CN104549435A - Rare-earth modified ZSM-5 molecular sieve based catalyst and preparation method and application thereof - Google Patents
Rare-earth modified ZSM-5 molecular sieve based catalyst and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a rare-earth modified ZSM-5 molecular sieve based catalyst. For a rare-earth modified ZSM-5 molecular sieve in the molecular sieve based catalyst, the silica-alumina ratio is (50-400):1, the particle size is 100-500 nm, and the specific surface area is 160-350 m<2>/g; an NH3-TPD technology represents that a characteristic absorption peak appears at a temperature of 170-200 DEG C. The invention also provides a method for preparing the catalyst and application of the catalyst in the preparation of propene through isopropanol dehydration. The catalyst provided by the invention can effectively convert isopropanol to propene in a relatively low temperature range, and improves the conversion rate of isopropanol and the selectivity of propene.
Description
Technical field
The present invention relates to a kind of rare earth modified ZSM-5 molecular sieve catalyzer, the preparation method of this catalyzer, and the application in propylene prepared by this catalyzer at isopropanol dehydration.
Background technology
Propylene is important basic organic.There is the technique such as conversion of olefines of preparing ethylene by steam cracking propylene simultaneously, refinery catalytic cracking device dry gas, dehydrogenating propane and methanol-to-olefins and development in recent years in the source of propylene in the world.In recent years, propylene Downstream Products is rapid, and the demand of propylene increases day by day.Therefore, utilizing level, developing the focus that new propylene production technology and technology become people's research of propylene is improved.
Acetone is a kind of important derivatives of propylene.In phynol/acetone manufacture, benzene and production of propylene isopropyl benzene, then prepare phenol through oxidising process, cogeneration of propanone.In recent years, along with progress and the development of phenol industrial technology, the total amount of cogeneration of propanone increases sharply, and the situation of acetone surplus has appearred in partial area.Therefore, comprehensive utilization acetone, exploitation acetone hydrogenation preparing isopropanol, Virahol becomes possibility through the technique of dehydration reaction propylene and technology, and can adjust production technique according to the demand of market to propylene and Virahol.
The report of relevant isopropanol dehydration propylene technology is less, and studied catalyzer mainly comprises aluminum oxide, heteropolyacid and molecular sieve etc.WO 0361755B1 discloses a kind of phenol preparation method and propylene reuse technology.Taking gama-alumina as catalyzer in this technology, at 320 DEG C, can be propylene by iso-propanol conversion, but iso-propanol conversion rate and Propylene Selectivity be all lower under 1MPa pressure condition.Fu Xiang waits clearly (Guyuan Journal of Teachers College, 2001,22 (6), 19-22) to find that MCM-41 is the best carrier of carried heteropoly acid, but prepared catalyzer catalytic activity in isopropanol dehydration reaction is lower.Zhang Hanpeng etc. have studied the heteropolyacid such as load phosphorus tungsten, silicon tungsten, phosphorus molybdenum on activated carbon, and for isopropanol dehydration reaction, but same iso-propanol conversion rate and Propylene Selectivity all lower.(the activity of the synthesis of solid-carrying heteropolyacid, sign and the reaction of catalysis isopropanol dehydration such as Liu Chunyan, Industrial Catalysis, 2011,19(5), 40-44) research of an acidic catalyst catalysis isopropanol dehydration propylene is found, SAPO-34 must have stronger iso-propanol conversion active at a higher temperature, higher Propylene Selectivity, ZSM-5 molecular sieve is modified through Zn, the preparation of propylene can be carried out under the cold condition of 280 DEG C, iso-propanol conversion rate 98.8%, Propylene Selectivity is 93.5%, but still needs to be improved further.
Therefore, need badly exploitation a kind of can at a lower temperature, high conversion and highly selective be the catalyzer of propylene by iso-propanol conversion.
Summary of the invention
The object of the invention is to prepare in the method for propylene to overcome existing isopropanol dehydration, desired reaction temperature is high, or iso-propanol conversion rate and the low defect of Propylene Selectivity, there is provided a kind of and there is higher iso-propanol conversion rate and the catalyzer of Propylene Selectivity at a lower temperature, and the preparation method of this catalyzer.
To achieve these goals, on the one hand, the invention provides a kind of rare earth modified ZSM-5 molecular sieve catalyzer, wherein, in this molecular sieve catalyst, the silica alumina ratio of described rare earth modified ZSM-5 molecular sieve is 50-400, particle diameter is 100-500nm, and specific surface area is 160-350m
2/ g; NH
3-TPD characterized by techniques has feature adsorption peak at 170-200 DEG C.
On the other hand, the invention provides a kind of method preparing rare earth modified ZSM-5 molecular sieve catalyzer, the method comprises:
(1) template is mixed with mineral alkali in water obtain solution A;
(2) aluminium source is mixed with alcoholic solvent obtain solution B;
(3) organosilicon source mixes with solution A and obtains gel C;
(4) gel C is mixed with solution B obtain gel D;
(5) described gel D is carried out solid-liquid separation, drying and roasting successively after crystallization under crystallization condition, obtain ZSM-5 molecular sieve;
(6) ZSM-5 molecular sieve and mineral acid and/or the solution containing ammonium ion are carried out ion-exchange, and the material after ion-exchange is carried out solid-liquid separation, drying and roasting successively;
(7) carry out rare earth modified to the product after the roasting obtained in step (6).
