CN101695667B - Preparation method for preparing low-carbon olefine catalyst by ethanol and reaction process - Google Patents
Preparation method for preparing low-carbon olefine catalyst by ethanol and reaction process Download PDFInfo
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- CN101695667B CN101695667B CN2009100711036A CN200910071103A CN101695667B CN 101695667 B CN101695667 B CN 101695667B CN 2009100711036 A CN2009100711036 A CN 2009100711036A CN 200910071103 A CN200910071103 A CN 200910071103A CN 101695667 B CN101695667 B CN 101695667B
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- molecular sieve
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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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Abstract
The invention provides a method for preparing a lanthanum-containing composite molecular sieve catalyst and applying the lanthanum-containing composite molecular sieve catalyst in a reaction of preparing low-carbon olefine by ethanol. Vulcanized lanthanum oxide prepared by adopting an HZSM-5 molecular sieve and a sol-gel method is used as a composite precursor, and the lanthanum-containing composite molecular sieve is synthesized through the baking treatment of the composite precursor. The method has the advantages that the preparation method for the catalyst is simple, has mild synthesis conditions, and only needs to prepare the composite precursor and simply bake the composite precursor; and the reaction for preparing the low-carbon olefine by ethanol through the catalyst has mild conditions.
Description
Technical field
The present invention relates to a kind ofly contain the preparation method of lanthanum composite molecular sieve catalyst and be applied to ethanol preparation low-carbon alkene reaction.
Background technology
Low-carbon alkene is as a kind of important chemicals raw material, and its main production method is to obtain through the oil boom cracking at present.In recent years, because the world energy sources crisis is serious day by day, the method that people have to seek environmental protection more economically obtains low-carbon alkene.At present, owing to ethanol can make through biofermentation, and the simple environmental protection of zymotechnique, cause many concerns of people by the ethanol preparation low-carbon alkene.Propylene is more remarkable in the status of chemical field as one of important member of low-carbon alkene, for example expoxy propane, the polyacrylic participation that all needs propylene such as synthetic.
In recent years, production of propylene has caused the attention that People more and more is many, and the conventional production methods of ethene and propylene is that the heat scission reaction through naphtha obtains, but this method need at high temperature carry out, and temperature generally will be at 600-1000 ℃.The MTO reaction that a kind of in addition method of producing low-carbon alkene is scientific worker's broad research in recent years.Because ethanol is unique product that can pass through the biofermentation acquisition, so compare the MTO process, the ethanol preparation low-carbon alkene has more its researching value.Early-stage Study result shows that the dehydration of oxygenatedchemicals can be carried out fast under acidic catalyst.At present catalyst system therefor mainly contains SAPO-34, Ni/MCM-41 but these catalyst all are not suitable for commercial production in the defective aspect stable.In addition, people have also transferred to the HZSM-5 catalyst with sight, are how to generate ethene through ethanol conversion but pay close attention to maximum, gasoline, aromatic compound etc., Zn for example, the HZSM-5 catalyst of Ga modification etc.
Propylene production mainly contains following three kinds: (1) catalytic cracking reaction, but because the restriction of reaction condition, the propylene effect of increasing production is also not obvious; (2) being raw material with ethene and butylene obtains propylene through the two displacement reaction; (3) under the situation that does not add raw material only by ethene Direct Production propylene.In the said method, the severity of reaction condition, the shortage property of catalyst have limited the large-scale production of propylene.
Summary of the invention
The present invention proposes a kind ofly to contain the preparation method of lanthanum composite molecular sieve catalyst and be applied in the reaction of ethanol preparation low-carbon alkene.It is composite precursor that this method adopts the sulfidation-oxidation lanthanum of HZSM-5 molecular sieve and Prepared by Sol Gel Method, synthesizes and contains the lanthanum composite molecular sieve catalyst through composite precursor being carried out calcination process.And will contain the lanthanum composite molecular sieve catalyst and be used for ethanol preparation low-carbon alkene reaction, catalyst of the present invention can obviously reduce arenes selectivity and improve selectivity of light olefin.
Characteristics of the present invention are that method for preparing catalyst is simple, and synthesis condition is gentle, only need prepare composite precursor and it is carried out simple roasting.Catalyst applications is gentle in the reaction condition of ethanol preparation low-carbon alkene, is fit to industrial mass production.
The technical scheme that the present invention adopted is following:
(1) at first takes by weighing a certain amount of lanthanum salt, under stirring at room, it is dissolved in the deionized water, add certain amount of ammonia water solution after the stirring and dissolving and regulate pH to 7-9 and obtain gel the gained gel is washed according to stoichiometric relationship.
