CN104117388B - A kind of SAPO-11/ZSM-5 mixed molecular sieve catalyst and preparation thereof and application - Google Patents
A kind of SAPO-11/ZSM-5 mixed molecular sieve catalyst and preparation thereof and application Download PDFInfo
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Abstract
The invention provides a kind of SAPO-11/ZSM-5 mixed molecular sieve catalyst, this catalyst comprises the SAPO-11 molecular sieve of 0.1-40 weight % and the ZSM-5 molecular sieve of 60-99.9 weight %. Present invention also offers a kind of method preparing this SAPO-11/ZSM-5 mixed molecular sieve catalyst, described method includes aluminum source, silicon source, template, SAPO-11 molecular sieve, water and optional pH adjusting agent are mixed to form raw slurry; Then carry out aging; By the described raw slurry crystallization under hydrothermal conditions after aging. Present invention also offers the method using this catalyst to be prepared gasoline by methanol feedstock. The content of isoparaffin in product gasoline can be significantly improved by the catalyst of the present invention, obtain high-octane gasoline products.
Description
Technical field
The present invention relates to chemical industry synthesis field, be more particularly to a kind of SAPO-11/ZSM-5 mixed molecular sieve catalyst, the preparation method of this catalyst, and use this catalyst by the method for methanol feedstock synthetic gasoline.
Background technology
Methanol is a kind of important basic organic chemical raw material, all has and have been widely used in the industries such as chemical industry, medicine, light industry, weaving. Acceleration consumption and exhaustion day by day along with world petroleum resource, world energy sources structure is faced with great adjustment, the alternative energy source that sight will just progressively be transferred to beyond oil by people, wherein prepares chemicals with methanol for raw material and fuel becomes an emerging focus. Significantly high yield of gasoline can be obtained with the route that methanol prepares gasoline for raw material, and gasoline products quality is higher, thus increasingly receive the concern of people.
First preparing gasoline by methanol (MTG) technique succeeded in developing by Mobil company, and realized industrialization in 1979 in New Zealand. The technique of Mobil takes two-part conversion process. Wherein there is condensation reaction in the first paragraph so that methanol dehydration forms dimethyl ether, this first paragraph can use the condensation catalyst of routine, for instance the fluoropolymer resin etc. of sulfonic acid functional. Enter second stage reactor from the equilibrium mixture of first paragraph methanol out, dimethyl ether and water, under the effect of ZSM-5 molecular sieve catalyst, generate gasoline component and liquefied gas component.
In order to improve the performance of gasoline product, people's catalyst to using has carried out various improvement, and in a large amount of reports, the catalyst used is mainly various modified and unmodified ZSM-5 molecular sieve.
CN102513142A reports and nano level ZSM-5 molecular sieve is carried out acid treatment, then shaping of catalyst is carried out, under hydrothermal conditions the catalyst of molding is carried out burin-in process subsequently, by catalyst is carried out above process, it is possible to make the yield of gasoline product reach 36-37%.
CN102049293A reports the binary structure zeolite of a kind of modified ZSM-5/AlPO4-5, and with phosphorus and at least one transition metal, this binary structure zeolite is modified.It is reported, this catalyst can obtain the gasoline selective of 68%.
CN102861608A discloses a kind of MCM-48 and ZSM-5 composite molecular sieve catalyst. This catalyst adopts two one-step hydrothermals to make molecular screen primary powder, then carries out acid treatment, finally by itself and binding agent kneading and compacting. This catalyst can improve the hydrocarbon distribution in the gasoline product that MTG technique prepares, and reduces carbon distribution, thus improve the stability of catalyst.
CN101186313 discloses the ZSM-5 molecular sieve catalyst of a kind of little crystal grain containing zirconium. Using this catalyst to prepare gasoline with methanol for raw material and can obtain the yield of gasoline of 90%, and catalyst shows splendid anti-carbon performance, single pass life is more than 1000 hours.
Up to now, the yield of gasoline of MTG technique still has greatly improved space, and meanwhile, the isoparaffin content in gasoline products is generally on the low side, if improving isoparaffin content to will assist in the octane number significantly improving oil product.
