CN101623651A - Catalyst for preparing propylene by methyl alcohol and/or dimethyl ether and preparation method thereof - Google Patents
Catalyst for preparing propylene by methyl alcohol and/or dimethyl ether and preparation method thereof Download PDFInfo
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- CN101623651A CN101623651A CN200910053795A CN200910053795A CN101623651A CN 101623651 A CN101623651 A CN 101623651A CN 200910053795 A CN200910053795 A CN 200910053795A CN 200910053795 A CN200910053795 A CN 200910053795A CN 101623651 A CN101623651 A CN 101623651A
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Abstract
The invention discloses a catalyst for preparing propylene by methyl alcohol and/or dimethyl ether and a preparation method thereof. The catalyst takes HZSM-5 molecular sieve with the crystallite dimension being less than 100 nanometers as raw material, and adopts fluorine-containing compound solution for dipping; after that, the catalyst is prepared by high temperature calcination and has the fluorous mass percentage of 2-20%. The catalyst prepared by the method has very high propylene yield and stability for the reaction for preparing the propylene by transforming the methyl alcohol.
Description
Technical field
The present invention relates to a kind of molecular sieve catalyst that is used for methyl alcohol and/or dimethyl ether production propylene and preparation method thereof.
Background technology
Propylene is a kind of important basic organic, is mainly used in chemical products such as producing polypropylene, acrylonitrile and expoxy propane.At present, the production of propylene is mainly from the catalytic cracking unit of preparing ethylene by steam cracking device and oil plant.Because oil is non-renewable resources, reserves are very limited, and the price of oil rises steadily, so countries in the world all begin to be devoted to the exploitation of non-petroleum path system propylene technology.Wherein, receive more and more widely concern by coal, natural gas and living beings through the technology of methyl alcohol or dimethyl ether system propylene, the key of this technology is the development of high performance catalyst.At present, to this reacting catalytic performance best surely belong to the HZSM-5 molecular sieve.Under the effect of HZSM-5 molecular sieve catalyst, methyl alcohol at first dewaters and generates dimethyl ether (DME), and DME and methanol mixture continue to be converted into the low-carbon alkene based on ethene, propylene and butylene then.The low-carbon alkene that is generated further generates accessory substances such as alkane, aromatic hydrocarbons and higher olefins by series reaction such as polycondensation, cyclisation, dehydrogenation, alkylation and hydrogen migrations.Therefore, for the selectivity that improves purpose product propylene can be taked to improve the methyl alcohol air speed and use diluted methyl alcohol as reactant, to shorten the time of staying of propylene at catalyst surface.But these two kinds of methods all can cause the significant wastage of material consumption and/or energy consumption, thereby the production cost of propylene is significantly increased.And adopt the less HZSM-5 sieve peg-raking catalyst of crystallite dimension can shorten the time of staying of propylene equally, thereby improve the selectivity of propylene and the stability of catalyst at catalyst surface." petrochemical industry ", reported crystallite dimension be the propylene selectivity of 0.5 micron HZSM-5 molecular sieve be higher than crystallite dimension be 3～5 micron HZSM-5 molecular sieve at 1983,12 (9): 531." catalysis journal ", reported crystallite dimension be the propylene selectivity (36.1%) of 0.25～0.5 micron HZSM-5 molecular sieve catalyst want obviously greater than crystallite dimension be 3～4 micron HZSM-5 molecular sieve catalyst (21.5%) at 1983,4 (3): 248." Chemical Reaction Engineering and technology ", 2007, reported grain size be respectively 0.6,2,10 and 20 micron four kind HZSM-5 molecular sieve catalysts with the yield that reduce propylene of zeolite crystal size gradually increase at 23 (6): 481, and peak has reached 44.1%.Chinese patent CN 101402049A disclosure employing crystallite dimension is that the HZSM-5 molecular sieve of 300 nanometers is a catalyst, and the yield of propylene can reach 42%.This shows, adopt the less HZSM-5 sieve peg-raking catalyst of crystallite dimension can improve the selectivity of methyl alcohol and/or dimethyl ether production propylene and the stability of catalyst.Yet, existingly being used for methyl alcohol or dimethyl ether production propylene catalyst for reaction all adopts the bigger micron order of crystallite dimension (＞100 nanometer) HZSM-5 molecular sieve, propene yield is lower and/or catalyst stability is relatively poor.