Again on the one hand, present invention also offers a kind of method that isopropanol dehydration prepares propylene, the method comprises: on continuous fixed-bed reactor, take Virahol as raw material, add or do not add thinner, propylene is prepared in reaction in the presence of a catalyst, wherein, and the ZSM-5 molecular sieve catalyzer that described catalyzer is ZSM-5 molecular sieve catalyzer as above or is prepared by method as above.
Method of the present invention, uses rare earth modified ZSM-5 molecular sieve as the catalyzer of isopropanol dehydration propylene, and by its silica alumina ratio, particle diameter, specific surface area and NH
3the temperature of the charateristic avsorption band of-TPD controls within the scope of the invention, effectively can solve the higher or transformation efficiency of Virahol of the temperature requirement of existing isopropanol dehydration catalyst reaction and all lower defect of the selectivity of propylene.As can be seen from the test case of the application, adopt the catalyzer of rare earth modified ZSM-5 molecular sieve catalyzer as isopropanol dehydration propylene of the application, can react at a lower temperature, the transformation efficiency of Virahol is greater than 99%, and the selectivity of propylene is greater than 96%.
Other features and advantages of the present invention are described in detail in embodiment part subsequently.
Accompanying drawing explanation
Accompanying drawing is used to provide a further understanding of the present invention, and forms a part for specification sheets, is used from explanation the present invention, but is not construed as limiting the invention with embodiment one below.In the accompanying drawings:
The XRD spectra of Fig. 1: ZSM-5 molecular sieve E1 prepared by embodiment 1;
The SEM spectrogram of Fig. 2: ZSM-5 molecular sieve E1 prepared by embodiment 1;
The EDS spectrogram of Fig. 3: La modified zsm-5 zeolite G1 prepared by embodiment 1;
The SEM spectrogram of Fig. 4: ZSM-5 molecular sieve E2 prepared by embodiment 2;
Fig. 5: the EDS spectrogram of the ZSM-5 molecular sieve G2 of Ce modification prepared by embodiment 2;
The SEM spectrogram of Fig. 6: ZSM-5 molecular sieve E3 prepared by embodiment 3.
Embodiment
Below the specific embodiment of the present invention is described in detail.Should be understood that, embodiment described herein, only for instruction and explanation of the present invention, is not limited to the present invention.
On the one hand, the invention provides a kind of rare earth modified ZSM-5 molecular sieve catalyzer, wherein, in this molecular sieve catalyst, the silica alumina ratio of described rare earth modified ZSM-5 molecular sieve is 50-400:1, and particle diameter is 100-500nm, and specific surface area is 160-350m
2/ g; NH
3-TPD characterized by techniques has feature adsorption peak at 170-200 DEG C.
In the present invention, term " particle diameter " refers to the size of (010) crystal face in molecular sieve crystal, and those skilled in the art all can know this, does not repeat them here.
In the present invention, term " silica alumina ratio " has implication well known in the art, refers to SiO
2and Al
2o
3mol ratio.
NH
3-TPD(temperature programmed desorption(TPD) technology) be comparatively classical and convenience, practical sign molecular sieve surface acidity method.As well known to those skilled in the art, according to NH
3the temperature of the charateristic avsorption band that-TPD technology obtains can judge the acidity on ZSM-5 molecular sieve surface, such as, show that ZSM-5 molecular sieve surface is in slightly acidic at 100-200 DEG C of existing characteristics absorption peak, show at 400 DEG C of charateristic avsorption bands occurred later, ZSM-5 molecular sieve surface is in middle strong acidity, then shows that ZSM-5 molecular sieve is strongly-acid at 200-400 DEG C of existing characteristics absorption peak.Rare earth modified ZSM-5 molecular sieve catalyzer provided by the invention, through NH
3-TPD characterized by techniques has feature adsorption peak at 170-200 DEG C, illustrates that rare earth modified ZSM-5 molecular sieve catalyst surface provided by the invention has slightly acidic.
Need it is noted that, although herein use NH
3the acidity of-TPD characterized by techniques molecular sieve surface, but can not be interpreted as that this technology can limit the scope of the invention, those skilled in the art can also adopt the conventional technology that can be used for characterizing ZSM-5 molecular sieve surface acidity, such as, and indicator method, spectrography, calorimetry etc.
Under normal circumstances, the most typical feature of ZSM-5 molecular sieve is exactly that surface has stronger acidity.But the present inventor finds, when the surface of ZSM-5 molecular sieve is slightly acidic, and its silica alumina ratio is controlled at higher scope (50-400:1, be preferably 100-300:1, be more preferably 150-250:1), in less scope, (100-500nm, is preferably 150-450 to size controlling, be more preferably 200-300), specific surface area controls at 160-350m
2/ g, preferably 250-330m
2/ g, be more preferably 280-320m
2/ g, and after rare earth modified, can catalysis isopropanol dehydration propylene at a lower temperature, and effectively improves the transformation efficiency of Virahol and the selectivity of propylene.
According to the present invention, although the Characteristics Control of rare earth modified ZSM-5 molecular sieve can effectively be realized object of the present invention in above scope, but the present inventor finds, when with the gross weight of described rare earth modified ZSM-5 molecular sieve catalyzer for benchmark, the content of rare earth element is 0.1-8 % by weight, is preferably 0.35-4.95 % by weight, is more preferably 1.5-4 % by weight, can improve the transformation efficiency of Virahol and the selectivity of propylene further.