In view of this, it is necessary to a kind of new catalyst of exploitation, being used for improving yield of gasoline, improving isoparaffin content in gasoline, thus improving the octane number of oil product simultaneously.
Summary of the invention
In order to solve the above-mentioned technical problem that this area exists, the present inventor is by furtheing investigate, develop a kind of SAPO-11/ZSM-5 mixed molecular sieve catalyst, this mixed molecular sieve catalyst can effectively improve the yield of gasoline of MTG technique, the content of isoparaffin in gasoline product can also be significantly improved, thus substantially increasing the octane number of oil product simultaneously.
The first aspect of the invention provides a kind of mixed molecular sieve catalyst, in reference count for the gross weight of described mixed molecular sieve catalyst, this catalyst comprises the SAPO-11 molecular sieve of 0.1-40 weight % and the ZSM-5 molecular sieve of 60-99.9 weight %, SiO in described ZSM-5 molecular sieve2And Al2O3Mol ratio be 10-200; SiO in described SAPO-11 molecular sieve2The mol ratio that molar content is 0-10%, P elements and aluminium element be P:Al=0.6-1.
The second aspect of the invention provides a kind of method preparing described mixed molecular sieve catalyst, said method comprising the steps of:
(1) aluminum source, silicon source, template, SAPO-11 molecular sieve, water and optional pH adjusting agent are mixed to form raw slurry;
(2) described raw slurry is carried out aging;
(3) by the described raw slurry crystallization under hydrothermal conditions after aging.
In an embodiment of the invention, SiO in the SAPO molecular sieve used in step (1)2The mol ratio that molar content is 0-10%, P elements and aluminium element be P:Al=0.6-1; Described pH adjusting agent is selected from NaOH, KOH, Na2CO3、NaHCO3, and combination in any.
In yet another embodiment of the present invention, described aging at room temperature carry out 1-10 hour, more preferably 1-5 hour; The temperature of described hydrothermal condition is 130-180 DEG C, more preferably 160-180 DEG C, under this hydrothermal condition crystallization 1-120 hour, more preferably 1-96 hour; After step (3), the product also step (3) prepared washs, dries, roasting, and sintering temperature is 300-600 DEG C, it is preferable that 400-550 DEG C, and roasting time is 1-20 hour, it is preferable that 8-14 hour.
In yet another embodiment of the present invention, in described raw slurry, the mol ratio of various components is as follows:
SiO2/Al2O3=10-220:1;
Na2O/SiO2=0.1-0.5:1;
Template/SiO2=0.05-0.5:1;
H2O/SiO2=5-50:1;
SAPO-11/SiO2=0.01-0.6:1;
The pH value of the raw slurry that step (1) prepares is 11-13.
In yet another embodiment of the present invention, described silicon source is selected from: tetraethyl orthosilicate, positive n-propyl silicate, positive isopropyl silicate, the positive butyl ester of positive silicic acid, Ludox, waterglass, white carbon, and combination in any.
In yet another embodiment of the present invention, source of aluminium is selected from: aluminum isopropylate., sodium aluminate, aluminium hydroxide, aluminum sulfate, aluminum nitrate, aluminum chloride, and combination in any.
In yet another embodiment of the present invention, described template is selected from: n-butylamine, triethylamine, ethylenediamine, TPAOH, and combination in any.
The third aspect of the invention provides a kind of method preparing gasoline for raw material with methanol, and the method includes, at reaction conditions so that methanol vapor contacts with the mixed molecular sieve catalyst of the present invention, thus reacting generation gasoline product. Preferably, described method carries out in fixed bed reactors or fluidized-bed reactor, and described reaction condition is as follows: reaction temperature is 100-500 DEG C, it is preferable that 250-500 DEG C, more preferably 300-450 DEG C; Reaction pressure is 0.1-10MPa; Methanol feed liquid air speed is 0.1-20 hour-1, it is preferred to 0.1-10 hour-1, more preferably 0.1-5 hour-1。
The present invention is further elaborated by the examples below.
Figure of description
Fig. 1 shows the XRD figure of the SAPO-11/ZSM-5 catalyst prepared according to one embodiment of the present invention.
