CN101176849B - Catalyzer for preparing propylene from methanol or dimethyl ether in high selectivity and preparation method thereof - Google Patents
Catalyzer for preparing propylene from methanol or dimethyl ether in high selectivity and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a catalyst for preparing propylene with a high selectivity using methanol or dimethyl ether and a preparation method, in particular to a fluidized bed catalyst for preparing propylene with a high selectivity using methanol or dimethyl ether which fits the manufacturing production and a preparation method thereof. The invention carries out a modification handling for the active component of ZSM-5 molecular sieve catalyst by means of stabilizing the molecular sieve structure with the lanthanon, changing the surface acidity with the alkaline matter, and adorning the pore canal with on-line silanization and other means, and prepares a fluidized bed catalyst for preparing propylene with a high selectivity after the sponging drying; the component of the catalyst is in the light of the weight percentage as follows, the rare-earth 0.1 to 8%, the alkalinity modifying agent 0.5 to 30%, the caking agent 20 to 80%, the silanization silicon 0.05 to 10%, the rest is ZSM-5 molecular sieve.
Description
Technical field
The present invention relates to catalyst technical field, is a kind of suitable industrial fluid catalyst and preparation method who is prepared propylene by methyl alcohol or dimethyl ether in high selectivity.
Background technology
By methyl alcohol or dimethyl ether is that catalytic material transforms that to produce low-carbon alkenes (MTO) such as ethene, propylene be the technology path that most possibly substitutes the Petroleum Production bulk chemical.As United States Patent (USP) 4025575,4083889,4433189, and 4476338 all described a kind of to be catalyst with the ZSM-5 molecular sieve, to be prepared the method for low-carbon alkene by methyl alcohol.Because bigger aperture and the stronger surface acidity of ZSM-5 molecular sieve makes it as the MTO catalyst time, the selectivity of low-carbon alkenes such as ethene, propylene is low, can produce accessory substances such as aromatic hydrocarbons and paraffin.Though some other molecular sieve such as erionite, chabasie, T zeolite and ZK-5 molecular sieve have improved olefine selective to a certain extent, their coking rates are big, and inactivation is very fast.
U.S. UCC company (US4440871) has developed novel SAPO series molecular sieve SAPO-n and has been used for the MTO repercussion study.Wherein, SAPO-34 reveals catalytic activity and selectivity of light olefin preferably to the MTO reaction table.Subsequently, the research of MTO catalyst is mainly concentrated on the SAPO-34 molecular sieve, and obtained breakthrough.
Along with the continuous expansion of market, produce propylene by the methyl alcohol high selectivity and caused that people more and more pay attention to the propylene demand.Preparing propylene from methanol (MTP) process and methanol-to-olefins (ethene, propylene) (MTO) process are compared, because product is single propylene, in the subsequent separation process of product, can avoid the cryogenic separation step, therefore, can simplify flow process, reduce investment outlay greatly.Though SAPO-34 is the desirable MTO catalyst of generally acknowledging, but because its aperture is less, can produce a large amount of ethene in the methanol conversion process, be the method for propylene if do not have effective with conversion of ethylene, and this molecular sieve is improper to be the MTP process of purpose product with the propylene.Therefore, the exploitation to MTP process catalyst concentrates on the ZSM-5 molecular sieve.
Germany LURGI has developed preparing propylene from methanol (MTP) technology (patent WO2004/018089), its technological principle is to utilize modified ZSM-5 catalyst series and fixed bed reactors, propylene one way selectivity is about 35～40%, heavy component circulation Returning reactor can make propene yield reach 70%.
Modification for the ZSM-5 molecular sieve has had a lot of researchs.By the modification of Si, P, metal ion and metal oxide, can improve the selectivity of low-carbon alkene on the ZSM-5 molecular sieve catalyst.United States Patent (USP) 4060568 and 4100219 has been described silica to improving the effect of selectivity of light olefin.United States Patent (USP) 6613951,4499314,4849573,4480145 all is to improve selectivity of light olefin to have done good try, and obtains effect preferably.
In United States Patent (USP) 5367100, princes and dukes console etc. and to have described a kind ofly by P and rare-earth element modified ZSM-5 catalyst, and are used for fixing a methanol conversion system olefin process, obtain 100% methanol conversion and C2～C4 olefin yields of 85%.
