CN104107707A - Binder-free ZSM-5 molecular sieve catalyst, and preparation method and use thereof - Google Patents
Binder-free ZSM-5 molecular sieve catalyst, and preparation method and use thereof Download PDFInfo
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Abstract
The invention relates to a binder-free ZSM-5 molecular sieve catalyst, and a preparation method and a use thereof. The problems of low activity of a binder-containing ZSM-5 molecular sieve in the prior art and low intensity of a binder-free ZSM-5 molecular sieve in the prior art are mainly solved. The catalyst comprises 90-100wt% of a ZSM-5 molecular sieve with the shape index of 3-100 (the shape index is defined as a length ratio of a longest edge to a shortest edge of a molecular sieve crystal in a three dimensional direction), 0-5wt% of phosphorus or oxide thereof, and 0-5wt% of at least one of rare earth elements or oxides thereof. The preparation method well solves the problems, and the binder-free ZSM-5 molecular sieve catalyst prepared in the invention can be used in the industrial production for preparing propylene and aromatic hydrocarbons by using methanol.
Description
Technical field
The present invention relates to a kind of adhesiveless ZSM-5 molecular sieve catalyst, Preparation method and use.
Background technology
Methyl alcohol is a kind of important Organic Chemicals, is widely used, and source is abundant, except obtaining from living beings, coal or natural gas are also the important source material of methanol, and the built many covers of going into operation of China be take the device that natural gas, coal are raw material methanol, and methanol output strengthens year by year.For the design and construction situation of China's methanol project, although various statistics there are differences, consistent conclusion is that the production capacity of methyl alcohol will be considerably beyond actual demand within the following short period.Carry out methanol conversion technology research, for China's methyl alcohol finds an outlet that reality is feasible, for the development tool of methanol industry, be of great significance.
In fact, methyl alcohol can transform the most of basic material that obtains petrochemical process, as triolefin (ethene, propylene, butadiene), triphen (benzene,toluene,xylene), also can obtain the automotive fuels such as gasoline, diesel oil.American UOP company and Norway Norsk Hydro company have developed preparing olefin by conversion of methanol (MTO) technology cooperatively, in the operation process of more than 90 day, methanol conversion approaches 100% all the time, ethene and propylene be selectively respectively 55(mol) % and 27(mol) %, and can flexible modulation ethene and propylene between ratio (Industrial Catalysis, 2001,9(4): 3～8).Germany LURGI has developed preparing propylene from methanol (MTP) technology (patent WO2004/018089), its technological principle is ZSM-5 catalyst series and the fixed bed reactors that utilize modification, propylene one way is selectively 35～40% left and right, heavy constituent Returning reactor, can make propene yield reach 70%.Exxon-Mobil company has developed MTG(methanol conversion gasoline processed) technology and MOGD(methanol conversion petrol and diesel oil processed), wherein the MTG technology Zeng New Zealand of Mobil company exploitation has built the commercial apparatus of producing 570000 tons of gasoline per year, and successfully turns round for 10 years.Domestic Dalian Chemistry and Physics Institute has developed DMTO(preparing olefin by conversion of methanol, comprises ethene and propylene) technology, formed independent intellectual property right (ZL99127143).The technology of methanol conversion for preparing arene (MTA) has been developed in Shanxi coalification, under suitable process conditions, adopts modified molecular sieve catalyst, and in liquid hydrocarbon product, aromatic hydrocarbons total content can reach more than 70% (CN 1880288A).In existing methanol conversion technology, product structure is single, such as preparing propylene from methanol technology, can only obtain propylene, and can not coproduction aromatic hydrocarbons; Methanol aromatic hydrocarbons technology, can only obtain aromatic hydrocarbons, again can not propylene enhancing, and raw material availability is not high.
Zeolite molecular sieve is because of its uniform sequential micropore, large specific surface, the high advantages such as hydrothermal stability, and is widely used in catalytic field.Zeolite powder is because particle size is too small, very inconvenient in actual applications, has the weakness such as difficult recovery, easy inactivation and gathering, therefore need to carry out in advance moulding.In forming process, generally need to add binding agent, binder content generally accounts for 30 ~ 40% of total catalyst weight, even higher, makes catalyst have certain specific shape and certain mechanical strength, and from this point, binding agent is necessary.Yet binding agent is generally inert component, adding in fact also of binding agent has " dilution " effect to the activated centre of molecular sieve, makes real reaction air speed become large, causes catalysqt deactivation to be accelerated.In addition, binding agent has certain plug-hole effect to molecular sieve, and diffusion is had to impact.Binder free zeolite molecular sieve refers in zeolite granular containing inert binder or only contains a small amount of binding agent (binder content is generally less than and equals 5%), there is higher zeolite content, therefore available effective surface area is larger, has better catalytic performance.In addition, binder free zeolite molecular sieve is exactly the binding agent adding in molecular sieve molded process to be changed into the active principle of molecular sieve in fact, has so just kept the high strength of molded molecular sieve.Document US4025576 has reported a kind ofly take methyl alcohol as raw material, and adopting the ZSM-5 molecular sieve of Zn modification is the method that catalyst is prepared gasoline, and it is binding agent that this molecular sieve catalyst adopts aluminium oxide, binder content 35%.Binding agent conversion method is one of method of preparing Adhesive-free Molecular Sieve, patent ZL 94112035.X has reported a kind of preparation method of binder free hydrophobic type silicon zeolite, after ZSM-5 type hydrophobic silicalite powder and silica containing binding agent mixed-forming is dry, in organic amine steam or organic quaternary ammonium base aqueous solution, through the hydrophobic type silicon zeolite that crystallization is processed, roasting makes a kind of binder free.Said method has adopted single template, and does not relate to the shape characteristic of molecular sieve.