Detailed description of the invention
" scope " disclosed herein is with the form of lower limit and the upper limit. Can respectively one or more lower limits, and one or more upper limit. Given range is defined by a selected lower limit and a upper limit. Selected lower limit and the upper limit define the border of special scope. All scopes that can be defined by this way comprise and can be combined, and namely any lower limit can form a scope with the combination of any upper limit. Such as, list the scope of 60-120 and 80-110 for special parameter, be interpreted as that the scope of 60-110 and 80-120 also expects. If additionally, the minimum zone value 1 and 2 listed, and if list maximum magnitude value 3,4 and 5, then scope below can all expect: 1-3,1-4,1-5,2-3,2-4 and 2-5.
In the present invention, unless otherwise indicated, numerical range " a-b " represents that the breviary of any real combinings between a to b represents, wherein a and b is real number. Such as numerical range " 0-5 " represents the whole real numbers all listing between " 0-5 " herein, and the breviary that " 0-5 " is these combinations of values represents.
Without particularly pointing out, the term " two kinds " used by this specification refers to " at least two ".
In the present invention, without special explanation, all embodiments mentioned in this article and preferred implementation can be mutually combined and form new technical scheme.
In the present invention, without special explanation, all technical characteristics mentioned in this article and preferred feature can be mutually combined and form new technical scheme.
In the present invention, without special explanation, mentioned in this article can sequentially carry out in steps, it is also possible to carry out at random, but preferably order carries out. Such as, described method includes step (a) and (b), represents that described method can include step (a) and (b) that order carries out, it is also possible to include step (b) and (a) that order carries out.Such as, described mention described method and may also include step (c), represent that step (c) random order can join described method, such as, described method can include step (a), (b) and (c), may also comprise step (a), (c) and (b), it is also possible to include step (c), (a) and (b) etc.
In the present invention, without special explanation, " including " mentioned in this article represents open, it is also possible to be closed. Such as, described " including " can expression can also comprise other elements do not listed, it is also possible to only includes the element listed.
The method of the present invention is the fabricated in situ ZSM-5 when there is SAPO-11 molecular sieve, thus obtaining SAPO-11/ZSM-5 mixed molecular sieve catalyst. Specifically, the present invention specifically includes following steps for the method preparing mixed molecular sieve:
(1) aluminum source, silicon source, template, SAPO-11 molecular sieve, water and optional pH adjusting agent are mixed to form raw slurry;
(2) described raw slurry is carried out aging;
(3) by the described raw slurry crystallization under hydrothermal conditions after aging;
(4) washing, dry, roasting, prepare SAPO-11/ZSM-5 mixed molecular sieve catalyst.
The silicon source that the present invention uses can be silicon-containing material commonly used in the art, it will be preferred that selected from tetraethyl orthosilicate, positive n-propyl silicate, positive isopropyl silicate, the positive butyl ester of positive silicic acid, Ludox, waterglass, white carbon, and combination in any. Ludox be silicon dioxide microparticle be suspended in water formed colloid, its granularity can be 10-100 nanometer, and the solids content in colloid reaches as high as 40 weight %. Waterglass is the hydrate of alkali silicate, and its molecular formula can write R2O·nSiO2, R in formula2O is alkali metal oxide, and n is the ratio of your number of silicon dioxide and alkali metal oxide, and modal alkali metal is sodium. White carbon is the general name of white powder amorphous silica and silicate product, is primarily referred to as precipitated silica, aerosil, superfine silicon dioxide gel etc. White carbon is porous material, the available SiO of its composition2·nH2O represents, wherein nH2O exists with the form of surface hydroxyl.
The aluminum source that the present invention uses can be any salt containing aluminum, it is preferable that selected from aluminum isopropylate., sodium aluminate, aluminium hydroxide, aluminum sulfate, aluminum nitrate, aluminum chloride, and combination in any. Other aluminum source known in the art can also be used as required.
The organic formwork agent that the present invention uses can include aminated compounds and/or organic ammonium compounds. Preferably, described organic formwork agent is selected from n-butylamine, triethylamine, ethylenediamine, TPAOH and combination in any thereof. By properly selecting kind and the content of organic formwork agent, it is possible to carry out effectively regulating and controlling to the microcosmic pore passage structure of zeolite.
