CN104549436B - A kind of molecular sieve catalysts of Hydrogen ZSM 5 and its preparation method and application - Google Patents
A kind of molecular sieve catalysts of Hydrogen ZSM 5 and its preparation method and application Download PDFInfo
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- CN104549436B CN104549436B CN201310476139.9A CN201310476139A CN104549436B CN 104549436 B CN104549436 B CN 104549436B CN 201310476139 A CN201310476139 A CN 201310476139A CN 104549436 B CN104549436 B CN 104549436B
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Abstract
The invention discloses a kind of molecular sieve catalysts of Hydrogen ZSM 5, wherein, in the molecular sieve catalyst, the silica alumina ratio of the molecular sieves of Hydrogen ZSM 5 is 50 400 to the molecular sieve catalyst：1, particle diameter is 100 500nm, and specific surface area is 160 350m2/g；NH3TPD characterized by techniques has feature adsorption peak at 170 200 DEG C.Additionally provide a kind of application of the preparation method and the catalyst of catalyst in isopropanol dehydration propylene.It just can be effectively propylene by iso-propanol conversion within the scope of relatively low temperature to use catalyst of the invention, improve the conversion ratio of isopropanol and the selectivity of propylene.
Description
Technical field
The present invention relates to a kind of Hydrogen ZSM-5 molecular sieve catalyst, the preparation method of the catalyst, and the catalyst exists
Isopropanol dehydration prepares the application in propylene.
Background technology
Propylene is important basic organic.There are preparing ethylene by steam cracking propylene simultaneously, refining in the source of propylene in the world
The technique such as factory catalytic cracking unit dry gas, dehydrogenating propane and methanol-to-olefins and the alkene conversion that develops in recent years.In recent years,
Propylene Downstream Products are rapid, and the demand of propylene increasingly increases.Therefore, improve the utilization level of propylene, develop new third
Alkene production technology and technology turn into the focus of people's research.
Acetone is a kind of important derivatives of propylene.In phynol/acetone production industry, benzene and production of propylene isopropylbenzene,
Oxidized process prepares phenol, cogeneration of propanone again.In recent years, with the progress and development of phenol industrial technology, cogeneration of propanone
Total amount increases sharply, and the superfluous situation of acetone have occurred in some areas.Therefore, acetone is comprehensively utilized, exploitation acetone hydrogenation system is different
Propyl alcohol, isopropanol is possibly realized through the technique and technology of dehydration propylene, and can be according to market to propylene and isopropanol
Demand adjusts production technology.
The report of relevant isopropanol dehydration propylene technology is less, and studied catalyst mainly includes aluminum oxide, miscellaneous many
Acid and molecular sieve etc..WO0361755B1 discloses a kind of phenol preparation method and propylene reuse technology.With γ-oxygen in the technology
Change aluminium is catalyst, can be propylene, but iso-propanol conversion rate and third by iso-propanol conversion under 1MPa pressure conditions at 320 DEG C
Alkene selectivity is relatively low.Fu Xiang is clear etc.（Guyuan Journal of Teachers College, 2001,22 (6), 19-22）It was found that MCM-41 is carried heteropoly acid
Best carrier, but the prepared catalyst catalysis activity in isopropanol dehydration reaction is relatively low.Zhang Hanpeng etc. have studied in work
Property carbon on load the heteropoly acids such as phosphorus tungsten, silicon tungsten, phosphorus molybdenum, and for isopropanol dehydration reaction, but same iso-propanol conversion rate and third
Alkene selectivity is relatively low.Liu Chunyan etc.（The synthesis of solid-carrying heteropolyacid, the activity for characterizing and being catalyzed isopropanol dehydration reaction, industry
Catalysis, 2011,19（5）, 40-44）Research to acidic catalyst catalysis isopropanol dehydration propylene finds that SAPO-34 is necessary
There is stronger iso-propanol conversion activity at a higher temperature, Propylene Selectivity higher, ZSM-5 molecular sieve is modified through Zn,
The preparation of propylene can be carried out under 280 DEG C of cryogenic conditions, iso-propanol conversion rate 98.8%, Propylene Selectivity is 93.5%, but still
Need further raising.
Therefore, need badly exploitation it is a kind of can at a lower temperature, high conversion and high selectivity turn isopropanol
Turn to the catalyst of propylene.
The content of the invention
The invention aims to overcome existing isopropanol dehydration to prepare propylene method in, required reaction temperature is high,
Or iso-propanol conversion rate and the low defect of Propylene Selectivity, there is provided it is a kind of that there is iso-propanol conversion higher at a lower temperature
The catalyst of rate and Propylene Selectivity, and the catalyst preparation method.