Because be to be purpose to produce low-carbon alkene (mainly being ethene and propylene), ethylene selectivity is all very high on the existing modified zsm-5 zeolite catalyst, these catalyst and to be not suitable for the propylene be the MTP process of purpose product.
Summary of the invention
Fluid catalyst and the preparation method that the purpose of this invention is to provide a kind of suitable suitability for industrialized production with methyl alcohol or dimethyl ether in high selectivity production propylene.
Be the high conversion of realization methyl alcohol and the high selectivity of propylene, the present invention adopts rare earth element stable molecule sieve structure, alkaline matter to change surface acidity and online silanization duct mode such as modify is carried out modification to active constituent ZSM-5 molecular sieve catalyst to handle, and spray-driedly prepares the catalyst that can be used for fluidized-bed reaction that high selectivity is produced propylene.The existence of rare earth element can increase the stability of zeolite catalyst under the high-temperature water heat condition; The effect of alkalescence modifier is to change the molecular sieve surface acidity on the one hand, is on the other hand to react with binding agent to form the carrier with certain mechanical strength and hydrothermal stability; The effect of online silanization is the pore size distribution of further regulating catalyst, forms to reach ethene suppressing, improves optionally effect of propylene.Middle rare earth element of the present invention is La, Ce and the mishmetal that is rich in La, Ce, is preferably La, Ce; Alkalescence modifier is the nitrate, carbonate, phosphate, chloride of alkaline earth oxide such as phosphoric acid, phosphorous acid, ammonium dihydrogen phosphate (ADP), diammonium hydrogen phosphate, ammonium phosphate, magnesia, calcium oxide, strontium oxide strontia, barium monoxide and alkaline earth oxide etc., is preferably phosphoric acid, phosphorous acid, magnesia, calcium oxide and calcium carbonate; Binding agent is aluminium oxide, silica, silicon aluminium microsphere, kaolin, magnesia, calcium phosphate, calcium carbonate, aluminum phosphate (directly being prepared by phosphoric acid and aluminium oxide reaction in the shaping of catalyst process), is preferably kaolin, aluminum phosphate, calcium phosphate, magnesia; The used silicon of silanization source is organosilicons such as quanmethyl silicate, tetraethyl orthosilicate, silicon tetraethyl, is preferably quanmethyl silicate and tetraethyl orthosilicate.The composition of catalyst is pressed following percentage by weight: rare earth 0.1～8%, and alkaline modifier 0.5～30%, binding agent 20～80%, silanization silicone content 0.05～10%, all the other are the ZSM-5 molecular sieve.In addition, it is 30～1000 that used its silica alumina ratio of ZSM-5 molecular sieve of catalyst of the present invention is preferably selected Si/Al, and content of rare earth is preferably 0.3～3%, and the content of alkaline modifier is preferably in 0.5～20%, binder content is preferably 20～40%, and the silanization silicone content is preferably 1～5%.
Catalyst preparation process of the present invention is as follows:
1, rare earth element dipping: the former powder of ZSM-5 (commodity zeolite or according to the conventional method synthetic zeolite) is added in the nitrate of rare earth element solution, as lanthanum nitrate, behind the normal temperature dipping 24 hours, be warming up to boiling, stir simultaneously, treat into to stop to stir after thick being warming up to 120 ℃ of oven dry, again in air 400～800 ℃ of roastings more than 3 hours, obtain the La/ZSM-5 zeolite, wherein content of rare earth is 0.1～10%.
2, alkaline modifier modification and shaping of catalyst: alkaline modifier (as calcium oxide) and binding agent (as boehmite) are mixed according to a certain percentage, add deionized water simultaneously, fully stir, add the La/ZSM-5 molecular sieve then, stir, cross colloid mill and grind spray-drying.In air, more than 3 hours, obtain containing the ZSM-5 microspherical catalyst of rare earth element and alkaline modifier 400～800 ℃ of roastings.Its neutral and alkali modifier content is 0.5～30%, molecular sieve content 20～80%.