SAPO-11 is a class silicoaluminophosphamolecular molecular sieves, is synthesized in 1984 by Lok et al. the earliest, and its skeleton is elementary composition by Si, P, Al and O four kinds, it is possible to regards as and uses Si to replace P and/or Al in imaginary aluminum phosphate skeleton and formed. This kind of molecular sieve is mesothyrid molecular sieve, forms oval duct by one-dimensional ten-ring. In described SAPO-11 molecular sieve, the content of Si can change in very wide scope, one of the present invention preferred embodiment in, the SiO in described SAPO-11 molecular sieve2Molar content can be 0-10%. In yet another embodiment of the present invention, in described SAPO-11 molecular sieve, the mol ratio of P elements and aluminium element is P:Al=0.6-1.
By controlling the consumption in silicon source and aluminum source in raw material, it is possible to effectively regulate the ratio shared by ZSM-5 molecular sieve and the silica alumina ratio in ZSM-5 molecular sieve in final mixed molecular sieve catalyst. In one preferred embodiment, in described step (1), the raw slurry of preparation has following mol ratio composition:
SiO2/Al2O3=10-220:1;
Na2O/SiO2=0.1-0.5:1;
Template/SiO2=0.05-0.5:1;
H2O/SiO2=5-50:1;
SAPO-11/SiO2=0.01-0.6:1;
The pH value of described raw slurry is 11-13.
At this it is important to note that SiO in above scale relation2、Al2O3、Na2O only refers to the material of the silicon source that derives from, aluminum source and optional pH adjusting agent, and the silicon comprised in SAPO-11, aluminum and sodium element is not counted. In other words, the various oxide components comprised in SAPO-11 totally represent with " SAPO-11 ", and do not count SiO2、Al2O3And Na2The mole of O. It addition, the water in this raw slurry is from not only the water being individually added into, but also it is probably derived from silicon source and aluminum source. Additionally, above scale relation is the form that Si, Al, Na element existed in system is all scaled oxide represents, these elements are actually likely to exist with the form of various salt or hydroxide, and this kind of representation is the way that molecular sieve art is conventional.
So that the raw slurry prepared has required pH value, it is also possible to be optionally added thereto to pH adjusting agent, for instance NaOH, KOH, Na2CO3、NaHCO3, and combination in any. In some embodiments, by selecting composition and the consumption of the raw material such as silicon source, aluminum source, just can so that the raw slurry prepared has required pH value, in the case, it is not necessary to add pH adjusting agent. In other embodiment, in addition it is also necessary to it is possible to additionally incorporate pH adjusting agent, so that raw slurry has required pH value.
The Na comprised in described raw slurry2O can derive from aluminum source, silicon source and pH adjusting agent. Such as, in one preferred embodiment, when the silicon source using the waterglass etc. of suitably composition and concentration containing sodium time, it is possible to required silicon and sodium are provided with silicon source simultaneously. Another preferred embodiment in, by it is possible to additionally incorporate NaOH in described raw slurry, thus introducing sodium.
In embodiments of the present invention, it is accelerate gelatinization that the raw slurry prepared carries out aging effect. In this ageing process, form activated gel, convenient follow-up crystallization steps. Preferably, this Aging Step at room temperature carries out. It is highly preferred that described aging lasting 1-10 hour, it is most preferred that 1-5 hour.
Hydrothermal crystallizing operation is in the reactor sealed, and carries out under high-temperature and high-pressure conditions. In crystallization process under hydrothermal conditions, described silicon source, aluminum source form the crystal unit structure of ZSM-5 molecular sieve under the effect of template, and the temperature of described hydrothermal condition is 130-180 DEG C, more preferably 160-180 DEG C, and now water is superheated steam state; The crystallization persistent period is 1-120 hour, more preferably 1-96 hour.
Described roasting is at the temperature of 300-600 DEG C, preferred 400-550 DEG C, carries out 1-20 hour, it is preferable that 8-14 hour in heating furnace. By steps such as washing above, dry and roastings, remove and be included on catalyst surface and template within pore passage structure and various impurity.