According to the present invention, described rare earth element can be this area routine for molecular sieve modified rare earth element, preferably, described rare earth element is one or more in lanthanum, cerium, praseodymium and neodymium, is more preferably lanthanum and/or cerium.
On the other hand, the invention provides a kind of method preparing rare earth modified ZSM-5 molecular sieve catalyzer, the method comprises:
(1) template is mixed with mineral alkali in water obtain solution A;
(2) aluminium source is mixed with alcoholic solvent obtain solution B;
(3) organosilicon source mixes with solution A and obtains gel C;
(4) gel C is mixed with solution B obtain gel D;
(5) described gel D is carried out solid-liquid separation, drying and roasting successively after crystallization under crystallization condition, obtain ZSM-5 molecular sieve;
(6) ZSM-5 molecular sieve and mineral acid and/or the solution containing ammonium ion are carried out ion-exchange, and the material after ion-exchange is carried out solid-liquid separation, drying and roasting successively;
(7) carry out rare earth modified to the product after the roasting obtained in step (6).
According to the present invention, in step (1), to the consumption of described template and the consumption of mineral alkali without particular requirement, as long as can form stable solution, under preferable case, the mass ratio of described template and mineral alkali is 1-20:1, is preferably 4.5-16:1; The consumption of mineral alkali 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 particular requirement, and preferably, the mass ratio of described template and water is 0.01-0.3:1, is preferably 0.04-0.2:1.
According to the present invention, described template can add in solid form, also can add as a solution, the amount of above-described template, fashionable when adding in solid form, refer to the consumption of template solid, fashionable when adding as a solution, refer to the consumption as the template of solute in solution.Preferably, described template adds as a solution, and the concentration of described solution can be 20-40 % by weight.
In addition, the not special requirement of order that the present invention mixes with mineral alkali template, can be added to the water simultaneously, also can be added to the water step by step.
According to the present invention, to the kind of described template without particular requirement, it can be the template that conventional synthesis ZSM-5 molecular sieve uses, such as, can be one or more in TPAOH, 4-propyl bromide and n-Butyl Amine 99, in preferred situation, described template is TPAOH and/or n-Butyl Amine 99.The present invention also without particular requirement, can, for conventional mineral alkali, such as, can be conventional sodium hydroxide and/or potassium hydroxide to the kind of described mineral alkali.
According to the present invention, in step (2), to the consumption in described aluminium source without particular requirement, as long as can ensure that the consumption in aluminium source makes the silica alumina ratio of the ZSM-5 molecular sieve of gained be 50-400:1, be preferably 100-300:1, be more preferably 150-250:1.The consumption of aluminium source and alcoholic solvent is also had no particular limits, as long as ensure that aluminium source can be dispersed in alcoholic solvent uniformly.Preferably, the mass ratio of described aluminium source and alcoholic solvent is 0.001-0.03:1, is preferably 0.01-0.02:1.
In addition, the not special requirement of order that the present invention mixes with alcoholic solvent aluminium source, as long as carry out conventional mixing.
According to the present invention, the present invention to the kind in described aluminium source without particular requirement, the various aluminium sources can commonly used for molecular sieve art, such as, can for one or more be containing the compound of aluminium, wherein, the preferred described aluminium source of the present invention is one or more in Tai-Ace S 150, aluminum nitrate, aluminum chloride, aluminium hydroxide, aluminum isopropylate and pseudo-boehmite, in particularly preferred situation, described aluminium source is one or more in Tai-Ace S 150, aluminum nitrate, aluminum chloride and aluminum isopropylate.The present invention to the kind of described alcoholic solvent also without particular requirement, as long as the dispersion that described aluminium source is good in alcoholic solvent can be realized, under preferable case, described alcoholic solvent is the alcoholic solvent of C1-C10, be more preferably the alcoholic solvent of C1-C5, one or more more preferably in methyl alcohol, ethanol, propyl alcohol, Virahol, propyl carbinol and isopropylcarbinol; In particularly preferred situation, described alcoholic solvent is one or more in methyl alcohol, ethanol and propyl carbinol.
According to the present invention, in step (3), to the special requirement of the consumption of organosilicon source and solution A, under preferable case, transparent or semitransparent gel can be obtained through hydrolysis after fully mixing with solution A to make described organosilicon source, the mass ratio of described organosilicon source and solution A is 0.1-1.5:1, is more preferably 0.3-0.9:1.
Although organosilicon source and solution A are mixed according to ratio as above and can realize object of the present invention, but the present inventor finds, by organosilicon source is joined in solution A several times, can effectively by the Characteristics Control of product that finally obtains in the preferred scope of the present invention.Join the amount in the organosilicon source in solution A, such as, can be 0.04-0.06g at every turn.
The present invention to the kind in described organosilicon source without particular requirement, it can be the conventional organosilicon source for the preparation of ZSM-5 molecular sieve of prior art, such as, can be one or more hydrolyzable silicoorganic compound, be more preferably one or more in butyl ester of quanmethyl silicate, tetraethyl orthosilicate and silicic acid four, particularly preferably in situation, described silicon source is quanmethyl silicate and/or tetraethyl orthosilicate.In the present invention, described hydrolyzable refers to silicoorganic compound under water molecules effect, and water molecules hydroxyl can with the alkoxyl group generation substitution reaction in silicoorganic compound, and the hydrolysis of silicoorganic compound Si-O-C key generates the process of Si-O-H key.