3, H type Preparation of Catalyst: above-mentioned what use in the microspherical catalyst of modifier modification and moulding is the former powder of ZSM-5, regulate if in sieve synthesis procedure, gel is carried out the pH value, need that then catalyst is converted to the H type and just can use with inorganic bases such as NaOH.Above-mentioned microspherical catalyst is exchanged with 0.1mol/l ammonium nitrate or hydrochloric acid solution, liquid volume (ml) is 3～30ml/g with the ratio of catalyst solid (g), and the best is 10～15ml/g, 70～100 ℃ of exchange temperature, each 1～2 hour, exchange altogether 2～3 times.Spend deionised water.110 ℃ of oven dry, 400～800 ℃ of roastings obtained H type microspherical catalyst more than 2 hours.Its Na content is less than 0.02% (weight).If in sieve synthesis procedure, use inorganic ammonia to be the template agent, do not use inorganic base adjusting pH values such as NaOH, then do not need this exchange process.
4, online silanization: H type microspherical catalyst is loaded in the fluidized-bed reactor, carries out silanization in 400～800 ℃ and handle.Tetraethyl orthosilicate is dissolved in the methyl alcohol, and its weight content is 0.1～100%, feeds in the reactor with given pace, makes that the air speed of organosilicon methanol solution is 0.1～30h
-1The reaction certain hour makes that the weight content of silanization silicon on catalyst is 0.05～10%.After Silanization reaction finished, bubbling air was in 400～800 ℃ of roastings more than 2 hours, to remove the carbon deposit of catalyst surface.Obtain being used for the zeolite catalyst that methanol conversion is a propylene.
The specific embodiment
Below by embodiment the present invention is further set forth.
Embodiment 1
Get ZSM-5 zeolite powder 1000g (SiO
2/ Al
2O
3=200), at room temperature carry out the dipping of La.Lanthanum nitrate hexahydrate 1500g, La loading 3%, room temperature dipping was warming up to boiling after 24 hours, stirred simultaneously, treat into to stop to stir after thick to be warming up to 120 ℃ of oven dry, again in air 600 ℃ of roastings 3 hours, obtain the La/ZSM-5 zeolite.Take by weighing 85% SPA (alkaline modifier) 1560g, butt is 65% boehmite (binding agent) 1420g, and deionized water 6000g stirs, reacted 20 minutes, adds the La/ZSM-5 zeolite, stirs 20 minutes, and colloid mill ground 30 minutes, spray shaping.400 ℃ of the inlet temperatures of control spray dryer, 200 ℃ of outlet temperatures, injection pressure 2.0MPa.The catalyst microballoon of moulding was in 600 ℃ of roastings 3 hours.The cooling back exchanges with 0.1mol/l hydrochloric acid, and liquid volume (ml) is 10ml/g with the ratio of catalyst solid (g), and 90 ℃ of exchange temperature each 1 hour, exchange 2 times altogether.Spending deionised water does not detect to there being chlorion.110 ℃ of oven dry, 600 ℃ of roastings obtained the PLa/HZSM-5 microspherical catalyst more than 2 hours.The 10gPLa/HZSM-5 microspherical catalyst is loaded in the fluidized-bed reactor, carries out silanization in 500 ℃.Tetraethyl orthosilicate is dissolved in the methyl alcohol, and its weight content was 10%, with reaction in the speed feeding reactor of 30ml/h 1 hour.After Silanization reaction finished, bubbling air was in 600 ℃ of roastings more than 2 hours, to remove the carbon deposit of catalyst surface.Obtain being used for the zeolite catalyst MTPC-l that methanol conversion is a propylene.
Embodiment 2
Get ZSM-5 zeolite powder 1000g (SiO
2/ Al
2O
3=200), at room temperature carry out the dipping of La.Lanthanum nitrate hexahydrate 1500g, La loading 3%, room temperature dipping was warming up to boiling after 24 hours, stirred simultaneously, treat into to stop to stir after thick to be warming up to 120 ℃ of oven dry, again in air 600 ℃ of roastings 3 hours, obtain the La/ZSM-5 zeolite.Utilize and soak the La identical operations and the La/ZSM-5 zeolite is soaked Mg handle, the Mg loading is 3.2%.Take by weighing contents on dry basis and be 84% kaolin 3567g, deionized water 6000g and above-mentioned PLa/ZSM-5 zeolite stirred 30 minutes, and colloid mill ground 30 minutes, spray shaping.Other operation is identical with embodiment 1.The catalyst that makes is labeled as MTPC-2.