To achieve these goals, on the one hand, the invention provides a kind of Hydrogen ZSM-5 molecular sieve catalyst, wherein,
In the molecular sieve catalyst, the silica alumina ratio of the Hydrogen ZSM-5 molecular sieve is 50-400, and particle diameter is 100-500nm, specific surface area
It is 160-350m2/g；NH3- TPD characterized by techniques has feature adsorption peak at 170-200 DEG C.
On the other hand, the invention provides a kind of method for preparing Hydrogen ZSM-5 molecular sieve catalyst, the method includes：
（1）Template is well mixed with inorganic base in water and obtains solution A；
（2）Silicon source is well mixed with alcoholic solvent and obtains solution B；
（3）Organic silicon source is well mixed with solution A and obtains gel C；
（4）Gel C is well mixed with solution B and obtains gel D；
（5）The gel D is carried out into separation of solid and liquid, drying and roasting successively after crystallization under crystallization condition, ZSM-5 is obtained
Molecular sieve；
（6）ZSM-5 molecular sieve and inorganic acid and/or solution containing ammonium ion are carried out into ion exchange, and ion is handed over
Material after changing carries out separation of solid and liquid, drying and roasting successively.
Another further aspect, present invention also offers a kind of method that isopropanol dehydration prepares propylene, the method includes：Continuous
On fixed bed reactors, with isopropanol as raw material, diluent is added or is added without, reaction in the presence of a catalyst prepares third
Alkene, wherein, the catalyst is ZSM-5 molecular sieve catalyst as above or is urged by ZSM-5 molecular sieve prepared by method as above
Agent.
The method of the present invention, using Hydrogen ZSM-5 molecular sieve as isopropanol dehydration propylene catalyst, and by its silicon
Aluminum ratio, particle diameter, specific surface area and NH3The temperature control of the characteristic absorption peak of-TPD within the scope of the invention, can be effective
Ground solves existing isopropanol dehydration catalyst higher to the temperature requirement of catalytic reaction or conversion ratio of isopropanol and third
The relatively low defect of the selectivity of alkene.Be can be seen that by the test case of the application and urged using the Hydrogen ZSM-5 molecular sieve of the application
Agent can be reacted at a lower temperature as the catalyst of isopropanol dehydration propylene, and the conversion ratio of isopropanol is big
In 99%, the selectivity of propylene is more than 96%.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Brief description of the drawings
Accompanying drawing is, for providing a further understanding of the present invention, and to constitute the part of specification, with following tool
Body implementation method is used to explain the present invention together, but is not construed as limiting the invention.In the accompanying drawings：
Fig. 1：The XRD spectra of Hydrogen ZSM-5 molecular sieve E1 prepared by embodiment 1；
Fig. 2：The SEM spectrograms of Hydrogen ZSM-5 molecular sieve E1 prepared by embodiment 1；
Fig. 3：The SEM spectrograms of Hydrogen ZSM-5 molecular sieve E2 prepared by embodiment 2；
Fig. 4：The SEM spectrograms of Hydrogen ZSM-5 molecular sieve E3 prepared by embodiment 3.
Specific embodiment
Specific embodiment of the invention is described in detail below.It should be appreciated that described herein specific
Implementation method is merely to illustrate and explain the present invention, and is not intended to limit the invention.
On the one hand, the invention provides a kind of Hydrogen ZSM-5 molecular sieve catalyst, wherein, in the molecular sieve catalyst,
The silica alumina ratio of the Hydrogen ZSM-5 molecular sieve is 50-400：1, particle diameter is 100-500nm, and specific surface area is 160-350m2/g；
NH3- TPD characterized by techniques has feature adsorption peak at 170-200 DEG C.
In the present invention, term " particle diameter " is referred in molecular sieve crystal（010）The size of crystal face, those skilled in the art
To this it is equal can know, will not be repeated here.
In the present invention, term " silica alumina ratio " has implication well known in the art, refers to SiO2And Al2O3Mol ratio.
NH3-TPD（Temperature programmed desorption technology）It is more classical and convenience, practical sign molecular sieve surface acidity
Method.It is as well known to those skilled in the art, according to NH3The temperature of the characteristic absorption peak that-TPD technologies are obtained may determine that ZSM-5 points
The acidity on son sieve surface, for example, show that ZSM-5 molecular sieve surface is in faintly acid in 100-200 DEG C of existing characteristics absworption peak,
200-400 DEG C of existing characteristics absworption peak shows ZSM-5 molecular sieve surface in middle strong acidity, and the feature occurred later at 400 DEG C is inhaled
Receive peak and then show that ZSM-5 molecular sieve is in highly acid.The Hydrogen ZSM-5 molecular sieve catalyst that the present invention is provided, through NH3- TPD technologies
Being characterized in 170-200 DEG C has feature adsorption peak, illustrates the Hydrogen ZSM-5 molecular sieve catalyst surface of present invention offer and has weak acid
Property.