Summary of the invention
Technical problem to be solved by this invention provides a kind of novel HZSM-5 molecular sieve catalyst that is used for methyl alcohol and/or dimethyl ether production propylene and preparation method thereof, and its propene yield is higher, stability is better.
Technical solution of the present invention: a kind of catalyst that is used for methyl alcohol and/or dimethyl ether production propylene, the crystallite dimension of its used HZSM-5 molecular sieve are less than 100 nanometers, and the quality percentage composition of fluorine is 2～20% in the catalyst, and its preparation method comprises the following steps:
A, fluoride dissolution is obtained the solution that concentration is 0.1～2M in deionized water, then crystallite dimension is poured in the above-mentioned solution less than 100 nanometer HZSM-5 molecular sieves, the usage ratio of described solution and described molecular sieve is every gram molecule sieve 1～10ml solution, at room temperature flood 1～10h, obtain fluorine-containing precursor at 50～150 ℃ of down dry 1～24h then, wherein said fluoride is fluoride salt or hydrofluoric acid or the mixture of the two;
B, above-mentioned fluorine-containing precursor is put into roaster,, make described catalyst at 300～600 ℃ of following roasting 1～12h.
Fluoride salt described in the steps A is an ammonium fluoride.
A kind of Preparation of catalysts method that is used for methyl alcohol and/or dimethyl ether production propylene comprises the following steps:
A, fluoride dissolution is obtained the solution that concentration is 0.1～2M in deionized water, then crystallite dimension is poured in the above-mentioned solution less than 100 nanometer HZSM-5 molecular sieves, the usage ratio of described solution and described molecular sieve is every gram molecule sieve 1～10ml solution, at room temperature flood 1～10h, obtain fluorine-containing precursor at 50～150 ℃ of down dry 1～24h then, wherein said fluoride is fluoride salt or hydrofluoric acid or the mixture of the two;
B, above-mentioned fluorine-containing precursor is put into roaster,, make described catalyst at 300～600 ℃ of following roasting 1～12h.
Fluoride salt described in the steps A is an ammonium fluoride.
Beneficial effect of the present invention: methanol molecules participates in reaction by the inner surface that diffusion enters into molecular sieve, if the crystallite dimension of molecular sieve is too big, methanol molecules is subjected to certain resistance, inner surface to molecular sieve more difficult to get access, and can only participate in reaction, thereby reduced the surperficial utilization rate of molecular sieve at the outer surface of molecular sieve.In addition, if the crystallite dimension of molecular sieve is too big, the path that the propylene that generated of reaction diffuses out in the molecule sieve aperture is longer, the time of staying on molecular sieve is also longer, further reaction generates accessory substances such as alkane, aromatic hydrocarbons and higher olefins, not only reduced propene yield, also made the catalyst rapid deactivation.Nano molecular sieve, crystallite dimension is less than 100 nanometers, because of having very little crystallite dimension and very big specific area, characteristics such as show more than the short and surface acid center quantity of tangible diffusion distance, thereby have catalytic activity height, carbon deposit is few and carbon accumulation resisting ability is strong remarkable advantage.The central principle of the inventive method is that to adopt nanometer HZSM-5 molecular sieve be raw material and prepares catalyst by methyl alcohol and/or dimethyl ether conversion system propylene by the fluorine modification, therefore have the advantage of methyl alcohol and/or dimethyl ether conversion rate and propylene selectivity height and good stability, effectively overcome and be used for the low shortcoming with poor stability of methyl alcohol and/or the existing propylene selectivity of dimethyl ether conversion system propylene catalyst for reaction in the prior art.
The specific embodiment
Below by embodiment the present invention is described in further detail, a kind of catalyst that is used for methyl alcohol and/or dimethyl ether production propylene, the crystallite dimension of its used HZSM-5 molecular sieve is less than 100 nanometers, the quality percentage composition of fluorine is 2～20% in the catalyst, its preparation method comprises the following steps: A, fluoride dissolution is obtained the solution that concentration is 0.1～2M in deionized water, then crystallite dimension is poured in the above-mentioned solution less than 100 nanometer HZSM-5 molecular sieves, the usage ratio of described solution and described molecular sieve is every gram molecule sieve 1～10ml solution, at room temperature flood 1～10h, obtain fluorine-containing precursor at 50～150 ℃ of down dry 1～24h then, wherein said fluoride is fluoride salt or hydrofluoric acid or the mixture of the two, and fluoride salt described in the steps A is an ammonium fluoride; B, above-mentioned fluorine-containing precursor is put into roaster,, make described catalyst at 300～600 ℃ of following roasting 1～12h.