Embodiment 3
Carry out Preparation of Catalyst by embodiment 2, the silanization time is 2 hours.Make catalyst MTPC-3.
Embodiment 4
Carry out Preparation of Catalyst by embodiment 2, in catalyst spray shaping process, kaolinic addition is 2930g.Make catalyst MTPC-4.
Embodiment 5
Molecular sieve catalyst is estimated
Adopt fixed fluidized bed reaction unit that catalyst is estimated.Loaded catalyst is 10g, 500 ℃ of reaction temperatures, reaction pressure normal pressure, 70% methanol aqueous solution, charging air speed 2h
-1React 1 hour the results are shown in preparing propylene by methanol transformation reaction result table 1:
Table 1
Claims (8)
1. one kind is used for the catalyst that methyl alcohol or dimethyl ether in high selectivity prepare propylene, it is characterized in that: the composition of catalyst is by weight percentage: rare earth 0.1～8%, alkaline modifier 0.5～30%, binding agent 20～80%, silanization silicone content 0.05～10%, all the other are the ZSM-5 molecular sieve;
Described alkaline modifier, a kind of in the nitrate of magnesia, calcium oxide, strontium oxide strontia, barium monoxide or ammonium dihydrogen phosphate (ADP), diammonium hydrogen phosphate, ammonium phosphate and alkaline-earth metal, carbonate, phosphate, the chloride.
2. methyl alcohol as claimed in claim 1 or dimethyl ether in high selectivity prepare propylene catalyst, it is characterized in that: it is 30～1000 that its silica alumina ratio of described ZSM-5 molecular sieve is selected Si/Al.
3. methyl alcohol as claimed in claim 1 or dimethyl ether in high selectivity prepare propylene catalyst, it is characterized in that: described rare earth is La, Ce, or is rich in the mishmetal of La, Ce.
4. methyl alcohol as claimed in claim 1 or dimethyl ether in high selectivity prepare propylene catalyst, it is characterized in that: described binding agent, a kind of in aluminium oxide, silica, silicon aluminium microsphere, kaolin, magnesia, calcium phosphate, calcium carbonate, the aluminum phosphate.
5. methyl alcohol as claimed in claim 1 or dimethyl ether in high selectivity prepare propylene catalyst, it is characterized in that: the percentage by weight of each component is: rare earth 0.3～3%, alkaline modifier 0.5～20%, binding agent 20～40%, silanization silicon 1～5%, other is the ZSM-5 molecular sieve.
6. methyl alcohol as claimed in claim 1 or dimethyl ether in high selectivity prepare the preparation method of propylene catalyst, it is characterized in that: the mode that adopts rare earth element stable molecule sieve structure, alkaline matter change surface acidity and online silanization that the duct is modified is carried out modification to active constituent ZSM-5 molecular sieve catalyst and is handled the spray-dried catalyst that is used for fluidized-bed reaction of preparing high selectivity production propylene; Its concrete steps are:
A, rare earth element dipping: the former powder of ZSM-5 is added in the nitrate of rare earth element solution, behind the normal temperature dipping 24 hours, be warming up to boiling, stir simultaneously, treat into to stop after thick stirring and be warming up to 120 ℃ of oven dry, more than 3 hours, obtain rare earth modified ZSM-5 zeolite 400～800 ℃ of roastings again in air, wherein content of rare earth is 0.1～10%;
B, alkaline modifier modification and shaping of catalyst: alkaline modifier and binding agent are mixed according to a certain percentage, add deionized water simultaneously, fully stir, add rare earth modified ZSM-5 molecular sieve then, stir, cross colloid mill and grind spray-drying; In air, more than 3 hours, obtain containing the ZSM-5 microspherical catalyst of rare earth element and alkaline modifier 400～800 ℃ of roastings;