(2) take by weighing an amount of polyvinylpyrrolidone (PVP), be made into 10% solution, add in (1) described gel rubber system and strong agitation.
(3) take by weighing an amount of sulfuric acid solution, add in (2) said system and fully and stir.Add a certain amount of self-control HZSM-5 molecular sieve then, stir the lanthana composite precursor that 2-5h obtains HZSM-5 molecular sieve and Prepared by Sol Gel Method.
(4) crucible of packing into after the precursor powder after will drying is ground, under air atmosphere with precursor roasting at a certain temperature 4 hours.Above-mentioned said catalyst can be used for the reaction of ethanol preparation low-carbon alkene.
The described lanthanum composite molecular sieve catalyst that contains is used for ethanol preparation low-carbon alkene reaction process and comprises the steps:
(1) catalyst is seated in the normal pressure continuous fixed bed reactor, under nitrogen atmosphere, is warming up to 500 ℃, and beds was purged 1 hour at 500 ℃, reduce temperature to 450 ℃ then, feed ethanol raw material, ethanol liquid charging air speed 1-2h
-1
Product analysis: product is after condensation, and through being furnished with the online gas chromatographic analysis of flame ionization ditector and thermal conductivity detector (TCD), the gas-chromatography chromatographic column is respectively Al
2O
3Packed column and GDX-102 packed column.Or
(2) catalyst is seated in the normal pressure continuous fixed bed reactor, under nitrogen atmosphere, is warming up to 450 ℃, and beds is purged 1h at 450 ℃.Feed ethanol raw material then, ethanol charging air speed 1-2h
-1
Product analysis: product is after condensation, and through being furnished with the online gas chromatographic analysis of flame ionization ditector and thermal conductivity detector (TCD), the gas-chromatography chromatographic column is respectively Al
2O
3Packed column and GDX-102 packed column.
Stoichiometric relationship described in the synthesis step is that the weight by the HZSM-5 molecular sieve is benchmark, counts by weight percentage element lanthanum component, calculates the quality of required lanthanum salt according to the amount of required simple substance lanthanum.The lanthanum component percentages is in the 5-15% scope; Described lanthanum salt is to analyze pure lanthanum nitrate or lanthanum chloride, and Prepared by Sol Gel Method pH value is 7-9, and the sintering temperature of composite precursor is 400-550 ℃.The reaction temperature 400-500 of ethanol preparation low-carbon alkene ℃, the charging air speed is 1-2h
-1
The beneficial effect that the present invention had is: the present invention is that to adopt the sulfidation-oxidation lanthanum and the HZSM-5 of Prepared by Sol Gel Method be composite catalyst, and purpose is in order to optimize the catalyst activity component, improves the catalyst acid center intensity and prolongs catalyst service life.Advantages such as this method for preparing catalyst is simple, is used for the reaction of ethanol preparation low-carbon alkene, and conversion ratio is high, and is renewable.
The specific embodiment
To product of the present invention and preparation method thereof further explain, but they are not that the present invention is done any restriction below in conjunction with embodiment.
These embodiment have explained the building-up process that contains lanthanum composite molecular sieve catalyst preparation method.
Comparative Examples 1
This Comparative Examples explanation Preparation of catalysts process.
Embodiment 1
At first take by weighing the lanthanum nitrate hexahydrate of 11.37g, under stirring at room, it is dissolved in the 27g deionized water, add certain amount of ammonia water solution after the stirring and dissolving and regulate pH value to 8 and obtain gel the gained gel is washed according to stoichiometric relationship; Take by weighing 0.5g polyvinylpyrrolidone (PVP), be made into 10% solution, add in the above-mentioned gel rubber system and strong agitation, drip concentrated sulfuric acid 0.8g and fully stirring; Add 15g self-control HZSM-5 molecular sieve at last, strong agitation 3h obtains the 10%La-1.5%S/HZSM-5 composite precursor.Afterwards with this composite precursor 100 ℃ of oven dry, the crucible of packing into after precursor powder after will drying is then ground, 500 ℃ of roastings are 4 hours under air atmosphere.Gained sample called after A.
Embodiment 2
The preparation process is identical with the preparation process of sample A, and the amount that only changes lanthanum nitrate hexahydrate is 21.6g, and other condition is constant.The gained sample is named as B.
Embodiment 3
The preparation process is identical with the preparation process of sample A, and only changing the pH of latex gel value is 9, and other condition is constant.The gained sample is named as C.
Embodiment 4
The preparation process is identical with the preparation process of sample A, and the lanthanum nitrate hexahydrate that only changes 11.37g is the seven hydration lanthanum trichlorides of 11.6g, and other condition is constant.The gained sample is named as D.