According to the present invention, in step (4), to the special requirement of the consumption of gel C and solution B, as long as homogeneous stable gel can be formed after mixing, under preferable case, the mass ratio of described gel C and solution B is 1-10:1, is more preferably 1.5-4.5:1.
Although gel C and solution B are mixed according to ratio as above and can realize object of the present invention, but the present inventor finds, by solution B is joined in gel C several times, can by the Characteristics Control of product that finally obtains in the preferred scope of the present invention.Each add-on such as, can be 0.04-0.06g.
According to the present invention, to the method in above each step, each component mixed without particular requirement, as long as described component can be mixed, generally under room temperature condition (10-40 DEG C), mix under agitation, do not repeat them here.
According to the present invention, in step (5), the present invention carries out the condition of crystallization without particular requirement to described gel D, can for the conventional crystallization condition preparing ZSM-5 molecular sieve, under preferable case, described crystallization condition comprises: the temperature of crystallization is 90-150 DEG C, and the time of crystallization is 1-10 days.Those skilled in the art are known, and described crystallization generally carrying out in booster reaction tank or autoclave, does not repeat them here.
According to the present invention, the present invention, can carry out with reference to prior art without particular requirement the condition of described solid-liquid separation, drying, roasting, and it is 80-200 DEG C that the condition of such as described drying generally comprises drying temperature, is preferably 90-150 DEG C; The dry time is 1-20h, is preferably 5-15h.It is 300-800 DEG C that the condition of described roasting is generally maturing temperature, is preferably 400-700 DEG C; The time of roasting is 1-20h, is preferably 5-15h.The method of described solid-liquid separation can adopt the method for solid-liquid separation of this area routine, such as, centrifugal or filter method.
According to the present invention, in step (6), the condition of the ZSM-5 molecular sieve obtained in step (5) and mineral acid and/or the solution containing ammonium ion being carried out ion-exchange can be the condition of the ion-exchange of this area routine, such as, can stir and reflux condition under carry out described ion-exchange, the method of described reflux is that skilled person is known, does not repeat them here.
According to the present invention, described mineral acid and the solution containing ammonium ion can be used for the mineral acid to molecular sieve modified routine and the solution containing ammonium ion for this area, under preferable case, described mineral acid is nitric acid and/or hydrochloric acid, and the described solution containing ammonium ion is one or more in ammonium nitrate solution, ammonium chloride solution and Spirit of Mindererus.For described mineral acid and the concentration of solution containing ammonium radical ion all without particular requirement, such as, the concentration of described mineral acid or ammonium ion can be 0.05-0.15mol/L respectively.In addition, the consumption of the present invention to described mineral acid and/or the solution containing ammonium radical ion does not have particular requirement yet, as long as ZSM-5 molecular sieve can be ensured fully to be modified as Hydrogen ZSM-5 molecular sieve, in preferred situation, relative to the ZSM-5 molecular sieve of every gram of step (5) gained, the consumption of described mineral acid and/or the solution containing ammonium radical ion can be 5-10mL.
According to the present invention, have no particular limits the time of described ion-exchange, those skilled in the art can adjust according to practical situation, under normal circumstances, can be 1-3 hour.
According to the present invention, the condition of described solid-liquid separation, drying and roasting can adopt condition as above, does not repeat them here.
According to the present invention, in step (7), carry out rare earth modified process can comprise: the product after the roasting obtained in step (6) and the solution containing rare earth ion are carried out ion-exchange, and the product after ion-exchange is carried out solid-liquid separation, drying and roasting successively.
According to the present invention, have no particular limits containing the rare earth ion concentration in the solution of rare earth ion described, as long as the product after its roasting that can obtain with step (6) carries out ion-exchange, preferably, the concentration of the described solution Rare Earth Ion containing rare earth ion is 0.03-0.08mol/L.In addition, the consumption of the solution containing rare earth ion of above-mentioned concentration is not also specially required, as long as make the described rare earth modified ZSM-5 molecular sieve catalyzer prepared contain the rare earth element of 0.1-8 % by weight, preferably 0.35-4.95 % by weight, more preferably 1.5-4 % by weight, in preferred situation, relative to the product obtained in every gram of step (5), the above-mentioned solution containing rare earth ion of 2-5.5mL can be used.
Preferably, rare earth element is one or more in lanthanum, cerium, praseodymium and neodymium, is more preferably lanthanum and/or cerium.
In addition, to the product after rare-earth element modified carry out ion-exchange, the method for solid-liquid separation, drying and roasting condition all can adopt method as above and condition.Do not repeat them here.
According to the present invention, method of the present invention also comprises carries out compressing tablet and fragmentation to through rare earth modified ZSM-5 molecular sieve, obtains rare earth modified ZSM-5 molecular sieve catalyzer.Described compressing tablet and broken method are conventionally known to one of skill in the art, do not repeat them here.Wherein, the degree pulverized can adjust according to the specification of the reactor for catalyzed reaction, such as, when being when carrying out catalyzed reaction in the stainless steel micro fixed-bed reactor of 14mm at the internal diameter of continuously feeding, can pulverize as particle diameter is 10-20 object catalyzer.
Again on the one hand, present invention also offers a kind of method that isopropanol dehydration prepares propylene, the method comprises: on continuous fixed-bed reactor, take Virahol as raw material, add or do not add thinner, propylene is prepared in reaction in the presence of a catalyst, wherein, and the ZSM-5 molecular sieve catalyzer that described catalyzer is ZSM-5 molecular sieve catalyzer as above or is prepared by method as above.