C, H type Preparation of Catalyst: above-mentioned what use in the microspherical catalyst of modifier modification and moulding is the former powder of ZSM-5, regulates if with the NaOH inorganic base gel is carried out the pH value in sieve synthesis procedure, needs that then catalyst is converted to the H type and just can use; Above-mentioned microspherical catalyst is exchanged with 0.1mol/l ammonium nitrate or hydrochloric acid solution, and the ratio of liquid volume ml and catalyst solid g is 3～30ml/g, and 70～100 ℃ of exchange temperature each 1～2 hour, exchange 2～3 times altogether; Spend deionised water; 110 ℃ of oven dry, 400～800 ℃ of roastings obtained H type microspherical catalyst more than 2 hours, and its Na content weight ratio is less than 0.02%; If in sieve synthesis procedure, use inorganic ammonia to be the template agent, do not use the NaOH inorganic base to regulate the pH value, then do not need this exchange process;
D, online silanization: H type microspherical catalyst is loaded in the fluidized-bed reactor, carries out silanization in 400～800 ℃ and handle; Tetraethyl orthosilicate is dissolved in the methyl alcohol, and its weight content is 0.1～100%, feeds in the reactor with given pace, makes that the air speed of organosilicon methanol solution is 0.1～30h
-1Reaction a period of time, make that the weight content of silanization silicon on catalyst is 0.05～10%;
After E, Silanization reaction finished, bubbling air more than 2 hours, to remove the carbon deposit of catalyst surface, obtained being used for the zeolite catalyst that methanol conversion is a propylene in 400～800 ℃ of roastings.
7. preparation method as claimed in claim 6 is characterized in that: the used silicon of described silanization source is quanmethyl silicate, tetraethyl orthosilicate, silicon tetraethyl.
8. preparation method as claimed in claim 6 is characterized in that: the described B ZSM-5 microspherical catalyst in the step, its neutral and alkali modifier content be 0.5～30%, molecular sieve content 20～80%.
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Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101844087B (en) * | 2010-06-22 | 2012-04-25 | 西南化工研究设计院 | Preparation method of catalyst for preparing propylene by methanol conversion |
| WO2013091335A1 (en) * | 2011-12-19 | 2013-06-27 | 中国科学院大连化学物理研究所 | Catalyst for preparing ethylene and propylene by using methyl alcohol and/or dimethyl ether, and preparation method and application of ethylene and propylene |
| CN104069887B (en) * | 2013-03-29 | 2016-09-14 | 上海碧科清洁能源技术有限公司 | A kind of method of the ZSM-5 molecular sieve catalyst preparing Si modification, catalyst obtained by this method and application thereof |
| CN104209139B (en) * | 2013-06-04 | 2016-04-06 | 中国石油天然气集团公司 | A kind of methanol conversion produces the Catalysts and its preparation method that propene yield taken into account by gasoline |
| CN104722328A (en) * | 2013-12-24 | 2015-06-24 | 高化学株式会社 | Catalyst system for preparing propylene through conversion of dimethyl ether as well as preparation method and application thereof, and method for preparing propylene through conversion of dimethyl ether |
| CN104107711A (en) * | 2014-07-18 | 2014-10-22 | 陕西煤化工技术工程中心有限公司 | Fluidized bed catalyst for preparing propylene from methanol and preparation method of fluidized bed catalyst |
| CN105772059A (en) * | 2014-12-26 | 2016-07-20 | 中国科学院大连化学物理研究所 | Catalyst for preparing propylene from methyl alcohol or/and dimethyl ether and preparation method of catalyst |
| CN106466619B (en) * | 2015-08-20 | 2019-05-14 | 中国石油化工股份有限公司 | Propylene catalyst from methanol conversion and preparation method thereof |
| CN112642395A (en) | 2019-10-11 | 2021-04-13 | 中国石油化工股份有限公司 | Molecular sieve compound and composite material as well as preparation method and application thereof |
| CN114605213B (en) * | 2020-12-09 | 2023-01-31 | 中国科学院大连化学物理研究所 | A method for producing propylene from synthesis gas and dimethyl ether |
| CN113617381A (en) * | 2021-08-18 | 2021-11-09 | 西北大学 | Method for improving stability of HZSM-5 molecular sieve catalyst |
| CN118416937A (en) * | 2024-07-04 | 2024-08-02 | 中国科学技术大学先进技术研究院 | Coal-fired catalyst and preparation method thereof |
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