We are for the specific reaction of preparing propylene from methanol and aromatic hydrocarbons, adopted the former powder of ZSM-5 molecular sieve with a sizing shape index, and adopt the mixed templates that contains halogenation organic amine and alkyl diamine, containing a ZSM-5 molecular sieve for sizing shape index and the mixture of binding agent, be converted into integrated novel adhesiveless ZSM-5 molecular sieve.Prepared integrated adhesiveless ZSM-5 molecular sieve has more macroporous structure simultaneously, can in actual catalytic reaction, act synergistically with the performance of molecular sieve intracrystalline micropore, for example using micropore as reacting environment, macropore is as the transport channel of reactant molecule, thereby eliminated to a certain extent diffusion restriction, molecular sieve can be used more effectively.
Summary of the invention
One of technical problem to be solved by this invention is the not high problem of poor catalyst stability, propylene and aromatics yield of existing preparing propylene by methanol transformation and aromatic hydrocarbons reaction, and a kind of adhesiveless ZSM-5 molecular sieve catalyst is provided.This catalyst is during for the reaction of preparing propylene by methanol transformation and aromatic hydrocarbons, has that catalyst stability is high, product propylene and a high feature of aromatics yield.
Two of technical problem to be solved by this invention is to provide the preparation method of a kind of preparing propylene by methanol transformation corresponding with one of technical solution problem and arenes catalytic agent.It is low that the method has cost of material, the feature that preparation is simple.
Three of technical problem to be solved by this invention is not high problems of poor catalyst stability, propylene and aromatics yield of existing preparing propylene by methanol transformation and aromatic hydrocarbons reaction, and a kind of method of new preparing propylene by methanol transformation and aromatic hydrocarbons is provided.The method is during for the reaction of preparing propylene by methanol transformation and aromatic hydrocarbons, has that catalyst stability is high, product propylene and a high feature of aromatics yield.
For one of solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of adhesiveless ZSM-5 molecular sieve catalyst, in catalyst weight percentage, comprises following component:
A) ZSM-5 molecular sieve that 90～100% type shape indexes are 3 ~ 100, its medium-sized shape Index Definition is the ratio of longest edge and bond length on molecular sieve crystal three-dimensional;
B) 0～5% phosphorus or its oxide;
C) at least one in 0 ~ 5% rare earth element or its oxide.
In technique scheme, preferred technical scheme is that the type shape index of described ZSM-5 molecular sieve is 5 ~ 80.Preferred technical scheme is that, in catalyst weight percentage, the content of phosphorus or its oxide is 0.01 ~ 3%; The content of rare earth element or its oxide is 0.01 ~ 3%; The content of ZSM-5 molecular sieve is 94 ~ 99.98%.Rare earth element preferred version is at least one being selected from La, Ce, Pr, Nd.Preferred technical scheme is that, in catalyst weight percentage, the content of phosphorus or its oxide is 0.1 ~ 2%; The content of rare earth element or its oxide is 0.1 ~ 2%; The content of ZSM-5 molecular sieve is 96 ~ 99.8%.
For solve the problems of the technologies described above two, the technical solution used in the present invention is as follows: the preparation method of adhesiveless ZSM-5 molecular sieve catalyst, comprises the following steps:
A), in the catalyst weight after shaping and roasting, after the compound of the NaZSM-5 molecular screen primary powder that the type shape index 20 ~ 80% is 3 ~ 100,2 ~ 20% aluminium and 10 ~ 70% silica mixed-forming are dry, obtain preformed catalyst precursor mixture
, mixture wherein
the compound weight content of middle aluminium is less than the weight content of silica;
B) by mixture
be placed in to contain and be selected from least one template steam of ammoniacal liquor, ethylenediamine, triethylamine, n-butylamine, hexamethylene diamine, 4-propyl bromide or TPAOH, 100 ~ 200 ℃ of crystallization, after 20 ~ 200 hours, obtain adhesiveless ZSM-5 molecular sieve catalyst precursor
;
C) catalyst precarsor
at 20～100 ℃, exchange with the ammonium salt aqueous solution of 5～10 % by weight, after washing, being dried, at 400～700 ℃, roasting is 4～8 hours, obtains binder free HZSM-5 molecular sieve catalyst precursor
;
D) the P element of employing 0～5% is to catalyst precarsor
carry out modification, obtain the adhesiveless ZSM-5 molecular sieve catalyst precursor that P modifies
;
E) get containing at least one nitrate solution in 0 ~ 5% La, Ce, Pr, Nd, the catalyst precarsor that step d) is obtained
in above-mentioned metal salt solution, flood 12～48 hours, at 60～100 ℃, in 450～600 ℃ of roastings, obtain required adhesiveless ZSM-5 molecular sieve catalyst after dry.