According to the present invention, when reacting under the condition adding thinner, described thinner can be nitrogen and/or water.Have no particular limits the consumption of described thinner, under preferable case, relative to the Virahol of 1mol, the consumption of described thinner can be 0.4-2.3mol.
According to the present invention, the condition of the routine of isopropanol dehydration propylene can be used for for this area to the condition of described reaction.The condition of described reaction can comprise: in continuous fixed-bed reactor, and loaded catalyst is 1-5g, and the mass space velocity of Virahol is 0.5-2h
-1.In addition, catalyzer provided by the invention and can reacting efficiently at the temperature more much lower for the catalyzer of this reaction than other according to catalyzer prepared by method provided by the invention, such as, the temperature of described reaction is 200-480 DEG C, be preferably 200-360 DEG C, most preferably be 240-280 DEG C.Therefore, it is possible to effectively reduce the production energy consumption of propylene.
Below will be described the present invention by embodiment.
In embodiment and comparative example, if not otherwise specified, used reagent is commercially available chemically pure reagent.
Below, XRD analysis is carried out on German Bruker AXS company D8Advance X-ray diffractometer; Sem analysis carries out on Dutch FEI Co. XL-30 scanner; EDS analyzes and carries out on NORAN company of U.S. Vantage ESI digital X-ray power spectrum (EDS) instrument; BET analyzes and carries out on Micromeritics Instrument Corp. U.S.A ASAP2020-M+C Full-automatic physical chemical adsorption instrument; TPD analyzes and carries out on Micromeritics Instrument Corp. U.S.A AutoChem 2920 full-automatic chemical adsorption instrument.
The preparation process preparing the aluminum trioxide catalyst of propylene for isopropanol dehydration is: by 200 order aluminum hydroxide solid elastomer 30 grams (containing the SiO of 1.40 % by weight
2with 0.045 % by weight Na
2o), in retort furnace with 5 DEG C/min of temperature programming to 600 DEG C constant temperature calcinings 6 hours.Products therefrom is obtained 10-20 object aluminium oxide catalyst through compressing tablet, fragmentation.
The reaction of isopropanol dehydration propylene is that the stainless steel micro fixed-bed reactor of 14mm carries out at the internal diameter of self-control continuously feeding, product gas chromatograph on-line analysis;
Embodiment 1
The present embodiment is for illustration of rare earth modified ZSM-5 molecular sieve Catalysts and its preparation method provided by the invention.
Take NaOH3.0g and TPAOH solution (30 % by weight) 45.0g, be dissolved in 300.0g distilled water, fully stir and obtain solution A; Getting 3.0g aluminum chloride is dissolved in 300.0g ethanol, fully stirs and obtains solution B; In solution A, dropwise add tetraethyl orthosilicate 114.6g, fully stir 10 minutes, obtain gel C; In gel C, dropwise drip solution B again, fully stir 30 minutes, obtain gel D, pH value is 11.Then gel D is proceeded in 1.5 liters of autoclaves, in 110 DEG C of static crystallizations 4 days.Products therefrom is through centrifugation, and in 110 DEG C of dryings 12 hours, then obtain small particle size ZSM-5 molecular sieve product (being denoted as E1) 26.2g in 550 DEG C of roastings, 8 hours removal template, silica alumina ratio is 50.
Under stirring and heated reflux condition, the ammonium nitrate solution of the 0.10mol/L of the E1 50mL of 8.2g is carried out ion-exchange 2 hours, again through centrifugation, distilled water wash, 150 DEG C of dryings 5 hours, 550 DEG C of roastings obtain Hydrogen small particle size ZSM-5 molecular sieve F1 for 8 hours;
Afterwards, with the lanthanum nitrate hexahydrate of the 0.05mol/L of 20mL dipping carry out ion-exchange, again through centrifugation, distilled water wash, 90 DEG C of dryings 15 hours, 550 DEG C of roasting 8h obtain the high silica alumina ratio small particle size ZSM-5 molecular sieve G1 of lanthanum modification;
The high silica alumina ratio small particle size ZSM-5 molecular sieve G1 of prepared lanthanum modification is carried out compressing tablet, then through broken, sieve that to obtain particle diameter be 10-20 molecules of interest sieve catalyst Cat-1.
As illustrated in fig. 1 and 2, XRD characterization result shows that gained molecular sieve is ZSM-5 molecular sieve to XRD and the SEM characterization result of molecular sieve E1, and SEM characterization result shows that molecular sieve is the small particle size molecular sieve of particle diameter within the scope of 200-250nm.Molecular sieve G1 characterizes through EDS, BET and TPD, and result shows the energy spectrogram (see figure 3) having obvious La in molecular sieve G1 near 2.01keV and 4.65keV, and the content of La is 0.36 % by weight; Specific surface area is 285m
2/ g, it is have charateristic avsorption band near 196 DEG C that ammonia temperature programming adsorption/desorption shows in temperature.
Embodiment 2
The present embodiment is for illustration of rare earth modified ZSM-5 molecular sieve Catalysts and its preparation method provided by the invention.