By the said method fabricated in situ ZSM-5 SAPO-11/ZSM-5 mixed molecular sieve catalyst prepared, compared with the catalyst prepared with directly ZSM-5 and SAPO-11 molecular sieve being mixed mutually, can cross-link with SAPO-11 when ZSM-5 prototype structure is formed, form composite construction, both close contacts, influence each other, thus in catalytic reaction, more effectively change product composition, contribute to generating isohydrocarbon.In other words, in the mixed molecular sieve catalyst of SAPO-11/ZSM-5 of the present invention, ZSM-5 and SAPO-11 is cross-linked with each other, thus effectively improving the catalytic performance of this kind of catalyst.
One of the present invention preferred embodiment in, in reference count for the gross weight of described mixed molecular sieve catalyst, this catalyst comprises the SAPO-11 molecular sieve of 0.1-40 weight % and the ZSM-5 molecular sieve of 60-99.9 weight %, SiO in described ZSM-5 molecular sieve2And Al2O3Mol ratio be 10-200; SiO in described SAPO-11 molecular sieve2Molar content be 0-10%, the mol ratio of P elements and aluminium element is P:Al=0.6-1.
One of the present invention preferred embodiment in, first the mixed molecular sieve catalyst of the present invention is carried out ion exchange, make ZSM-5 molecular sieve therein and SAPO-11 molecular sieve all become hydrogen type molecular sieve, be then used further to prepare with methanol for raw material the reaction of gasoline.
Further illustrate the preferred embodiment of the present invention below by specific embodiment, but protection scope of the present invention is not limited only to this. By the preferred embodiment of the present invention being carried out various change or combination, under the premise of the protection domain limited without departing from claims of the present invention, it is thus achieved that other embodiment of the present invention, can still be capable of similar technique effect.
Embodiment
In the examples below, unless otherwise indicated, the water otherwise used is deionized water, and the chemical reagent of use is analytical pure. Ludox is silica concentration is the Ludox of 30 weight %, solid particle mean diameter 15 nanometers, pH value=9; Dioxide-containing silica in the solid particle of white carbon > 99.9 weight %.
Embodiment 1
According to following mol ratio preparation raw material serosity: SiO2:Al2O3:Na2O: n-butylamine: SAPO-11:H2O=1:0.013:0.50:0.15:0.3:50. weigh 0.87 gram of aluminum sulfate, be dissolved in 30 ml deionized water and form solution, in this solution, then add 1.1 grams of n-butylamines and 4.0 grams of sodium hydroxide, mixing and stirring, wiring solution-forming A, then weigh 20 grams of Ludox, be added thereto to 45 ml deionized water, wiring solution-forming B, B is joined in A and is uniformly mixed, obtain colloid C, continue stirring 0.5 hour. then 1.8 grams of SAPO-11(Si:Al:P (mol ratio)=1:10:9 are weighed) join in colloid C, stir aging 1.5 hours at ambient temperature, then material is proceeded in stainless steel cauldron, seal this reactor, heating is to 180 DEG C, crystallization 72 hours under this hydrothermal condition, it is quickly cooled to room temperature afterwards, by product centrifugation, it is washed with water to the pH value < 8 of supernatant, transferred product is entered in infrared baking oven, 6 hours are processed to be baked at 120 DEG C, then transfer the sample in Muffle furnace, roasting 12 hours under the air atmosphere of 550 DEG C. this sample is carried out XRD sign, result as it is shown in figure 1, wherein in 2 θ=23.19,24.04,24.53 etc. the characteristic diffraction peak signals observing ZSM-5 molecular sieve, it was demonstrated that be synthetically derived ZSM-5, in 2 θ=20.96,21.81,26.69 etc. the characteristic diffraction peak signals observing SAPO-11 molecular sieve.