Wherein, in the catalyst weight after shaping and roasting, the consumption of template is 5 ~ 200%, and the compound of aluminium is selected from least one in the hydroxide of the oxide of aluminium salt, aluminium, the hydrous oxide of aluminium or aluminium.Ammonium salt is selected from least one in ammonium nitrate or ammonium chloride.
In technique scheme, preferred technical scheme is that P derives from least one in phosphoric acid, ammonium dihydrogen phosphate (ADP), trimethyl phosphate; Rare earth element is all selected from its solubility nitrate.The type shape index of ZSM-5 molecular sieve is preferably 5 ~ 20.
Preferred technical scheme is, the preparation method of adhesiveless ZSM-5 molecular sieve catalyst, comprise the following steps: a) in the catalyst weight after shaping and roasting, after the compound of the NaZSM-5 molecular screen primary powder that the type shape index 30 ~ 80% is 3 ~ 20,2 ~ 20% aluminium and 10 ~ 70% silica mixed-forming are dry, obtain preformed catalyst precursor mixture
, mixture wherein
the compound weight content of middle aluminium is less than the weight content of silica; B) by mixture
be placed in to contain and be selected from least one template steam of ammoniacal liquor, ethylenediamine, triethylamine, n-butylamine, hexamethylene diamine, 4-propyl bromide or TPAOH, 130 ~ 190 ℃ of crystallization, after 10 ~ 100 hours, obtain adhesiveless ZSM-5 molecular sieve catalyst precursor
; C) catalyst precarsor
at 70～90 ℃, exchange with the ammonium salt aqueous solution of 5～10 % by weight, after washing, being dried, at 500～600 ℃, roasting is 4～8 hours, obtains binder free HZSM-5 molecular sieve catalyst precursor
; D) the P element of employing 0.1～5% is to catalyst precarsor
carry out modification, obtain the adhesiveless ZSM-5 molecular sieve catalyst precursor that P modifies
; E) get La, Ce, at least one nitrate solution of Pr, Nd containing 0.01 ~ 5%, the catalyst precarsor that step d) is obtained
in above-mentioned metal salt solution, flood 12～48 hours, at 60～100 ℃, in 450～600 ℃ of roastings, obtain required adhesiveless ZSM-5 molecular sieve catalyst after dry.Wherein, in the catalyst weight after shaping and roasting, the consumption of template is 5 ~ 200%, and the compound of aluminium is selected from least one in the hydroxide of the oxide of aluminium salt, aluminium, the hydrous oxide of aluminium or aluminium.Ammonium salt is selected from least one in ammonium nitrate or ammonium chloride.
For solve the problems of the technologies described above three, the technical solution used in the present invention is as follows: a kind of method of preparing propylene from methanol and aromatic hydrocarbons, take methyl alcohol as raw material, in reaction temperature, be 300 ~ 600 ℃, reaction pressure 0.01 ~ 2MPa, methyl alcohol weight space velocity is 0.1 ~ 8h
-1, under the condition that water/methyl alcohol weight ratio is 0 ~ 5, raw material contacts with any one catalyst in claim 1 to 5 by beds, and reaction generates that to take propylene and aromatic hydrocarbons be main product.
In technique scheme, preferred technical scheme is that the reaction of methanol conversion divides two sections to carry out, the aromatization of preparing propylene by methanol transformation reaction and preparing propylene from methanol byproduct of reaction.The operating temperature of preparing propylene from methanol reaction unit is 350～550 ℃, and operating pressure is 0.02～2MPa, and methyl alcohol weight space velocity is 0.2～8h
-1, water/methyl alcohol weight ratio is 0.5 ~ 3; The reaction temperature of preparing propylene from methanol accessory substance aromatization is 450～600 ℃, and the operating pressure of reaction unit is 0.3～1MPa.
Preferably technical scheme is, take methyl alcohol as raw material, in reaction temperature, is 300 ~ 600 ℃, reaction pressure 0.01 ~ 1MPa, and methyl alcohol weight space velocity is 0.1 ~ 6h
-1, under the condition that water/methyl alcohol weight ratio is 0 ~ 3, raw material contacts with catalyst by beds, and reaction generates that to take propylene and aromatic hydrocarbons be main product.The reaction of methanol conversion divides two sections to carry out, the aromatization of preparing propylene by methanol transformation reaction and preparing propylene from methanol byproduct of reaction.Wherein the operating temperature of preparing propylene from methanol reaction unit is 350～500 ℃, and operating pressure is 0.02～0.5MPa, and methyl alcohol weight space velocity is 0.2～6h
-1, water/methyl alcohol weight ratio is 0.5 ~ 4.The reaction temperature of preparing propylene from methanol accessory substance aromatization is 450～600 ℃, and the operating pressure of reaction unit is 0.3～0.8MPa.
The ZSM-5 molecular sieve with a sizing shape index adopts hydro-thermal method synthetic: take tetrapropyl amine bromide or TPAOH as template, aluminum nitrate or aluminum sulfate are aluminium source, waterglass or ethyl orthosilicate are silicon source, first raw material is fully hydrolyzed, then transfers in stainless steel autoclave, under suitable salinity and basicity, hydrothermal condition, control the direction of growth of molecular sieve crystal, 80～200 ℃ of crystallization 30～100 hours, the raw material proportioning by different, can obtain silica alumina ratio (SiO
2/ Al
2o
3) be 50～800, ZSM-5 molecular sieve that type shape index is 5 ~ 80.The mensuration of type shape index adopts ESEM or transmission electron microscope.