Although it should be pointed out that using NH herein3The acidity of-TPD characterized by techniques molecular sieve surfaces, but be not understood that
For the technology can limit the scope of the present invention, those skilled in the art can also can be used for ZSM-5 points of sign using conventional
The technology of son sieve surface acidity, for example, indicator method, spectroscopic methodology, calorimetry etc..
Under normal circumstances, the most typical feature of ZSM-5 molecular sieve is exactly that surface has stronger acidity.But hair of the invention
A person of good sense has been found that, when the surface of ZSM-5 molecular sieve is in faintly acid, and by the control of its silica alumina ratio in scope higher（50-
400：1, preferably 100-300：1, more preferably 150-250：1）, size controlling is in less scope（100-500nm, preferably
It is 150-450, more preferably 200-300）, specific surface area control is in 160-350m2/ g, preferably 250-340m2/ g, more preferably
It is 280-340m2/ g, and through over hydrogenation after, can at a lower temperature be catalyzed isopropanol dehydration propylene, and effectively
Improve the conversion ratio of isopropanol and the selectivity of propylene.
On the other hand, the invention provides a kind of method for preparing Hydrogen ZSM-5 molecular sieve catalyst, the method includes：
（1）Template is well mixed with inorganic base in water and obtains solution A；
（2）Silicon source is well mixed with alcoholic solvent and obtains solution B；
（3）Organic silicon source is well mixed with solution A and obtains gel C；
（4）Gel C is well mixed with solution B and obtains gel D；
（5）The gel D is carried out into separation of solid and liquid, drying and roasting successively after crystallization under crystallization condition, ZSM-5 is obtained
Molecular sieve；
（6）ZSM-5 molecular sieve and inorganic acid and/or solution containing ammonium ion are carried out into ion exchange, and ion is handed over
Material after changing carries out separation of solid and liquid, drying and roasting successively.
According to the present invention, step（1）In, the consumption of consumption and inorganic base to the template without particular/special requirement, only
The solution of stabilization can be formed, under preferable case, the template is 1-20 with the mass ratio of inorganic base:1, preferably
4.5-16:1；The consumption of inorganic base can ensure that the pH value of gel D in crystallization process is 9-12.The present invention is to the consumption of water without spy
It is different to require, it is preferable that the template is 0.01-0.3 with the mass ratio of water:1, preferably 0.04-0.2:1.
According to the present invention, the template can be added in solid form, it is also possible to be added as a solution, the above
The amount of described template, when adding in solid form, refers to the consumption of template solid, when as a solution plus
It is fashionable, refer to the consumption of the template in solution as solute.Preferably, the template is added as a solution, institute
The concentration for stating solution can be 20-40 weight %.
In addition, the present invention is not required particularly the order that template mixes with inorganic base, water can be simultaneously added to
In, it is also possible to it is added to the water step by step.
Can be that conventional synthesis ZSM-5 molecular sieve make to the species of the template without particular/special requirement according to the present invention
Template, for example, can be one or more in TPAOH, 4-propyl bromide and n-butylamine, preferably
In the case of, the template is TPAOH and/or n-butylamine.The present invention is to the species of the inorganic base also without spy
It is different to require, can be conventional inorganic base, for example, can be conventional NaOH and/or potassium hydroxide.
According to the present invention, step（2）In, to the consumption of source of aluminium without particular/special requirement, as long as ensure that the use of silicon source
Amount makes the silica alumina ratio of the ZSM-5 molecular sieve of gained be 50-400：1, preferably 100-300：1, more preferably 150-250：1.It is right
Silicon source also has no particular limits with the consumption of alcoholic solvent, as long as ensureing that silicon source can be uniformly dispersed in alcoholic solvent.
Preferably, source of aluminium and the mass ratio of alcoholic solvent are 0.001-0.03:1, preferably 0.01-0.02:1.
In addition, the present invention is not required particularly the order that silicon source mixes with alcoholic solvent, as long as carrying out conventional mixing
.
According to the present invention, the present invention to the species of source of aluminium without particular/special requirement, can be molecular sieve art commonly use it is each
Silicon source is planted, for example, can be one or more compound containing aluminium, wherein, the present invention preferably source of aluminium is aluminum sulfate, nitric acid
One or more in aluminium, aluminium chloride, aluminium hydroxide, aluminium isopropoxide and boehmite, particularly preferably in the case of, the aluminium
Source is one or more in aluminum sulfate, aluminum nitrate, aluminium chloride and aluminium isopropoxide.The present invention to the species of the alcoholic solvent also without
Particular/special requirement, as long as the good dispersion in alcoholic solvent of source of aluminium can be realized, under preferable case, the alcoholic solvent is
The alcoholic solvent of the alcoholic solvent of C1-C10, more preferably C1-C5, more preferably methyl alcohol, ethanol, propyl alcohol, isopropanol, n-butanol
With one or more in isobutanol；In the case of particularly preferably, the alcoholic solvent is the one kind in methyl alcohol, ethanol and n-butanol
Or it is various.