Embodiment 2
According to following mol ratio preparation raw material serosity: SiO2:Al2O3:Na2O: ethylenediamine: SAPO-11:H2O=1:0.009:0.52:0.18:0.25:45. Weigh 0.60 gram of aluminum sulfate, be dissolved in 30 ml deionized water and form solution, in this solution, add 1.08 grams of ethylenediamines and 4.16 grams of sodium hydroxide mixing and stirring, wiring solution-forming A;Then weigh 6 grams of white carbons, add 50 ml deionized water, be made into suspension B, B is joined in A and is uniformly mixed, obtain colloid C, continue stirring 0.5 hour. then 1.5 grams of SAPO-11(Si:Al:P (mol ratio)=1:10:9 are weighed) join in colloid C, while being kept stirring at room temperature aging 1.5 hours, material is proceeded in stainless steel cauldron, seal this reactor, heating is to 180 DEG C, crystallization 72 hours under this hydrothermal condition, it is quickly cooled to room temperature afterwards, by product centrifugation, it is washed with water to the pH value < 8 of supernatant, transferred product is entered in infrared baking oven, 6 hours are processed to be baked at 120 DEG C, then transfer the sample in Muffle furnace, roasting 12 hours under the air atmosphere of 550 DEG C. this sample is carried out XRD sign, and result is similar with Fig. 1, in 2 θ=23.19,24.04,24.53 etc. the characteristic diffraction peak signals observing ZSM-5 molecular sieve, it was demonstrated that be synthetically derived ZSM-5, in 2 θ=20.96,21.81,26.69 etc. the characteristic diffraction peak signals observing SAPO-11 molecular sieve.
Embodiment 3
According to following mol ratio preparation raw material serosity: SiO2:Al2O3:Na2O: TPAOH: SAPO-11:H2O=1:0.012:0.53:0.18:0.3:50. Weigh 0.25 gram of aluminum isopropylate., be dissolved in 40 ml deionized water and form solution, in this solution, add the TPAOH aqueous solution of 14.64 gram of 25 weight % and 4.24 grams of sodium hydroxide and mix, stirring, wiring solution-forming A; Then weigh 6 grams of white carbons, add 38 ml deionized water, be made into suspension B; B is joined in A and is uniformly mixed, obtain colloid C, continue stirring 0.5 hour. Then 1.8 grams of SAPO-11(Si:Al:P (mol ratio)=1:10:9 are weighed) join in colloid C, continue stirring, aged at room temperature 1.5 hours, this material is proceeded in stainless steel cauldron, seal this reactor, heating is to 180 DEG C, crystallization 96 hours under this hydrothermal condition, it is quickly cooled to room temperature afterwards, by product centrifugation, is washed with water to the pH value < 8 of supernatant, transferred product is entered in infrared baking oven, at 120 DEG C, process 6 hours to be baked to, then transfer the sample in Muffle furnace, roasting 12 hours under the air atmosphere of 550 DEG C. This sample is carried out XRD sign, and result is similar with Fig. 1, in 2 θ=23.19,24.04,24.53 etc. the characteristic diffraction peak signals observing ZSM-5 molecular sieve, it was demonstrated that be synthetically derived ZSM-5; In 2 θ=20.96,21.81,26.69 etc. the characteristic diffraction peak signals observing SAPO-11 molecular sieve.
Embodiment 4
First the embodiment 1-3 catalyst prepared is carried out ion exchange. Concretely comprise the following steps at 80 DEG C, use the ammonium nitrate solution of 0.1mol/L according to solid-liquid weight ratio 1:10, catalyst ion to be exchanged 2 hours, filter, repeat exchange 3 times. The last time after ion exchange, filtered sample, transferred product is entered in infrared baking oven, at 120 DEG C, process 6 hours to be baked to, then transfer the sample in Muffle furnace, roasting 6 hours under the air atmosphere of 500 DEG C.
Catalyst breakage after roasting is sieved as 20-40 order.
Weigh 8 grams of Catalyst packings to enter in the rustless steel fixed bed reactors that internal diameter is 10mm, at reaction conditions, pass into methanol vapor wherein, to react. Concrete reaction condition is: reaction temperature: 385 DEG C, pressure: 0.3Mpa, the liquid air speed of methanol: 1.5h-1.Methanol enters preheater by constant-flux pump in liquid form, and the temperature of preheater is 260 DEG C, makes methanol liquid gasification form steam in this preheater, and then insulation entrance reactor reacts. Product uses gas chromatogram to carry out on-line analysis when insulation, and gas chromatogram adopts PLOTQ capillary column and hydrogen flame detector, and the temperature in gas chromatograph is 180 DEG C.