Take KOH 1.5g and n-Butyl Amine 99 24.0g, be dissolved in 135.0g distilled water, fully stir and obtain solution A; Get 1.80g Al (NO
3)
39H
2o is dissolved in 100.0g methyl alcohol, obtains solution B; In solution A, dropwise add quanmethyl silicate 145.0g, fully stir 10 minutes, fully stir and obtain gel C; In gel C, dropwise drip B solution again, fully stir 30 minutes, obtain gel D, pH value is 9.5.Then gel D is proceeded in 500 milliliters of spontaneous pressure stainless steel reaction tanks, in 150 DEG C of static crystallizations 2 days.Products therefrom is through centrifugal, separation, and in 110 DEG C of dryings 12 hours, then obtain small particle size ZSM-5 molecular sieve product (being denoted as E2) 45.5g in 400 DEG C of roastings, 15 hours removal template, silica alumina ratio is 400.
Under stirring and heated reflux condition, the ammonium chloride solution of the 0.05mol/L of the E2 100mL of 10.0g is carried out ion-exchange 1 hour, then after centrifugation, drying, within 5 hours, obtains Hydrogen small particle size ZSM-5 molecular sieve F2 in 700 DEG C of roastings.
Afterwards, under stirring and heated reflux condition, carry out ion-exchange with the cerous nitrate solution of the 0.03mol/L of 52mL, again after centrifugation, washing, drying, obtain cerium modified high silica alumina ratio small particle size ZSM-5 molecular sieve G2 in 550 DEG C of roasting 8h.
Prepared cerium modified high silica alumina ratio small particle size ZSM-5 molecular sieve G2 is carried out compressing tablet, then through broken, sieve that to obtain particle diameter be 10-20 molecules of interest sieve catalyst Cat-2.
XRD and Fig. 1 of molecular sieve E2 is identical, and SEM characterization result is as Fig. 4, and molecular sieve particle diameter is 150-300nm.Molecular sieve G2 characterizes through EDS, BET and TPD, and result shows the energy spectrogram (see figure 5) having obvious Ce in molecular sieve G2 near 2.01keV and 4.84keV, and the content of Ce is 1.52 % by weight; Specific surface area is 316m
2/ g, it is have charateristic avsorption band near 176 DEG C that ammonia temperature programming adsorption/desorption shows in temperature.
Experimental example 3
The present embodiment is for illustration of rare earth modified ZSM-5 molecular sieve Catalysts and its preparation method provided by the invention.
Take NaOH 1.0g and TPAOH solution (40 % by weight) 30.0g, be dissolved in 160.0g distilled water, fully stir and obtain solution A; Get 1.2g Al
2(SO
4)
318H
2o is dissolved in 60.0g propyl carbinol, obtains solution B; In solution A, dropwise add tetraethyl orthosilicate 72.0g, fully stir 10 minutes, obtain gel C; In gel C, dropwise drip B solution again, fully stir 30 minutes, obtain gel D, pH value is 12.Then gel D is proceeded in 500 milliliters of spontaneous pressure stainless steel reaction tanks, in 90 DEG C of static crystallizations 7 days.Products therefrom is through centrifugal, separation, and in 110 DEG C of dryings 12 hours, then obtain small particle size ZSM-5 molecular sieve product (being denoted as E3) 17.6g in 550 DEG C of roastings, 8 hours removal template, silica alumina ratio is 200.
Under stirring and heated reflux condition, the salpeter solution of the 0.15mol/L of the E3 25mL of 5.0g is carried out ion-exchange 3 hours, then after centrifugation, drying, within 8 hours, obtains Hydrogen small particle size ZSM-5 molecular sieve F3 in 550 DEG C of roastings.
Afterwards, under stirring and heated reflux condition, carry out ion-exchange with the lanthanum nitrate hexahydrate of the 0.08mol/L of 27mL, again after centrifugation, washing, drying, obtain the high silica alumina ratio small particle size ZSM-5 molecular sieve G3 of lanthanum modification in 550 DEG C of roasting 8h.
The high silica alumina ratio small particle size ZSM-5 molecular sieve G3 of prepared lanthanum modification is carried out compressing tablet, then through broken, sieve that to obtain particle diameter be 10-20 molecules of interest sieve catalyst Cat-3.
XRD and Fig. 1 of molecular sieve E3 is identical, and SEM characterization result is as Fig. 6, and molecular sieve particle diameter is 200-300nm.Molecular sieve G3 characterizes through EDS, BET and TPD, and result shows to have near 2.01keV and 4.65keV in molecular sieve G3 the energy spectrogram of obvious La (spectrogram and Fig. 3 similar), and the content of La is 3.92 % by weight; Specific surface area is 300m
2/ g, it is have charateristic avsorption band near 186 DEG C that ammonia temperature programming adsorption/desorption shows in temperature.
Embodiment 4
The present embodiment is for illustration of rare earth modified ZSM-5 molecular sieve Catalysts and its preparation method provided by the invention.
Rare earth modified ZSM-5 molecular sieve catalyzer Cat-4 is prepared according to the method identical with embodiment 1.Unlike, join in solution A by disposable for organosilicon source, solution B divided and disposablely join in gel C, the difference of the molecular sieve of gained and the molecular sieve of embodiment gained is, it is 100-500nm that SEM characterizes molecular sieve particle diameter, and specific surface area is 210m
2/ g.
Embodiment 5
The present embodiment is for illustration of rare earth modified ZSM-5 molecular sieve Catalysts and its preparation method provided by the invention.
Rare earth modified ZSM-5 molecular sieve catalyzer Cat-5 is prepared according to the method identical with embodiment 3.Unlike, the consumption of lanthanum nitrate hexahydrate makes the content of lanthanum in ZSM-5 molecular sieve catalyzer be 0.1 % by weight, and other characteristics are identical.