According to the present invention, step（3）In, organic silicon source is not required particularly with the consumption of solution A, preferable case
Under, in order that transparent or semitransparent gel can be obtained through hydrolysis after organic silicon source is sufficiently mixed with solution A, it is described to have
Machine silicon source is 0.1-1.5 with the mass ratio of solution A:1, more preferably 0.3-0.9:1.
Although organic silicon source and solution A being mixed according to ratio as above and being capable of achieving the purpose of the present invention, the present invention
Inventor find, be added in solution A several times by by organic silicon source, the spy of the product that will effectively can be finally given
Property control in currently preferred scope.The amount of the organic silicon source being added to every time in solution A, for example, can be 0.04-
0.06g。
The present invention, without particular/special requirement, can be dividing for preparing ZSM-5 for prior art to the species of organic silicon source
The organic silicon source of routine of son sieve, for example, can be one or more hydrolyzable organo-silicon compound, more preferably silicic acid tetramethyl
One or more in ester, tetraethyl orthosilicate and the butyl ester of silicic acid four, particularly preferably in the case of, the silicon source be quanmethyl silicate
And/or tetraethyl orthosilicate.In the present invention, the hydrolyzable refer to organo-silicon compound hydrone effect under, hydrone hydroxyl
Base can occur substitution reaction, organo-silicon compound Si-O-C keys hydrolysis generation Si-O-H keys with the alkoxy in organo-silicon compound
Process.
According to the present invention, step（4）In, gel C is not required particularly with the consumption of solution B, as long as energy after mixing
The gel of homogeneous stabilization is enough formed, under preferable case, the gel C is 1-10 with the mass ratio of solution B:1, more preferably
It is 1.5-4.5:1.
Although gel C and solution B are capable of achieving into the purpose of the present invention, the present invention according to ratio as above is well mixed
Inventor find, be added in gel C several times by by solution B, the Characteristics Control of the product that will can be finally given exists
In currently preferred scope.Each addition, for example, can be 0.04-0.06g.
According to the present invention, each component is carried out into well mixed method without particular/special requirement in each step to more than, as long as energy
It is enough that the component is well mixed, typically in room temperature condition（10-40℃）Under, mix under agitation, herein
Repeat no more.
According to the present invention, step（5）In, the present invention carries out the condition of crystallization to the gel D without particular/special requirement, Ke Yiwei
The conventional crystallization condition for preparing ZSM-5 molecular sieve, under preferable case, the crystallization condition includes：The temperature of crystallization is 90-
150 DEG C, the time of crystallization is 1-10 days.Known in those skilled in the art, the crystallization is general from booster reaction tank or reaction under high pressure
Carried out in kettle, will not be repeated here.
According to the present invention, the present invention, without particular/special requirement, is referred to existing to the separation of solid and liquid, drying, the condition being calcined
Having technology is carried out, such as described dry condition generally comprises drying temperature for 80-200 DEG C, preferably 90-150 DEG C；It is dry
Time is 1-20h, preferably 5-15h.It is 300-800 DEG C, preferably 400-700 that the condition of the roasting is generally sintering temperature
℃；The time of roasting is 1-20h, preferably 5-15h.The method of the separation of solid and liquid can be using this area routine for solid
The method that liquid is separate, for example, the method for centrifugation or filtering.
According to the present invention, step（6）In, by step（5）In the ZSM-5 molecular sieve that obtains and inorganic acid and/or contain ammonium
The condition that the solution of ion carries out ion exchange can be the condition of the conventional ion exchange in this area, for example, can be in stirring
Be heated to reflux under conditions of carry out the ion exchange, the method being heated to reflux is well known to skilled person,
This is repeated no more.
According to the present invention, the inorganic acid and the solution containing ammonium ion can be used for molecular sieve modified for this area
Conventional inorganic acid and the solution containing ammonium ion, under preferable case, the inorganic acid is nitric acid and/or hydrochloric acid, described to contain
The solution of ammonium ion is one or more in ammonium nitrate solution, ammonium chloride solution and ammonium acetate solution.For the inorganic acid
With the concentration of the solution containing ammonium ion without particular/special requirement, for example, the concentration of the inorganic acid or ammonium ion can be respectively
It is 0.05-0.15mol/L.In addition, the consumption of solution of the present invention to the inorganic acid and/or containing ammonium ion does not have yet
Particular/special requirement, ZSM-5 molecular sieve is fully modified as Hydrogen ZSM-5 molecular sieve as long as ensure that, it is preferred in the case of,
Relative to every gram of step（5）The consumption of the ZSM-5 molecular sieve of gained, the inorganic acid and/or the solution containing ammonium ion can
Think 5-10mL.