At present, in the reaction of preparing propylene by methanol transformation and aromatic hydrocarbons, have that catalyst stability is not high, propylene and aromatics yield problem on the low side, this is mainly because ZSM-5 molecular sieve grain morphology used is single and contain a large amount of binding agents, diffusion is poor, when reaction intermediates or product molecule pass through, easily produce and be detained therein, the reactant molecule that makes to enter in duct is difficult for diffusing out and causes unwanted degree of depth side reaction, assemble gradually coking, stop up molecular sieve pore passage, thereby catalyst activity is reduced greatly, finally cause catalysqt deactivation.We adopt the adhesiveless ZSM-5 molecular sieve catalyst with a sizing shape index to solve this problem, and product is diffusion rapidly in molecular sieve pore passage, and large molecular product coking degree obviously reduces, and catalyst stability obviously improves.
The catalyst of preparing propylene by methanol transformation of the present invention and aromatic hydrocarbons has effectively overcome the low shortcoming of poor catalyst stability, propylene and aromatics yield in prior art, by optimizing reaction condition, the yield of propylene and aromatic hydrocarbons can reach more than 32% simultaneously, catalyst stability surpasses 350 hours, has obtained good technique effect.
Below by embodiment, the present invention is further elaborated.
The specific embodiment
[embodiment 1]
Take tetrapropyl amine bromide as template, and aluminum nitrate is aluminium source, and Ludox is silicon source, first by raw material SiO in molar ratio
2/ Al
2o
3=200; OH
-/ SiO
2=0.3; R/SiO
2=0.5; H
2o/SiO
2=40 ratio is mixed, and under room temperature, hydrolysis completely, packs stainless steel cauldron into, under hydrothermal condition, controls the direction of growth of molecular sieve crystal, and 100 ℃ of crystallization 60 hours, obtain silica alumina ratio SiO
2/ Al
2o
3the NaZSM-5 molecular sieve that be 200, type shape index is 50.
Take 70 grams of above-mentioned silica alumina ratio SiO
2/ Al
2o
3the NaZSM-5 molecular sieve, 5 grams of white carbons, the 6.5 grams of aluminium oxide that be 200, type shape index are 50, add the Ludox (SiO of 62.5 grams
2quality percentage composition is 40%) carry out kneading and compacting, preformed catalyst dries 3 hours at 100 ℃.In reactor, add in advance the triethylamine of 15 grams, 10 grams of ethylenediamines and 10 grams of distilled water, the cylindric product of 60 grams of above-mentioned preparations is placed in and at 120 ℃, carries out gas-solid after the online side sealing of reactor porous stainless steel and process mutually 3 days.
Product washs with distilled water after taking out, after drying in air atmosphere in 550 ℃ of roastings, in 80 ℃ of 5% ammonium nitrate solution, exchange three times, after oven dry, roasting 8 hours in 550 ℃ of Muffle furnaces, obtains the adhesiveless ZSM-5 molecular sieve catalyst that type shape index is 50 again.
[embodiment 2]
Take tetrapropyl oxyammonia as template, and aluminum sulfate is aluminium source, and waterglass is silicon source, and raw material is SiO in molar ratio
2/ Al
2o
3=500; OH
-/ SiO
2=0.05; R/SiO
2=1.5; H
2o/SiO
2=10 ratio is mixed, and adopts method described in embodiment 1, and 80 ℃ of crystallization 100 hours, obtain silica alumina ratio SiO
2/ Al
2o
3the NaZSM-5 molecular sieve that be 500, type shape index is 3.
Take 50 grams of above-mentioned silica alumina ratio SiO
2/ Al
2o
3the NaZSM-5 molecular sieve that be 50, type shape index is 3,2.8 grams of sodium metaaluminates, add 90 grams of Ludox (SiO
2quality percentage composition is 40%) carry out kneading and compacting, preformed catalyst dries 3 hours at 100 ℃.The triethylamine and the 10 grams of distilled water that in reactor, add in advance 50 grams, be placed in the cylindric product of 60 grams of above-mentioned preparations at 180 ℃, to carry out gas-solid after the online side sealing of reactor porous stainless steel and process mutually 5 days.
After product takes out with distilled water washing, after drying in air atmosphere in 550 ℃ of roastings, then exchange three times in 90 ℃ of 5% ammonium chloride solution, after oven dry, roasting 4 hours in 600 ℃ of Muffle furnaces, obtains the adhesiveless ZSM-5 molecular sieve catalyst that type shape index is 3.
Get 10 grams of phosphoric acid solutions containing P 0.5%, the above-mentioned 10 grams of Adhesive-free Molecular Sieve catalyst of incipient impregnation 24 hours are dried in 80 ℃ of baking ovens, and 500 ℃ of roastings 4 hours, obtain the adhesiveless ZSM-5 molecular sieve catalyst that required 0.5%P modifies.