Embodiment 6
The present embodiment is for illustration of rare earth modified ZSM-5 molecular sieve Catalysts and its preparation method provided by the invention.
Rare earth modified ZSM-5 molecular sieve catalyzer Cat-6 is prepared according to the method identical with embodiment 3.Unlike, described rare earth element is praseodymium element.
Test case 1
The rare earth modified ZSM-5 molecular sieve catalyzer that this test case is prepared for illustration of the present invention is to the catalytic effect of isopropanol dehydration propylene.
In 6 continuously feeding fixed bed stainless steel tube reactors, be respectively charged into catalyzer Cat-1, Cat-2, Cat-3, Cat-4, Cat-5 and Cat-6 prepared by 2.00g embodiment 1-6.Thinner is nitrogen, in mole, Virahol: (Virahol+nitrogen) is 0.3:1.Reaction pressure is normal pressure, and temperature of reaction is 240 DEG C, and the weight space velocity of Virahol is 0.5h
-1, iso-propanol conversion rate is respectively 99.5%, 99.6%, 99.8%, 99.3%, 99.2% and 99%; Propylene Selectivity is respectively 98.5%, 98.4%, 98.1%, 97.8%, 97.8% and 97.7%.
Test case 2
The rare earth modified ZSM-5 molecular sieve catalyzer that this test case is prepared for illustration of the present invention is to the catalytic effect of isopropanol dehydration propylene.
In 6 continuously feeding fixed bed stainless steel tube reactors, be respectively charged into catalyzer Cat-1, Cat-2, Cat-3, Cat-4, Cat-5 and Cat-6 prepared by 2.00g embodiment 1-6.Thinner is nitrogen, in mole, Virahol: (Virahol+nitrogen) is 0.7:1.Reaction pressure is normal pressure, and temperature of reaction is 260 DEG C, and the weight space velocity of Virahol is 1h
-1, iso-propanol conversion rate is respectively 99.8%, 99.7%, 99.9%, 99.4%, 99.2% and 99.1%; Propylene Selectivity is respectively 98.1%, 98.2%, 98.4%, 97.5%, 97.3% and 97.2%.
Test case 3
The rare earth modified ZSM-5 molecular sieve catalyzer that this test case is prepared for illustration of the present invention is to the catalytic effect of isopropanol dehydration propylene.
In 6 continuously feeding fixed bed stainless steel tube reactors, be respectively charged into catalyzer Cat-1, Cat-2, Cat-3, Cat-4, Cat-5 and Cat-6 prepared by 2.00g embodiment 1-6.Do not add thinner.Reaction pressure is normal pressure, and temperature of reaction is 280 DEG C, and the weight space velocity of Virahol is 2h
-1, iso-propanol conversion rate is respectively 99.9%, 100%, 100%, 99.4%, 99.3% and 99.1%; Propylene Selectivity is respectively 98.4%, 98.8%, 98.6%, 97.5%, 98.1% and 97.7%.
Test case 4
The rare earth modified ZSM-5 molecular sieve catalyzer that this test case is prepared for illustration of the present invention is to the catalytic effect of isopropanol dehydration propylene.
The preparation of propylene is carried out according to the condition identical with EXPERIMENTAL EXAMPLE 1, unlike, the temperature of reaction is 360 DEG C.Iso-propanol conversion rate is 100%, and Propylene Selectivity is respectively 97.1%, 97.2%, 97.0%, 96.4%, 96.1% and 96.4%.
In following contrast test example example, the ZSM-5 molecular sieve of Zn modification be according to (reaction of an acidic catalyst catalysis isopropanol dehydration propylene, Industrial Catalysis, 2011,19(5) such as Liu Chunyan, 40-44) in method be prepared and obtain.
Contrast test example 1-4
The preparation of propylene is carried out respectively according to the method for test case 1-4, unlike, the catalyzer used in each contrast test example is ZSM-5 molecular sieve and the aluminium sesquioxide of Zn modification.
In contrast test example 1, iso-propanol conversion rate is respectively 52.5% and 72%; Propylene Selectivity is respectively 97.2% and 86.4%;
In contrast test example 2, iso-propanol conversion rate is respectively 75.6% and 80%; Propylene Selectivity is respectively 97.8% and 88%.
In contrast test example 3, iso-propanol conversion rate is respectively 98.5% and 85.2%; Propylene Selectivity is respectively 93.0% and 94.1%.
In contrast test example 4, iso-propanol conversion rate is 100%; Propylene Selectivity is respectively 40.2% and 97.5%.
As can be seen from above embodiment and comparative example and test result, the acidity on the silica alumina ratio of rare earth modified ZSM-5 molecular sieve, particle diameter, specific surface area and surface is controlled within the scope of the invention, in lower temperature range, namely can be transformed into propylene by the isopropanol dehydration of catalysis efficiently, had significant raising compared to the catalytic efficiency of the ZSM-5 molecular sieve of existing Zn modification.And adopt existing aluminium sesquioxide to find out, at a lower temperature, it is all lower to the selectivity of the transformation efficiency of Virahol and propylene, only has and at high temperature just shows good catalytic performance.
More than describe the preferred embodiment of the present invention in detail; but the present invention is not limited to the detail in above-mentioned embodiment, within the scope of technical conceive of the present invention; can carry out multiple simple variant to technical scheme of the present invention, these simple variant all belong to protection scope of the present invention.
