through and the joining Agilent gas chromatographic analysis of system, draw the content of propylene.
3. a kind of method that improves Propylene Selectivity in MTP reaction as claimed in claim 1, is characterized in that, the catalyzer in fixed-bed micro-reactor is H-ZSM-5 molecular sieve, and Si/Al is than being 16-80, and the specific surface area of catalyst molecule sieve is 360-500m
2/ g.
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| CN201410131794.5A CN103922882B (en) | 2014-04-02 | 2014-04-02 | A kind of method improving Propylene Selectivity in MTP reaction |
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|---|---|---|---|
| CN201410131794.5A CN103922882B (en) | 2014-04-02 | 2014-04-02 | A kind of method improving Propylene Selectivity in MTP reaction |
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| CN103922882B CN103922882B (en) | 2016-01-06 |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1915937A (en) * | 2005-08-15 | 2007-02-21 | 中国石油化工股份有限公司 | Method for producing propylene, ethene in hihg yield |
| CN101023048A (en) * | 2004-09-21 | 2007-08-22 | 环球油品公司 | Conversion of oxygenate to propylene with selective hydrogen treatment of heavy olefin recycle stream |
| CN101659592A (en) * | 2009-09-10 | 2010-03-03 | 惠生工程（中国）有限公司 | Method for directly preparing propylene from crude methanol |
| CN103030505A (en) * | 2011-09-29 | 2013-04-10 | 中国石油化工股份有限公司 | MTP (methanol to propylene) method |
-
2014
- 2014-04-02 CN CN201410131794.5A patent/CN103922882B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101023048A (en) * | 2004-09-21 | 2007-08-22 | 环球油品公司 | Conversion of oxygenate to propylene with selective hydrogen treatment of heavy olefin recycle stream |
| CN1915937A (en) * | 2005-08-15 | 2007-02-21 | 中国石油化工股份有限公司 | Method for producing propylene, ethene in hihg yield |
| CN101659592A (en) * | 2009-09-10 | 2010-03-03 | 惠生工程（中国）有限公司 | Method for directly preparing propylene from crude methanol |
| CN103030505A (en) * | 2011-09-29 | 2013-04-10 | 中国石油化工股份有限公司 | MTP (methanol to propylene) method |
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