[embodiment 3]
Take tetrapropyl oxyammonia and ammoniacal liquor as template, and sodium aluminate is aluminium source, and Ludox is silicon source, and raw material is SiO in molar ratio
2/ Al
2o
3=300; OH
-/ SiO
2=0.08; R/SiO
2=0.5; H
2o/SiO
2=20 ratio is mixed, and adopts method described in embodiment 1, and 180 ℃ of crystallization 40 hours, obtain silica alumina ratio SiO
2/ Al
2o
3the NaZSM-5 molecular sieve that be 300, type shape index is 60.
Take 10 grams of above-mentioned SiO
2/ Al
2o
3the NaZSM-5 molecular sieve, 120 grams of white carbons, the 4.2 grams of aluminum sulfate that be 300, type shape index are 60, add the Ludox (SiO of 175 grams
2quality percentage composition is 40%) carry out kneading and compacting, preformed catalyst dries 3 hours at 100 ℃.The mixture that adds in advance 30 grams of ethamine and 3 grams of distilled water in reactor, is placed in the cylindric product of 20 grams of above-mentioned preparations at 100 ℃, to carry out respectively gas-solid after the online side sealing of reactor porous stainless steel and process mutually 8 days.
After product takes out with distilled water washing, after drying in air atmosphere in 550 ℃ of roastings.In 90 ℃ of 5% ammonium nitrate solution, exchange three times, after oven dry, roasting 4 hours in 500 ℃ of Muffle furnaces, obtains the adhesiveless ZSM-5 molecular sieve catalyst that type shape index is 60 again.
Get 10 grams of ammonium dihydrogen phosphates containing P 1%, the above-mentioned 10 grams of Adhesive-free Molecular Sieve catalyst of incipient impregnation 24 hours are dried in 80 ℃ of baking ovens, and 500 ℃ of roastings 4 hours, obtain the adhesiveless ZSM-5 molecular sieve catalyst that required 1%P modifies.
[embodiment 4]
Take etamon chloride and ammoniacal liquor as template, and aluminum phosphate is aluminium source, and waterglass is silicon source, and raw material is SiO in molar ratio
2/ Al
2o
3=600; OH
-/ SiO
2=1.0; R/SiO
2=0.06; H
2o/SiO
2=50 ratio is mixed, and adopts method described in embodiment 1, and 200 ℃ of crystallization 30 hours, obtain silica alumina ratio SiO
2/ Al
2o
3the NaZSM-5 molecular sieve that be 600, type shape index is 80.
Take 30 grams of above-mentioned silica alumina ratio SiO
2/ Al
2o
3the NaZSM-5 molecular sieve that be 600, type shape index is 80,4.2 grams of aluminum nitrates, add 60 grams of Ludox (SiO
2quality percentage composition is 40%) carry out kneading and compacting, preformed catalyst dries 3 hours at 100 ℃.In reactor, add in advance the hexamethylene diamine of 15 grams and the mixture of 10 grams of distilled water, the cylindric product of 10 grams of above-mentioned preparations is placed in and at 150 ℃, carries out gas-solid after the online side sealing of reactor porous stainless steel and process mutually 5 days.
After product takes out with distilled water washing, after drying in air atmosphere in 550 ℃ of roastings.In 80 ℃ of 10% ammonium nitrate solution, exchange three times, after oven dry, roasting 4 hours in 550 ℃ of Muffle furnaces, obtains the adhesiveless ZSM-5 molecular sieve catalyst that type shape index is 80 again.
Get 10 grams of tripotassium phosphate ester solutions containing P 5%, the above-mentioned 10 grams of Adhesive-free Molecular Sieve catalyst of incipient impregnation 24 hours are dried in 80 ℃ of baking ovens, and 500 ℃ of roastings 4 hours, obtain the adhesiveless ZSM-5 molecular sieve catalyst that required 5% P modifies.
[embodiment 5]
Take etamon chloride as template, and sodium aluminate is aluminium source, and ethyl orthosilicate is silicon source, and raw material is SiO in molar ratio
2/ Al
2o
3=800; OH
-/ SiO
2=1.5; R/SiO
2=0.02; H
2o/SiO
2=30 ratio is mixed, and adopts method described in embodiment 1, and 120 ℃ of crystallization 50 hours, obtain silica alumina ratio SiO
2/ Al
2o
3the NaZSM-5 molecular sieve that be 800, type shape index is 10.
Take 50 grams of above-mentioned SiO
2/ Al
2o
3the NaZSM-5 molecular sieve, 15 grams of white carbons, the 6.5 grams of aluminium oxide that be 800, type shape index are 10, add the Ludox (SiO of 62.5 grams
2quality percentage composition is 40%) carry out kneading and compacting, preformed catalyst dries 3 hours at 100 ℃.The mixture that adds in advance 5 grams of n-propylamines and 50 grams of distilled water in reactor, is placed in the cylindric product of 20 grams of above-mentioned preparations at 170 ℃, to carry out respectively gas-solid after the online side sealing of reactor porous stainless steel and process mutually 3 days.
After product takes out with distilled water washing, after drying in air atmosphere in 550 ℃ of roastings.In 80 ℃ of 10% ammonium nitrate solution, exchange three times, after oven dry, roasting 4 hours in 550 ℃ of Muffle furnaces, obtains the adhesiveless ZSM-5 molecular sieve catalyst that type shape index is 80 again.