According to the present invention, the time to the ion exchange has no particular limits, and those skilled in the art can basis
Actual conditions are adjusted, it is generally the case that can be 1-3 hours.
According to the present invention, the condition of the separation of solid and liquid, drying and roasting can use condition as described above, herein not
Repeat again.
According to the present invention, the method for the present invention is also included step（6）The product of gained carries out compressing tablet and crushes, and obtains hydrogen
Type ZSM-5 molecular sieve catalyst.The compressing tablet and broken method are known to those skilled in the art, will not be repeated here.
Wherein, the degree of crushing can be adjusted according to the specification of the reactor for catalytic reaction, for example, when in continuous feed
When internal diameter in the stainless steel micro fixed-bed reactor of 14mm to carry out catalytic reaction, can crush as particle diameter is 10-20 purposes
Catalyst.
Another further aspect, present invention also offers a kind of method that isopropanol dehydration prepares propylene, the method includes：Continuous
On fixed bed reactors, with isopropanol as raw material, diluent is added or is added without, reaction in the presence of a catalyst prepares third
Alkene, wherein, the catalyst is ZSM-5 molecular sieve catalyst as above or is urged by ZSM-5 molecular sieve prepared by method as above
Agent.
According to the present invention, when when being reacted under conditions of adding diluent, the diluent can for nitrogen and/or
Water.Consumption to the diluent has no particular limits, under preferable case, the isopropanol relative to 1mol, the diluent
Consumption can be 0.4-2.3mol.
According to the present invention, the condition to the reaction can be conventional bar of this area for isopropanol dehydration propylene
Part.The condition of the reaction can include：In continuous fixed bed reactors, loaded catalyst is 1-5g, the matter of isopropanol
Amount air speed is 0.5-2h-1.In addition, catalyst prepared by the present invention catalyst for providing and the method provided according to the present invention can
To be used to efficiently be reacted at the much lower temperature of the catalyst of the reaction than other, for example, the temperature of the reaction
It is 200-480 DEG C, preferably 200-320 DEG C, more preferably 240-280 DEG C.Therefore, it is possible to be effectively reduced the production energy of propylene
Consumption.
Below will the present invention will be described in detail by embodiment.
In embodiment and comparative example, if not otherwise specified, used reagent is commercially available chemically pure reagent.
Hereinafter, XRD analysis are carried out on German Bruker AXS companies D8Advance X-ray diffractometers；Sem analysis exist
Carried out on Dutch FEI Co. XL-30 scanners；BET is analyzed in Micromeritics Instrument Corp. U.S.A's ASAP2020-M+C Full-automatic physicals
Carried out on chemical adsorption instrument；TPD analyses are carried out on Micromeritics Instrument Corp. U.S.A AutoChem2920 full-automatic chemical adsorption instruments.
The preparation process that the aluminum trioxide catalyst of propylene is prepared for isopropanol dehydration is：By 200 mesh aluminium hydroxides
30 grams of dry glue（SiO containing 1.40 weight %2With the Na of 0.045 weight %2O）, in Muffle furnace with 5 DEG C/min of temperature programmings extremely
600 DEG C of constant temperature calcinings 6 hours.By products therefrom through compressing tablet, the broken aluminium oxide catalyst for obtaining 10-20 mesh.
The reaction of isopropanol dehydration propylene is anti-in the miniature fixed bed of stainless steel that the internal diameter of self-control continuous feed is 14mm
Answer and carried out on device, product gas chromatograph on-line analysis.
Embodiment 1
The present embodiment is used to illustrate Hydrogen ZSM-5 molecular sieve catalyst of present invention offer and preparation method thereof.
Weigh NaOH3.0g and TPAOH solution（30 weight %）45.0g, is dissolved in 300.0g distilled water, fills
Stirring is divided to obtain solution A；Take 3.0g alchlors to be dissolved in 300.0g ethanol, be sufficiently stirred for obtaining solution B；To in solution A by
Tetraethyl orthosilicate 114.6g is added dropwise to, is sufficiently stirred for 10 minutes, obtain gel C；Again to solution B is dropwise added dropwise in gel C, fully
Stirring 30 minutes, obtains gel D, and pH value is 11.Then gel D is transferred in 1.5 liters of autoclaves, it is static brilliant in 110 DEG C
Change 4 days.Products therefrom is centrifuged, and in 110 DEG C of dryings 12 hours, goes template agent removing to obtain within 8 hours then at 550 DEG C of roastings small
Particle diameter ZSM-5 molecular sieve product（It is denoted as E1）26.2g, silica alumina ratio is 50.
Under stirring and heated reflux condition, by the E1 of 8.2g carried out with the ammonium nitrate solution of the 0.10mol/L of 50mL from
Son is exchanged 2 hours, then is centrifuged, is distilled water washing, 150 DEG C of dryings 5 hours, and 550 DEG C of roastings obtain Hydrogen granule in 8 hours
Footpath ZSM-5 molecular sieve F1.