Comparative example 1
In comparative example 1, prepare catalyst by the step described in embodiment 1, be distinctive in that and do not add SAPO-11. This sample is carried out XRD sign, in 2 θ=23.19,24.04,24.53 etc. the characteristic diffraction peak signals observing ZSM-5 molecular sieve, it was demonstrated that be synthetically derived ZSM-5. Then using this catalyst, the step described in embodiment 4 carries out ion exchange and catalytic reaction.
Comparative example 2
The SAPO-11 that this comparative example 2 uses mol ratio to be Si:Al:P=1:10:9, the step described in embodiment 4 carries out ion exchange and catalytic reaction.
Comparative example 3
In this comparative example, it is separately synthesized first ZSM-5, then it is mixed with SAPO-11, be used for the catalytic effect with embodiment 1 gained catalyst and contrast. Concretely comprise the following steps:
According to following mol ratio preparation raw material serosity: SiO2:Al2O3:Na2O: n-butylamine: H2O=1:0.013:0.50:0.15:50. Weigh 0.87 gram of aluminum sulfate, be dissolved in 30 ml deionized water and form solution, in this solution, then add 1.1 grams of n-butylamines and 4.0 grams of sodium hydroxide, mixing and stirring, wiring solution-forming A; Then weigh 20 grams of Ludox, be added thereto to 45 ml deionized water, be made into colloid B; B is joined in A and is uniformly mixed, obtain colloid C, continue stirring 0.5 hour. Stir aging 1.5 hours at ambient temperature, then proceeding in stainless steel cauldron by material, seal this reactor, heating is to 180 DEG C, crystallization 72 hours under this hydrothermal condition, it is quickly cooled to room temperature afterwards, by product centrifugation, is washed with water to the pH value < 8 of supernatant, transferred product is entered in infrared baking oven, at 120 DEG C, process 6 hours to be baked to, then transfer the sample in Muffle furnace, roasting 12 hours under the air atmosphere of 550 DEG C. This sample is carried out XRD sign, in 2 θ=23.19,24.04,24.53 etc. the characteristic diffraction peak signals observing ZSM-5 molecular sieve, it was demonstrated that be synthetically derived ZSM-5.
Weigh 1.8 grams of SAPO-11(Si:Al:P=1:10:9 subsequently) catalyst, it is added in whole ZSM-5 that above step prepares, uses mortar that it is ground halfhour grinding and mix.
Prepared catalyst is carried out ion exchange and catalytic reaction by the method described in embodiment 4.
The reaction result of above example and comparative example collects and is listed in table 1 below.
Table 1
* note: yield of gasoline=C5 +The quality * 100 of quality/methanol
From the result of upper table it will be seen that compared with the comparative example 1 being used alone ZSM-5 catalyst, the catalyst of the present invention can significantly improve the content of isoparaffin in oil product, this octane number being conducive to significantly improving product oil product, improve its anti-knock properties. This is because the acidity of ZSM-5 is significantly high, individually uses ZSM-5 catalyst, methanol conversion and yield of gasoline all high, but isoparaffin content is low. And compared with the comparative example 2 being used alone SAPO-11, the catalyst of the present invention can significantly improve methanol conversion and yield of gasoline, the selectivity of isoparaffin in product is better than SAPO-11 catalyst by catalyst of the present invention too.
Meanwhile, compared with comparative example 3, the catalyst of the present invention is also all significantly improved in the selectivity of methanol conversion, yield of gasoline and isoparaffin. Limit without wishing to by concrete theory, it is the fabricated in situ ZSM-5 when there is SAPO-11 that the applicant speculates that its reason is likely due to embodiments of the invention, the ZSM-5 process formed will necessarily make a degree of mutual crosslinking between the structure of ZSM-5 and SAPO-11 structure, the characteristic such as distribution and pore passage structure in two kinds of molecular sieve acid sites can be brought special impact, thus affecting the performances such as its catalysis activity, selectivity. By comparison, comparative example 3 is only that molecular sieves different for both is carried out simple physical mixed, and is absent from above-described influencing each other, and therefore wants inferior many in catalysis activity and selectivity.
As can be seen here, the present invention is by the situ synthesis of ZSM-5 when there is SAPO-11 molecular sieve, define a kind of novel unique bimolecular sieve nest system, two kinds of molecular sieves in this system influence each other, create significant synergism, prepare the bimolecular sieve catalyst system with splendid catalysis activity and selectivity of product.