Get 10 grams of phosphoric acid solutions containing P 2%, the above-mentioned 10 grams of Adhesive-free Molecular Sieve catalyst of incipient impregnation 24 hours are dried in 80 ℃ of baking ovens, and 500 ℃ of roastings 4 hours, obtain the adhesiveless ZSM-5 molecular sieve catalyst that required 2%P modifies.
[embodiment 6]
Take tetrapropyl amine bromide as template, and aluminum nitrate is aluminium source, and Ludox is silicon source, first by raw material SiO in molar ratio
2/ Al
2o
3=200; OH
-/ SiO
2=0.3; R/SiO
2=0.5; H
2o/SiO
2=40 ratio is mixed, and under room temperature, hydrolysis completely, packs stainless steel cauldron into, under hydrothermal condition, controls the direction of growth of molecular sieve crystal, and 100 ℃ of crystallization 60 hours, obtain silica alumina ratio SiO
2/ Al
2o
3the NaZSM-5 molecular sieve that be 200, type shape index is 100.
Take 70 grams of above-mentioned silica alumina ratio SiO
2/ Al
2o
3the NaZSM-5 molecular sieve, 5 grams of white carbons, the 6.5 grams of aluminium oxide that be 200, type shape index are 100, add the Ludox (SiO of 62.5 grams
2quality percentage composition is 40%) carry out kneading and compacting, preformed catalyst dries 3 hours at 100 ℃.In reactor, add in advance the triethylamine of 15 grams, 10 grams of ethylenediamines and 10 grams of distilled water, the cylindric product of 60 grams of above-mentioned preparations is placed in and at 120 ℃, carries out gas-solid after the online side sealing of reactor porous stainless steel and process mutually 3 days.
Product washs with distilled water after taking out, after drying in air atmosphere in 550 ℃ of roastings, in 80 ℃ of 5% ammonium nitrate solution, exchange three times, after oven dry, roasting 8 hours in 550 ℃ of Muffle furnaces, obtains the adhesiveless ZSM-5 molecular sieve catalyst that type shape index is 100 again.
Get 10 grams of ammonium dihydrogen phosphates containing P 1.5 %, the above-mentioned 10 grams of Adhesive-free Molecular Sieve catalyst of incipient impregnation 24 hours are dried in 80 ℃ of baking ovens, and 500 ℃ of roastings 4 hours, obtain the adhesiveless ZSM-5 molecular sieve catalyst that required 1.5%P modifies.
[embodiment 7]
Take ammoniacal liquor as template, and aluminum nitrate is aluminium source, and ethyl orthosilicate is silicon source, and raw material is SiO in molar ratio
2/ Al
2o
3=500; OH
-/ SiO
2=0.6; R/SiO
2=1.2; H
2o/SiO
2=30 ratio is mixed, and adopts method described in embodiment 1, and 150 ℃ of crystallization 40 hours, obtain silica alumina ratio SiO
2/ Al
2o
3the NaZSM-5 molecular sieve that be 500, type shape index is 30.
Take 50 grams of above-mentioned silica alumina ratio SiO
2/ Al
2o
3the NaZSM-5 molecular sieve that be 500, type shape index is 30,2.8 grams of sodium metaaluminates, add 90 grams of Ludox (SiO
2quality percentage composition is 40%) carry out kneading and compacting, preformed catalyst dries 3 hours at 100 ℃.The triethylamine and the 10 grams of distilled water that in reactor, add in advance 50 grams, be placed in the cylindric product of 60 grams of above-mentioned preparations at 180 ℃, to carry out gas-solid after the online side sealing of reactor porous stainless steel and process mutually 5 days.
Product washs with distilled water after taking out, after drying in air atmosphere in 550 ℃ of roastings, in 90 ℃ of 5% ammonium chloride solution, exchange three times, after oven dry, roasting 4 hours in 600 ℃ of Muffle furnaces, obtains the adhesiveless ZSM-5 molecular sieve catalyst that type shape index is 30 again.
Get 10 grams of phosphoric acid solutions containing P 3%, the above-mentioned 10 grams of Adhesive-free Molecular Sieve catalyst of incipient impregnation 24 hours are dried in 80 ℃ of baking ovens, and 500 ℃ of roastings 4 hours, obtain the adhesiveless ZSM-5 molecular sieve catalyst that required 3%P modifies.
[embodiment 8]
Adopt fixed-bed catalytic reactor, reactor is stainless steel tube, catalyst prepared by [embodiment 7] has carried out preparing propylene by methanol transformation and the evaluation of aromatic hydrocarbons reactivity, investigating process conditions used is: preparing propylene from methanol reaction unit and aromatisation device respectively fill 1 gram of catalyst, the operating temperature of preparing propylene from methanol reaction unit is 380 ℃, operating pressure is 0.05MPa, and methyl alcohol weight space velocity is 0.2h
-1, water/methyl alcohol weight ratio is 0.5.The operating temperature of aromatization device is 450 ℃, and operating pressure is 0.5MPa.Appraisal result is as shown in table 1, and propylene and aromatic hydrocarbons obtain higher yield simultaneously.
Table 1
[embodiment 9]
Catalyst prepared by [embodiment 7] adopts the cerous nitrate solution incipient impregnation 24 hours that Ce weight percentage is 1%, and 80 ~ 100 ℃ of oven dry, then roasting 3 ~ 6 hours in 500 ~ 550 ℃ of Muffle furnaces, obtain the catalyst that 1%Ce modifies.