Prepared molecular sieve F1 is carried out into compressing tablet, then particle diameter is obtained for 10-20 molecules of interest sieves catalysis through broken, sieving
Agent Cat-1.
As illustrated in fig. 1 and 2, XRD characterization results show that gained molecular sieve is to XRD the and SEM characterization results of molecular sieve E1
ZSM-5 molecular sieve, SEM characterization results show that molecular sieve is small particle molecular sieve of the particle diameter in the range of 200-250nm.Molecular sieve
F1 shows that specific surface area is 280m through BET and TPD2/ g, ammonia temperature programming adsorption/desorption shows that in temperature be near 194 DEG C
There is characteristic absorption peak.
Embodiment 2
The present embodiment is used to illustrate Hydrogen ZSM-5 molecular sieve catalyst of present invention offer and preparation method thereof.
KOH1.5g and n-butylamine 24.0g is weighed, is dissolved in 135.0g distilled water, be sufficiently stirred for obtaining solution A；Take 1.80g
Al(NO3)3·9H2O is dissolved in 100.0g methyl alcohol, obtains solution B；To quanmethyl silicate 145.0g is added dropwise in solution A, fill
Divide stirring 10 minutes, be sufficiently stirred for obtaining gel C；Again to B solution is dropwise added dropwise in gel C, it is sufficiently stirred for 30 minutes, is coagulated
Glue D, pH value is 9.5.Then gel D is transferred in 500 milliliters of spontaneous pressure stainless steel reaction tanks, in 150 DEG C of static crystallizations 2 days.
Products therefrom through centrifugation, separate, in 110 DEG C of dryings 12 hours, go template agent removing to obtain small particle within 15 hours then at 400 DEG C of roastings
ZSM-5 molecular sieve product（It is denoted as E2）45.5g, silica alumina ratio is 400.
Under stirring and heated reflux condition, the E2 of 10.0g is carried out with the ammonium chloride solution of the 0.05mol/L of 100mL
Ion exchange 1 hour, then be centrifuged, dry after, obtain within 5 hours Hydrogen small particle ZSM-5 molecular sieve in 700 DEG C of roastings
F2。
Prepared molecular sieve F2 is carried out into compressing tablet, then particle diameter is obtained for 10-20 molecules of interest sieves catalysis through broken, sieving
Agent Cat-2.
The XRD of molecular sieve E2 is identical with Fig. 1, SEM characterization results such as Fig. 3, and molecular sieve particle diameter is 150-300nm.Molecular sieve
F2 shows that specific surface area is 320m through BET and TPD2/ g, ammonia temperature programming adsorption/desorption shows that in temperature be near 176 DEG C
There is characteristic absorption peak.
Experimental example 3
The present embodiment is used to illustrate Hydrogen ZSM-5 molecular sieve catalyst of present invention offer and preparation method thereof.
Weigh NaOH1.0g and TPAOH solution（40 weight %）30.0g, is dissolved in 160.0g distilled water, fills
Stirring is divided to obtain solution A；Take 1.2g Al2(SO4)3·18H2O is dissolved in 60.0g n-butanols, obtains solution B；To in solution A by
Tetraethyl orthosilicate 72.0g is added dropwise to, is sufficiently stirred for 10 minutes, obtain gel C；Again to B solution is dropwise added dropwise in gel C, fully
Stirring 30 minutes, obtains gel D, and pH value is 12.Then gel D is transferred in 500 milliliters of spontaneous pressure stainless steel reaction tanks, in 90
DEG C static crystallization 7 days.Products therefrom through centrifugation, separate, in 110 DEG C of dryings 12 hours, then at 550 DEG C of roastings, 8 hours removal moulds
Plate agent obtains small particle ZSM-5 molecular sieve product（It is denoted as E3）17.6g, silica alumina ratio is 200.
Under stirring and heated reflux condition, the E3 of 5.0g is carried out into ion with the salpeter solution of the 0.15mol/L of 25mL
Exchange 3 hours, then be centrifuged, dry after, obtain within 8 hours Hydrogen small particle ZSM-5 molecular sieve F3 in 550 DEG C of roastings.
Prepared ZSM-5 molecular sieve F3 is carried out into compressing tablet, then particle diameter is obtained for 10-20 molecules of interest through broken, sieving
Sieve catalyst Cat-3.
The XRD of molecular sieve E3 is identical with Fig. 1, SEM characterization results such as Fig. 4, and molecular sieve particle diameter is 200-300nm.Molecular sieve
F3 shows that specific surface area is 340m through BET and TPD2/ g, ammonia temperature programming adsorption/desorption shows that in temperature be near 186 DEG C
There is characteristic absorption peak.