A kind of Preparation of catalysts method that is used for methyl alcohol and/or dimethyl ether production propylene, comprise the following steps: A, fluoride dissolution is obtained the solution that concentration is 0.1～2M in deionized water, then crystallite dimension is poured in the above-mentioned solution less than 100 nanometer HZSM-5 molecular sieves, the usage ratio of described solution and described molecular sieve is every gram molecule sieve 1～10ml solution, at room temperature flood 1～10h, obtain fluorine-containing precursor at 50～150 ℃ of down dry 1～24h then, wherein said fluoride is fluoride salt or hydrofluoric acid or the mixture of the two, and fluoride salt described in the steps A is an ammonium fluoride; B, above-mentioned fluorine-containing precursor is put into roaster,, make described catalyst at 300～600 ℃ of following roasting 1～12h.
The using method of the catalyst of the present invention preparation is a raw material when using described Preparation of Catalyst propylene with methyl alcohol and/or dimethyl ether, is diluent with water, and the mixture of raw material and diluent is contained the effluent of propylene with the catalyst reaction generation that contacts.Reaction temperature is 400～550 ℃ when using catalyst, and the air speed of material benzenemethanol or dimethyl ether is 0.2～10h
-1, the mass ratio of methyl alcohol or dimethyl ether and water is 0.2～5: 1.The catalyst of the present invention preparation can be used for fixed bed reactors and also can be applicable to fluidized-bed reactor, both can methyl alcohol or dimethyl ether be raw material, also can methyl alcohol and the mixture of dimethyl ether be raw material.
An example of the inventive method of using fixed bed reactors is hereinafter described.It is 6mm that a certain amount of catalyst granules (20～40 order) is loaded in internal diameter, and length is in the stainless steel reaction pipe of 300mm.Reactor adopts electrical heating, and temperature is controlled automatically.Reaction tube bottom filling 20～40 purpose inert materials are as supporter, and filling 20～40 purpose inert materials in catalyst top are made the usefulness of raw material preheating.By beds, raw material is a methyl alcohol to raw material from top to bottom, and water is diluent, and the mass ratio of methyl alcohol and water is 3: 7; The air speed of methyl alcohol is 1h
-1Reaction pressure is that normal pressure, temperature are 500 ℃.The 6820 type gas chromatographs that product adopts Agilent company to produce carry out on-line analysis.
Embodiment 1
1 gram is analyzed pure NH
4F is dissolved in 10 milliliters the deionized water, stirs it is dissolved fully.Then the 5 HZSM-5 molecular sieves that the gram silica alumina ratios are 25, crystallite dimension is 50～80 nanometers are poured in the above-mentioned solution, room temperature place after 4 hours 100 ℃ dry 12 hours down, place Muffle furnace 500 ℃ of following roastings 4 hours again, make described catalyst A.
Embodiment 2
Make catalyst B with embodiment 1, just NH
4The amount of F is 0.2 gram.
Embodiment 3
Make catalyst C with embodiment 1, just NH
4The amount of F is 0.5 gram.
Embodiment 4
Make catalyst D with embodiment 1, just NH
4The amount of F is 1.5 grams.
Embodiment 5
Make catalyst E with embodiment 1, just NH
4The amount of F is 2 grams.
Embodiment 6
Make catalyst F with embodiment 1, just sintering temperature is 300 ℃.
Embodiment 7
Make catalyst G with embodiment 1, just sintering temperature is 400 ℃.
Embodiment 8
Make catalyst H with embodiment 1, just sintering temperature is 450 ℃.
Embodiment 9
Make catalyst I with embodiment 1, just sintering temperature is 550 ℃.
Embodiment 10
Make catalyst J with embodiment 1, just sintering temperature is 600 ℃.
Embodiment 11-20
1 gram catalyst A～J is packed in the fixed bed reactors, and (30 ml/min) temperature that raises gradually is 500 ℃ under stream of nitrogen gas, keeps after 1 hour, nitrogen is switched to the mixture (mass ratio of methyl alcohol and water is 3: 7) of methyl alcohol and water; The charging rate of methyl alcohol is 1 Grams Per Hour; Reaction temperature is 500 ℃.Take a sample after 4～6 hours when reaction, the 6820 type gas chromatographs that adopt Agilent company to produce carry out on-line analysis, the results are shown in Table 1.