Claims (12)
1. the method preparing mixed molecular sieve catalyst, said method comprising the steps of:
(1) aluminum source, silicon source, template, SAPO-11 molecular sieve, water and optional pH adjusting agent are mixed to form raw slurry;
(2) described raw slurry is carried out aging;
(3) by the described raw slurry crystallization under hydrothermal conditions after aging;
In reference count for the gross weight of described mixed molecular sieve catalyst, this mixed molecular sieve catalyst comprises the SAPO-11 molecular sieve of 0.1-40 weight % and the ZSM-5 molecular sieve of 60-99.9 weight %, SiO in described ZSM-5 molecular sieve2And Al2O3Mol ratio be 10-200; SiO in described SAPO-11 molecular sieve2Molar content be 0-10%, the mol ratio of P elements and aluminium element is P:Al=0.6-1.
2. the method for claim 1, it is characterised in that SiO in the SAPO molecular sieve used in step (1)2Molar content be 0-10%, the mol ratio of P elements and aluminium element is P:Al=0.6-1 (mole); Described pH adjusting agent is selected from NaOH, KOH, Na2CO3、NaHCO3, and combination in any.
3. the method for claim 1, it is characterised in that described aging at room temperature carry out 1-10 hour; The temperature of described hydrothermal condition is 130-180 DEG C, under this hydrothermal condition crystallization 1-120 hour; After step (3), the product also step (3) prepared washs, dries, roasting, and sintering temperature is 300-600 DEG C, and roasting time is 1-20 hour.
4. the method for claim 1, it is characterised in that described aging at room temperature carry out 1-5 hour; The temperature of described hydrothermal condition is 160-180 DEG C, under this hydrothermal condition crystallization 1-96 hour; After step (3), the product also step (3) prepared washs, dries, roasting, and sintering temperature is 400-550 DEG C, and roasting time is 8-14 hour.
5. the method for claim 1, it is characterised in that in described raw slurry, the mol ratio of various components is as follows:
SiO2/Al2O3=10-220:1;
Na2O/SiO2=0.1-0.5:1;
Template/SiO2=0.05-0.5:1;
H2O/SiO2=5-50:1;
SAPO-11/SiO2=0.01-0.6:1;
The pH value of the raw slurry that step (1) prepares is 11-13.
6. the method for claim 1, it is characterised in that described silicon source is selected from: tetraethyl orthosilicate, positive n-propyl silicate, positive isopropyl silicate, the positive butyl ester of positive silicic acid, Ludox, waterglass, white carbon, and combination in any.
7. the method for claim 1, it is characterised in that source of aluminium is selected from: aluminum isopropylate., sodium aluminate, aluminium hydroxide, aluminum sulfate, aluminum nitrate, aluminum chloride, and combination in any.
8. the method for claim 1, it is characterised in that described template is selected from: n-butylamine, triethylamine, ethylenediamine, TPAOH, and combination in any.
9. the method preparing gasoline with methanol for raw material, the method includes, at reaction conditions so that methanol vapor is contacted with the mixed molecular sieve catalyst prepared by the method according to any one of claim 1-8, thus reacting generation gasoline product.
10. method as claimed in claim 9, it is characterised in that described method carries out in fixed bed reactors or fluidized-bed reactor, and described reaction condition is as follows: reaction temperature is 100-500 DEG C; Reaction pressure is 0.1-10MPa; Methanol feed liquid air speed is 0.1-20 hour-1。
11. method as claimed in claim 9, it is characterised in that described method carries out in fixed bed reactors or fluidized-bed reactor, and described reaction condition is as follows: reaction temperature is 250-500 DEG C; Reaction pressure is 0.1-10MPa; Methanol feed liquid air speed is 0.1-10 hour-1。
12. method as claimed in claim 9, it is characterised in that described method carries out in fixed bed reactors or fluidized-bed reactor, and described reaction condition is as follows: reaction temperature is 300-450 DEG C; Reaction pressure is 0.1-10MPa; Methanol feed liquid air speed is 0.1-5 hour-1。
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