Embodiment 4
The present embodiment is used to illustrate Hydrogen ZSM-5 molecular sieve catalyst of present invention offer and preparation method thereof.
Hydrogen ZSM-5 molecular sieve catalyst Cat-4 is prepared according to method same as Example 1.Unlike, will be organic
Silicon source is disposably added in solution A, and solution B point is disposably added in gel C, molecular sieve and the embodiment gained of gained
The difference of molecular sieve be that it is 100-500nm that SEM characterizes molecular sieve particle diameter, and specific surface area is 210m2/g。
Test case 1
This test case is used to illustrate the Hydrogen ZSM-5 molecular sieve catalyst of present invention preparation to isopropanol dehydration propylene
Catalytic effect.
In 6 continuous feed fixed bed stainless steel tube reactors, the catalysis of 2.00g embodiments 1-4 preparations is respectively charged into
Agent Cat-1, Cat-2, Cat-3 and Cat-4.Diluent is nitrogen, in mol, isopropanol：（Isopropanol+nitrogen）It is 0.3：1.
Reaction pressure is normal pressure, and reaction temperature is 240 DEG C, and the weight space velocity of isopropanol is 0.5h-1, iso-propanol conversion rate is respectively
99.4%th, 99.7%, 99.5% and 99%；Propylene Selectivity is respectively 98.4%, 98.5%, 98.2% and 97.5%.
Test case 2
This test case is used to illustrate the Hydrogen ZSM-5 molecular sieve catalyst of present invention preparation to isopropanol dehydration propylene
Catalytic effect.
In 6 continuous feed fixed bed stainless steel tube reactors, the catalysis of 2.00g embodiments 1-4 preparations is respectively charged into
Agent Cat-1, Cat-2, Cat-3 and Cat-4.Diluent is nitrogen, in mol, isopropanol：（Isopropanol+nitrogen）It is 0.7：1.
Reaction pressure is normal pressure, and reaction temperature is 260 DEG C, and the weight space velocity of isopropanol is 1h-1, iso-propanol conversion rate is respectively 99.8%,
99.6%th, 99.8% and 99.2%；Propylene Selectivity is respectively 98.2%, 98.3%, 98.4% and 97.6%.
Test case 3
This test case is used to illustrate the Hydrogen ZSM-5 molecular sieve catalyst of present invention preparation to isopropanol dehydration propylene
Catalytic effect.
In 6 continuous feed fixed bed stainless steel tube reactors, the catalysis of 2.00g embodiments 1-4 preparations is respectively charged into
Agent Cat-1, Cat-2, Cat-3 and Cat-4.It is added without diluent.Reaction pressure is normal pressure, and reaction temperature is 280 DEG C, isopropanol
Weight space velocity be 2h-1, iso-propanol conversion rate is respectively 100%, 99.9%, 99.9% and 99.4%；Propylene Selectivity is respectively
98.7%th, 98.5%, 98.8% and 97.8%.
Test case 4
This test case is used to illustrate the Hydrogen ZSM-5 molecular sieve catalyst of present invention preparation to isopropanol dehydration propylene
Catalytic effect.
According to the preparation for carrying out with the identical condition of EXPERIMENTAL EXAMPLE 1 propylene, unlike, the temperature of reaction is 320 DEG C.
Iso-propanol conversion rate is 100%, and Propylene Selectivity is respectively 97.4%, 97.5%, 97.2% and 96.5%.
In following contrast test example, Zn modified ZSM-5 molecular sieve is according to Liu Chunyan etc.（Acidic catalyst is catalyzed isopropyl
Dehydration of alcohols propylene reacts, Industrial Catalysis, 2011,19（5）, 40-44）In method be prepared what is obtained.
Contrast test example 1-4
The preparation of propylene is carried out according to the method for test case 1-4 respectively, unlike, used in each contrast test example
Catalyst be the modified ZSM-5 molecular sieves and alundum (Al2O3) of Zn.
Iso-propanol conversion rate is respectively 52.5% and 72% in contrast test example 1；Propylene Selectivity is respectively 97.2% He
86.4%；
Iso-propanol conversion rate is respectively 75.6% and 80% in contrast test example 2；Propylene Selectivity is respectively 97.8% and 88%.
Iso-propanol conversion rate is respectively 98.5% and 85.2% in contrast test example 3；Propylene Selectivity is respectively 93.0% He
94.1%。
Iso-propanol conversion rate is 100% in contrast test example 4；Propylene Selectivity is respectively 45.2% and 96.9%.
Be can be seen that the silica alumina ratio of Hydrogen ZSM-5 molecular sieve, grain by above example and comparative example and test result
The acid control on footpath, specific surface area and surface within the scope of the invention, i.e. can be efficient within the scope of relatively low temperature
Catalysis isopropanol dehydration is transformed into propylene, and the catalytic efficiency of the ZSM-5 molecular sieve being modified compared to existing Zn has significantly
Improve.And be can be seen that at a lower temperature using existing alundum (Al2O3), its conversion ratio and propylene to isopropanol
Selectivity it is relatively low, preferable catalytic performance is only just shown at high temperature.