It should be noted that in addition, each the concrete technical characteristic described in above-mentioned embodiment, in reconcilable situation, can be combined by any suitable mode.In order to avoid unnecessary repetition, the present invention illustrates no longer separately to various possible array mode.
In addition, also can carry out arbitrary combination between various different embodiment of the present invention, as long as it is without prejudice to thought of the present invention, it should be considered as content disclosed in this invention equally.
Claims (15)
1. a rare earth modified ZSM-5 molecular sieve catalyzer, is characterized in that, in this molecular sieve catalyst, the silica alumina ratio of described rare earth modified ZSM-5 molecular sieve is 50-400:1, and particle diameter is 100-500nm, and specific surface area is 160-350m
2/ g; NH
3-TPD characterized by techniques has feature adsorption peak at 170-200 DEG C.
2. molecular sieve catalyst according to claim 1, wherein, with the gross weight of described rare earth modified ZSM-5 molecular sieve catalyzer for benchmark, the content of rare earth element is 0.1-8 % by weight.
3. molecular sieve catalyst according to claim 1 and 2, wherein, described rare earth element is one or more in lanthanum, cerium, praseodymium and neodymium.
4. prepare a method for rare earth modified ZSM-5 molecular sieve catalyzer, the method comprises:
(1) template is mixed with mineral alkali in water obtain solution A;
(2) aluminium source is mixed with alcoholic solvent obtain solution B;
(3) organosilicon source mixes with solution A and obtains gel C;
(4) gel C is mixed with solution B obtain gel D;
(5) described gel D is carried out solid-liquid separation, drying and roasting successively after crystallization under crystallization condition, obtain ZSM-5 molecular sieve;
(6) ZSM-5 molecular sieve and mineral acid and/or the solution containing ammonium ion are carried out ion-exchange, and the material after ion-exchange is carried out solid-liquid separation, drying and roasting successively;
(7) carry out rare earth modified to the product after the roasting obtained in step (6).
5. method according to claim 4, wherein,
In step (1), described template is one or more in TPAOH, 4-propyl bromide and n-Butyl Amine 99, and described mineral alkali is sodium hydroxide and/or potassium hydroxide;
In step (2), described aluminium source is one or more in Tai-Ace S 150, aluminum nitrate, aluminum chloride and aluminum isopropylate; Described alcoholic solvent is one or more in methyl alcohol, ethanol and propyl carbinol;
In step (3), described organosilicon source is quanmethyl silicate and/or tetraethyl orthosilicate.
6. the method according to claim 4 or 5, wherein,
In step (1), the mass ratio of described template and mineral alkali is 1-20:1; The mass ratio of described template and water is 0.01-0.3:1;
In step (2), the mass ratio of described aluminium source and alcoholic solvent is 0.001-0.03:1;
In step (3), the mass ratio of described organosilicon source and solution A is 0.1-1.5:1;
In step (4), described gel C and solution B mass ratio are 1-10:1.
7. according to the method in claim 4-6 described in any one, wherein,
In step (3), joined several times in solution A in organosilicon source, each add-on is 0.04-0.06g;
In step (4), solution B joined several times in gel C, each add-on is 0.04-0.06g.
8. method according to claim 4, wherein, in step (5), the condition of described crystallization comprises: the temperature of crystallization is 90-150 DEG C, and the time of crystallization is 1-10 days.
9. method according to claim 4, wherein, in step (6), described mineral acid is nitric acid and/or hydrochloric acid; The described solution containing ammonium ion is one or more in ammonium nitrate solution, ammonium chloride solution and Spirit of Mindererus; The concentration of described mineral acid or ammonium ion is 0.05-0.15mol/L.
10. method according to claim 4, wherein, in step (7), rare earth modified process comprises: the product after the roasting obtained in step (6) and the solution containing rare earth ion are carried out ion-exchange, and the product after ion-exchange is carried out solid-liquid separation, drying and roasting successively;
Preferably, the concentration of the described solution Rare Earth Ion containing rare earth ion is 0.03-0.08mol/L;
Preferably, rare earth element is one or more in lanthanum, cerium, praseodymium and neodymium.
11. methods according to claim 10, wherein, the consumption of the described solution containing rare earth ion makes the described rare earth modified ZSM-5 molecular sieve catalyzer prepared contain the rare earth element of 0.1-8 % by weight.
12. according to the method in claim 4-11 described in any one, and wherein, the method also comprises: carry out compressing tablet and fragmentation to through rare earth modified ZSM-5 molecular sieve, obtains rare earth modified ZSM-5 molecular sieve catalyzer.
13. 1 kinds of isopropanol dehydrations prepare the method for propylene, the method comprises: in continuous fixed-bed reactor, take Virahol as raw material, add or do not add thinner, propylene is prepared in reaction in the presence of a catalyst, it is characterized in that, the ZSM-5 molecular sieve catalyzer that described catalyzer is prepared for the method in the ZSM-5 molecular sieve catalyzer in claim 1-3 described in any one or claim 4-12 described in any one.
14. methods according to claim 13, wherein, react under the condition adding thinner, and described thinner is nitrogen and/or water; Relative to the Virahol of 1mol, the consumption of described thinner is 0.4-2.3mol.
15. methods according to claim 13 or 14, wherein, the condition of described reaction comprises: the mass space velocity of Virahol is 0.5-2h
-1, the temperature of reaction is 200-480 DEG C, is preferably 200-360 DEG C, most preferably is 240-280 DEG C.
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