Comparative Examples 2
This Comparative Examples contains the reaction that the lanthanum composite molecular sieve catalyst is applied to the ethanol preparation low-carbon alkene in order to explanation
Embodiment 1
Take by weighing above-mentioned catalyst A 5mL and mix 5mL quartz sand, be seated in the normal pressure continuous fixed bed reactor, under nitrogen atmosphere, be warming up to 500 ℃, and beds was purged 1 hour at 500 ℃, reduce temperature to 450 ℃ then, feed ethanol raw material.Ethanol liquid air speed 1.0h
-1, question response conditional stability is after 5 hours, and product adopts gas chromatographic analysis after condensation.Be labeled as A1.
Catalyst activity is shown in table one.
Embodiment 2
Take by weighing above-mentioned catalyst A 5mL and mix 5mL quartz sand, be seated in the normal pressure continuous fixed bed reactor, under nitrogen atmosphere, be warming up to 450 ℃, and beds was purged 1 hour at 450 ℃, feed ethanol raw material.Ethanol liquid air speed 1.0h
-1, question response conditional stability is after 5 hours, and product adopts gas chromatographic analysis after condensation.Be labeled as A2.
Catalyst activity is shown in table one.
Embodiment 3
Take by weighing above-mentioned catalyst A 5mL and mix 5mL quartz sand, be seated in the normal pressure continuous fixed bed reactor, under nitrogen atmosphere, be warming up to 450 ℃, and beds was purged 1 hour at 450 ℃, feed ethanol raw material.Ethanol liquid air speed 2.0h
-1, question response conditional stability is after 5 hours, and product adopts gas chromatographic analysis after condensation.Be labeled as A3.
Catalyst activity is shown in table one.
Embodiment 4
Take by weighing above-mentioned catalyst A 5mL and mix 5mL quartz sand, be seated in the normal pressure continuous fixed bed reactor, under nitrogen atmosphere, be warming up to 500 ℃, and beds was purged 1 hour at 500 ℃, feed ethanol raw material.Ethanol liquid air speed 2h
-1, question response conditional stability is after 5 hours, and product adopts gas chromatographic analysis after condensation.Be labeled as A4.
Catalyst activity is shown in table one.
Embodiment 5
Take by weighing self-control pure state HZSM-5 catalyst 5mL and mix 5mL quartz sand; Be seated in the normal pressure continuous fixed bed reactor, under nitrogen atmosphere, be warming up to 500 ℃, and beds was purged 1 hour at 500 ℃; Reduce temperature to 450 ℃ then, feed ethanol raw material.Ethanol liquid air speed 1.0h
-1, question response conditional stability is after 5 hours, and product adopts gas chromatographic analysis after condensation.Be labeled as HZSM-5.
Catalyst activity is shown in table one.
Table one. contain the lanthanum composite molecular sieve catalyst and be applied to ethanol preparation low-carbon alkene reaction evaluating result
| Catalyst | Ethanol conversion (%) | Propylene selectivity (%) |
| A1 | 100 | 20 |
| A2 | 100 | 18 |
| A3 | 100 | 15 |
| A4 | 100 | 21 |
| HZSM-5 | 100 | 1.5 |
Claims (1)
1. preparation method who contains the lanthanum composite molecular sieve catalyst; It is characterized in that comprising following steps: the lanthanum nitrate hexahydrate that at first takes by weighing 11.37g; Under stirring at room, it is dissolved in the 27g deionized water; Add certain amount of ammonia water solution adjusting pH value to 8 after the stirring and dissolving and obtain gel, the gained gel is washed; Take by weighing the 0.5g polyvinylpyrrolidone, be made into 10% solution, add in the above-mentioned gel rubber system and strong agitation, drip concentrated sulfuric acid 0.8g and fully stirring; Add 15g self-control HZSM-5 molecular sieve at last, strong agitation 3h obtains the 10%La-1.5%S/HZSM-5 composite precursor; Afterwards with this composite precursor 100 ℃ of oven dry, the crucible of packing into after precursor powder after will drying is then ground, 500 ℃ of roastings are 4 hours under air atmosphere.
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| CN2009100711036A CN101695667B (en) | 2009-11-03 | 2009-11-03 | Preparation method for preparing low-carbon olefine catalyst by ethanol and reaction process |
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| CN2009100711036A CN101695667B (en) | 2009-11-03 | 2009-11-03 | Preparation method for preparing low-carbon olefine catalyst by ethanol and reaction process |
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| CN101695667B true CN101695667B (en) | 2012-01-25 |
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| CN116463140A (en) * | 2023-05-12 | 2023-07-21 | 中国科学技术大学 | Method for preparing aviation kerosene by using low-carbon mixed alcohol |
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