The preferred embodiment of the present invention described in detail above, but, the present invention is not limited in above-mentioned implementation method
Detail, in range of the technology design of the invention, various simple variants can be carried out to technical scheme, this
A little simple variants belong to protection scope of the present invention.
It is further to note that each particular technique feature described in above-mentioned specific embodiment, in not lance
In the case of shield, can be combined by any suitable means.In order to avoid unnecessary repetition, the present invention to it is various can
The combination of energy is no longer separately illustrated.
Additionally, can also be combined between a variety of implementation methods of the invention, as long as it is without prejudice to originally
The thought of invention, it should equally be considered as content disclosed in this invention.
Claims (12)
1. a kind of method that isopropanol dehydration prepares propylene, the method includes：In continuous fixed bed reactors, it is with isopropanol
Raw material, adds or is added without diluent, and reaction in the presence of a catalyst prepares propylene, it is characterised in that the catalyst is
Hydrogen ZSM-5 molecular sieve catalyst；
Wherein, in the molecular sieve catalyst, the silica alumina ratio of the Hydrogen ZSM-5 molecular sieve is 50-400：1, particle diameter is 100-
500nm, specific surface area is 160-350m2/g；NH3- TPD characterized by techniques has feature adsorption peak at 170-200 DEG C.
2. method according to claim 1, wherein, being reacted under conditions of diluent is added, the diluent is
Nitrogen and/or water；Isopropanol relative to 1mol, the consumption of the diluent is 0.4-2.3mol.
3. method according to claim 1 and 2, wherein, the condition of the reaction includes：The mass space velocity of isopropanol is
0.5-2h-1, the temperature of reaction is 200-480 DEG C.
4. method according to claim 3, wherein, the temperature of reaction is 200-320 DEG C.
5. method according to claim 4, wherein, the temperature of reaction is 240-280 DEG C.
6. method according to claim 1, wherein, the Hydrogen ZSM-5 molecular sieve catalyst is entered by following method
It is prepared by row：
(1) template is well mixed with inorganic base in water and obtains solution A；
(2) silicon source is well mixed with alcoholic solvent and obtains solution B；
(3) organic silicon source is well mixed with solution A and obtains gel C；
(4) gel C is well mixed with solution B and obtains gel D；
(5) the gel D is carried out into separation of solid and liquid, drying and roasting successively after crystallization under crystallization condition, obtains ZSM-5 molecules
Sieve；
(6) ZSM-5 molecular sieve and inorganic acid and/or solution containing ammonium ion are carried out into ion exchange, and by after ion exchange
Material carry out separation of solid and liquid, drying and roasting successively.
7. method according to claim 6, wherein,
In step (1), the template is one or more in TPAOH, 4-propyl bromide and n-butylamine,
The inorganic base is NaOH and/or potassium hydroxide；
In step (2), source of aluminium is one or more in aluminum sulfate, aluminum nitrate, aluminium chloride and aluminium isopropoxide；The alcohol is molten
Agent is one or more in methyl alcohol, ethanol and n-butanol；
In step (3), organic silicon source is quanmethyl silicate and/or tetraethyl orthosilicate.
8. the method according to claim 6 or 7, wherein,
In step (1), the template is 1-20 with the mass ratio of inorganic base:1；The template is with the mass ratio of water
0.01-0.3:1；
In step (2), source of aluminium is 0.001-0.03 with the mass ratio of alcoholic solvent:1；
In step (3), organic silicon source is 0.1-1.5 with the mass ratio of solution A:1；
In step (4), the gel C is 1-10 with solution B mass ratio:1.
9. the method according to claim 6 or 7, wherein,
In step (3), organic silicon source is added in solution A several times, each addition is 0.04-0.06g；
In step (4), solution B is added in gel C several times, each addition is 0.04-0.06g.
10. method according to claim 6, wherein, in step (5), the condition of the crystallization includes：The temperature of crystallization is
90-150 DEG C, the time of crystallization is 1-10 days.
11. methods according to claim 6, wherein, in step (6), the inorganic acid is nitric acid and/or hydrochloric acid；It is described
Solution containing ammonium ion is one or more in ammonium nitrate solution, ammonium chloride solution and ammonium acetate solution；The inorganic acid
Or the concentration of ammonium ion is 0.05-0.15mol/L.
12. method according to any one in claim 6-7 and 10-11, wherein, the Hydrogen ZSM-5 molecular sieve is urged
The preparation method of agent also includes：Compressing tablet is carried out to the product that step (6) is obtained and is crushed, obtained Hydrogen ZSM-5 molecular sieve and urge
Agent.
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