Adopt the condition of [embodiment 8] to carry out preparing propylene by methanol transformation and the evaluation of aromatic hydrocarbons reactivity to above-mentioned catalyst.Appraisal result is listed in table 1.
[comparative example 1]
Take 40 grams of silica alumina ratio (SiO
2/ Al
2o
3) be 500, NaZSM-5 molecular sieve, 2.8 grams of sodium metaaluminates that type shape index is 1, add 90 grams of Ludox (SiO
2quality percentage composition is 40%) carry out kneading and compacting, preformed catalyst dries 3 hours at 100 ℃.The triethylamine and the 10 grams of distilled water that in reactor, add in advance 50 grams, be placed in the cylindric product of 60 grams of above-mentioned preparations at 180 ℃, to carry out gas-solid after the online side sealing of reactor porous stainless steel and process mutually 5 days.After product takes out with distilled water washing, after drying in air atmosphere in 550 ℃ of roastings, then exchange three times in 90 ℃ of 5% ammonium chloride solution, after oven dry, roasting 4 hours in 600 ℃ of Muffle furnaces, obtains the adhesiveless ZSM-5 molecular sieve catalyst that type shape index is 1.
Adopt the condition of [embodiment 8] to carry out preparing propylene by methanol transformation and the evaluation of aromatic hydrocarbons reactivity to above-mentioned catalyst.Appraisal result is listed in table 1.
[embodiment 10～13]
According to [embodiment 8] process conditions used, the catalyst of embodiment 1 preparation is carried out to preparing propylene by methanol transformation and the evaluation of aromatic hydrocarbons reactivity, just change the operating temperature of preparing propylene from methanol reaction, appraisal result is listed in table 2.
Table 2
[embodiment 14～17]
According to [embodiment 8] process conditions used, the catalyst of embodiment 2 preparations is carried out to preparing propylene by methanol transformation and the evaluation of aromatic hydrocarbons reactivity, just change the operating pressure of preparing propylene from methanol reaction, appraisal result is listed in table 3.
Table 3
[embodiment 18～21]
According to [embodiment 8] process conditions used, the catalyst of embodiment 3 preparations is carried out to preparing propylene by methanol transformation and the evaluation of aromatic hydrocarbons reactivity, just change the weight space velocity of methyl alcohol in preparing propylene from methanol reaction, appraisal result is listed in table 4.
Table 4
[embodiment 22～25]
According to [embodiment 8] process conditions used, the catalyst of embodiment 5 preparations is carried out to preparing propylene by methanol transformation and the evaluation of aromatic hydrocarbons reactivity, just change water/methyl alcohol weight ratio, appraisal result is listed in table 5.
Table 5
[embodiment 26]
According to [embodiment 8] process conditions used, respectively the catalyst of embodiment 7 and comparative example 1 preparation has been carried out to activity stability investigation, table 6 has been listed methanol conversion data on each catalyst of differential responses time.
Table 6
Claims (10)
1. an adhesiveless ZSM-5 molecular sieve catalyst, in catalyst weight percentage, comprises following component:
A) ZSM-5 molecular sieve that 90～100% type shape indexes are 3 ~ 100, its medium-sized shape Index Definition is the ratio of longest edge and bond length on molecular sieve crystal three-dimensional;
B) 0～5% phosphorus or its oxide;
C) at least one in 0 ~ 5% rare earth element or its oxide.
2. adhesiveless ZSM-5 molecular sieve catalyst according to claim 1, is characterized in that the type shape index of ZSM-5 molecular sieve is 5 ~ 80.
3. adhesiveless ZSM-5 molecular sieve catalyst according to claim 1, is characterized in that in catalyst weight percentage, and the content of phosphorus or its oxide is 0.01 ~ 3%; The content of rare earth element or its oxide is 0.01 ~ 3%; The content of ZSM-5 molecular sieve is 94 ~ 99.98%.
4. adhesiveless ZSM-5 molecular sieve catalyst according to claim 1, is characterized in that rare earth element is selected from least one in La, Ce, Pr, Nd.
5. adhesiveless ZSM-5 molecular sieve catalyst according to claim 1, is characterized in that in catalyst weight percentage, and the content of phosphorus or its oxide is 0.1 ~ 2%; The content of rare earth element or its oxide is 0.1 ~ 2%; The content of ZSM-5 molecular sieve is 96 ~ 99.8%.