The reactivity worth of table 1 catalyst
| Catalyst | Propene yield (%) | Keep the time (h) that methyl alcohol 100% transforms |
| ??A | ??46.8 | ??145 |
| ??B | ??40.5 | ??85 |
| ??C | ??42.6 | ??110 |
| ??D | ??46.3 | ??115 |
| ??E | ??41.2 | ??95 |
| ??F | ??37.5 | ??80 |
| ??G | ??39.6 | ??92 |
| ??H | ??38.2 | ??85 |
| ??I | ??41.8 | ??96 |
| ??J | ??40.3 | ??87 |
By data in the table as seen, adopt the catalyst of the inventive method preparation,, have very high propene yield and stability for the preparing propylene by methanol transformation reaction.
Foregoing only is the basic explanation of the present invention under conceiving, and according to any equivalent transformation that technical scheme of the present invention is done, all should belong to protection scope of the present invention.
Claims (4)
1. catalyst that is used for methyl alcohol and/or dimethyl ether production propylene, the crystallite dimension of its used HZSM-5 molecular sieve is less than 100 nanometers, and the quality percentage composition of fluorine is 2～20% in the catalyst, and its preparation method comprises the following steps:
A, fluoride dissolution is obtained the solution that concentration is 0.1～2M in deionized water, then crystallite dimension is poured in the above-mentioned solution less than 100 nanometer HZSM-5 molecular sieves, the usage ratio of described solution and described molecular sieve is every gram molecule sieve 1～10ml solution, at room temperature flood 1～10h, obtain fluorine-containing precursor at 50～150 ℃ of down dry 1～24h then, wherein said fluoride is fluoride salt or hydrofluoric acid or the mixture of the two;
B, above-mentioned fluorine-containing precursor is put into roaster,, make described catalyst at 300～600 ℃ of following roasting 1～12h.
2. according to the described catalyst that is used for methyl alcohol and/or dimethyl ether production propylene of claim 1, it is characterized in that: fluoride salt described in the steps A is an ammonium fluoride.
3. a Preparation of catalysts method that is used for methyl alcohol and/or dimethyl ether production propylene comprises the following steps:
A, fluoride dissolution is obtained the solution that concentration is 0.1～2M in deionized water, then crystallite dimension is poured in the above-mentioned solution less than 100 nanometer HZSM-5 molecular sieves, the usage ratio of described solution and described molecular sieve is every gram molecule sieve 1～10ml solution, at room temperature flood 1～10h, obtain fluorine-containing precursor at 50～150 ℃ of down dry 1～24h then, wherein said fluoride is fluoride salt or hydrofluoric acid or the mixture of the two;
B, above-mentioned fluorine-containing precursor is put into roaster,, make described catalyst at 300～600 ℃ of following roasting 1～12h.
4. according to the described a kind of Preparation of catalysts method that is used for methyl alcohol and/or dimethyl ether production propylene of claim 3, it is characterized in that: fluoride salt described in the steps A is an ammonium fluoride.
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| Application Number | Priority Date | Filing Date | Title |
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| CN200910053795A CN101623651A (en) | 2009-06-25 | 2009-06-25 | Catalyst for preparing propylene by methyl alcohol and/or dimethyl ether and preparation method thereof |
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| CN200910053795A CN101623651A (en) | 2009-06-25 | 2009-06-25 | Catalyst for preparing propylene by methyl alcohol and/or dimethyl ether and preparation method thereof |
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| CN101623651A true CN101623651A (en) | 2010-01-13 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102527427A (en) * | 2012-01-06 | 2012-07-04 | 厦门大学 | Modified molecular sieve catalyst for preparing propylene by methinehalide and preparation method of modified molecular sieve catalyst |
| CN114073976A (en) * | 2020-08-10 | 2022-02-22 | 中国科学院大连化学物理研究所 | Modified ZSM-5 molecular sieve and preparation method and application thereof |
-
2009
- 2009-06-25 CN CN200910053795A patent/CN101623651A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102527427A (en) * | 2012-01-06 | 2012-07-04 | 厦门大学 | Modified molecular sieve catalyst for preparing propylene by methinehalide and preparation method of modified molecular sieve catalyst |
| CN114073976A (en) * | 2020-08-10 | 2022-02-22 | 中国科学院大连化学物理研究所 | Modified ZSM-5 molecular sieve and preparation method and application thereof |
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Open date: 20100113 |