6. the preparation method of adhesiveless ZSM-5 molecular sieve catalyst claimed in claim 1, comprises the following steps:
A), in the catalyst weight after shaping and roasting, after the compound of the NaZSM-5 molecular screen primary powder that the type shape index 20 ~ 80% is 3 ~ 100,2 ~ 20% aluminium and 10 ~ 70% silica mixed-forming are dry, obtain preformed catalyst precursor mixture
, mixture wherein
the compound weight content of middle aluminium is less than the weight content of silica;
B) by mixture
be placed in to contain and be selected from least one template steam of ammoniacal liquor, ethylenediamine, triethylamine, n-butylamine, hexamethylene diamine, 4-propyl bromide or TPAOH, 100 ~ 200 ℃ of crystallization, after 20 ~ 200 hours, obtain adhesiveless ZSM-5 molecular sieve catalyst precursor
;
C) catalyst precarsor
at 20～100 ℃, exchange with the ammonium salt aqueous solution of 5～10 % by weight, after washing, being dried, at 400～700 ℃, roasting is 4～8 hours, obtains binder free HZSM-5 molecular sieve catalyst precursor
;
D) the P element of employing 0～5% is to catalyst precarsor
carry out modification, obtain the adhesiveless ZSM-5 molecular sieve catalyst precursor that P modifies
;
E) get containing at least one nitrate solution in 0 ~ 5% La, Ce, Pr, Nd, the catalyst precarsor that step d) is obtained
in above-mentioned metal salt solution, flood 12～48 hours, at 60～100 ℃, in 450～600 ℃ of roastings, obtain required adhesiveless ZSM-5 molecular sieve catalyst after dry;
Wherein, in the catalyst weight after shaping and roasting, the consumption of template is 5 ~ 200%, and the compound of aluminium is selected from least one in the hydroxide of the oxide of aluminium salt, aluminium, the hydrous oxide of aluminium or aluminium; Ammonium salt is selected from least one in ammonium nitrate or ammonium chloride.
7. the preparation method of adhesiveless ZSM-5 molecular sieve catalyst according to claim 6, is characterized in that P derives from least one in phosphoric acid, ammonium dihydrogen phosphate (ADP), trimethyl phosphate; Rare earth element is all selected from its solubility nitrate.
8. a method for preparing propylene from methanol and aromatic hydrocarbons, take methyl alcohol as raw material, in reaction temperature, is 300 ~ 600 ℃, reaction pressure 0.01 ~ 2MPa, and methyl alcohol weight space velocity is 0.1 ~ 8h
-1, under the condition that water/methyl alcohol weight ratio is 0 ~ 5, raw material contacts with any one catalyst in claim 1 to 5 by beds, and reaction generates that to take propylene and aromatic hydrocarbons be main product.
9. the method for preparing propylene from methanol according to claim 8 and aromatic hydrocarbons, is characterized in that the reaction of methanol conversion divides two sections to carry out, the aromatization of preparing propylene by methanol transformation reaction and preparing propylene from methanol byproduct of reaction, two reactor cascade reaction.
10. the method for preparing propylene from methanol according to claim 9 and aromatic hydrocarbons, the operating temperature that it is characterized in that preparing propylene from methanol reaction unit is 350～550 ℃, and operating pressure is 0.02～2MPa, and methyl alcohol weight space velocity is 0.2～8h
-1, water/methyl alcohol weight ratio is 0.5 ~ 3; The reaction temperature of preparing propylene from methanol accessory substance aromatization is 450～600 ℃, and the operating pressure of reaction unit is 0.3～1MPa.
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| CN111111752A (en) * | 2018-10-30 | 2020-05-08 | 中国石油化工股份有限公司 | Binder-free monolithic catalyst, preparation method and application thereof |
| CN114713278A (en) * | 2022-03-30 | 2022-07-08 | 中触媒新材料股份有限公司 | Preparation method of full-crystalline ZSM-35 molecular sieve and application thereof in olefin isomerization reaction |
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| CN101954291A (en) * | 2010-09-26 | 2011-01-26 | 华中科技大学 | Zinc isomorphism-substituted nano molecular sieve catalyst and preparation method and application thereof |
| CN102372571A (en) * | 2010-08-23 | 2012-03-14 | 中国石油化工股份有限公司 | Method for producing propylene by oxygen-containing compound conversion |
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| CN101885659A (en) * | 2009-05-13 | 2010-11-17 | 中国石油化工股份有限公司 | Method for producing propylene with methanol or dimethyl ether |
| CN102372571A (en) * | 2010-08-23 | 2012-03-14 | 中国石油化工股份有限公司 | Method for producing propylene by oxygen-containing compound conversion |
| CN101954291A (en) * | 2010-09-26 | 2011-01-26 | 华中科技大学 | Zinc isomorphism-substituted nano molecular sieve catalyst and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107185596A (en) * | 2016-03-14 | 2017-09-22 | 中国科学院大连化学物理研究所 | A kind of method for improving Adhesive-free Molecular Sieve catalytic mechanical intensity |
| CN107185596B (en) * | 2016-03-14 | 2021-06-04 | 中国科学院大连化学物理研究所 | Method for improving mechanical strength of binder-free molecular sieve catalyst |
| CN111111752A (en) * | 2018-10-30 | 2020-05-08 | 中国石油化工股份有限公司 | Binder-free monolithic catalyst, preparation method and application thereof |
| CN111111752B (en) * | 2018-10-30 | 2022-09-06 | 中国石油化工股份有限公司 | Binder-free monolithic catalyst, preparation method and application thereof |
| CN114713278A (en) * | 2022-03-30 | 2022-07-08 | 中触媒新材料股份有限公司 | Preparation method of full-crystalline ZSM-35 molecular sieve and application thereof in olefin isomerization reaction |
| CN114713278B (en) * | 2022-03-30 | 2023-10-27 | 中触媒新材料股份有限公司 | Preparation method of full-crystallization ZSM-35 molecular sieve and application of full-crystallization ZSM-35 molecular sieve in olefin isomerization reaction |
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