CN104828842A - Preparation method of SAPO-5 and SAPO-34 symbiotic composite molecular sieve - Google Patents
Preparation method of SAPO-5 and SAPO-34 symbiotic composite molecular sieve Download PDFInfo
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Abstract
The invention discloses a preparation method of an SAPO-5/SAPO-34 composite molecular sieve. The SAPO-5 and SAPO-34 symbiotic composite molecular sieve is obtained through a one-time hydrothermal synthesis and crystallization step, wherein natural or synthetic clay type mineral matter with a molar ratio of SiO2/Al2O3 of 0.05-1.5 or a mixture of the mineral matters is used as a silicon source and aluminum source complex. A large amount of macropores and mesopores in an SAPO-5 molecular sieve effectively makes up the insufficient number of macropores and mespores in an SAPO-34 molecular sieve, so when the composite molecular sieve is used to catalyze a reaction for preparing low carbon olefins from organic oxygen-containing compounds, the yield of propylene and the yield of butylene are improved.
Description
Technical field
The present invention relates to a kind of preparation method by the composite molecular screen of SAPO-5 molecular sieve and the symbiosis of SAPO-34 molecular sieve.
Background technology
The catalytic material that methanol to olefins reaction uses is mainly the acid zeolite of aperture and mesopore.Nineteen eighty-two, union carbide corporation of the U.S. (UCC) scientist Wilson S T and Flanigen E M is that template has synthesized novel aluminum phosphate molecule sieve first with organic amine in hydrothermal system, subsequently, has the AlPO of aperture, mesoporous and macropore
4-n series of micropores molecular sieve occurs in succession.1984, first Si was introduced AlPO by the people such as Lok
4in Series Molecules sieve, synthesize a class new aluminosilicophosphate (SAPO-n) molecular sieve, this molecular sieve analog includes 13 kinds of three dimensional skeletal structure be made up of tetrahedron, and have the pore passage structure from six-ring to twelve-ring, aperture is between 0.3 ~ 0.8nm.Silicoaluminophosphamolecular molecular sieve (SAPO-n) is by [SiO
4], [AlO
4]
-[PO
4]
+the microporous crystal with aperture, mesopore or macropore that three kinds of tetrahedron elements are formed, wherein, n represents different crystalline structure.
SAPO-34 micro porous molecular sieve has three dimensional intersection duct, and mean pore size is about 0.38-0.43nm.SAPO-34 has less aperture, and during its catalyzer as methanol to olefins reaction, reaction easily generates micromolecular ethene and propylene.Because SAPO-34 molecular sieve has suitable Bronsted acidity and pore passage structure, larger specific surface area, good absorption property and good hydrothermal stability, it presents good catalytic activity and selectivity to methanol to olefins reaction, usually can to reach the selectivity of low-carbon alkene or close to 90%, at present, SAPO-34 molecular sieve is the optimal catalyst promoting methanol to olefins reaction.
But, in reaction for preparing light olefins from methanol, though SAPO-34 shows ethene and the more excellent product selectivity of propylene as micro porous molecular sieve, but in reaction process, easily form carbon distribution fast and make rapid catalyst deactivation.
Usually, micro porous molecular sieve has regular microvoid structure, suitable acidity, good hydrothermal stability, but micro porous molecular sieve also can generate comparatively macromole in reaction process, narrow duct very easily induce reaction thing and product mass transfer diffusional resistance excessive, inside, reactant crystal duct extremely difficult to get access is reacted, and product is out also comparatively difficult from duct internal divergence, thus, exacerbate the coking of molecular sieve catalyst duct, and cause catalyst deactivation.
For methanol to olefins reaction, molecular sieve inside diffusional resistance have impact on the rate of diffusion of reactant and product; Generate target product-alkene in the cage of molecular sieve after, alkene is in the process of external diffusion, hydrogen transfer reactions can be there is further in the acidic site in molecular sieve, generate by product alkane or polymerization reaction take place generation Jiao, this reduces the selectivity of object product-alkene, and cause catalyzer coking and deactivation.
Above-mentioned situation may be cause the one of the main reasons of SAPO-34 molecular sieve catalyst fast deactivation, therefore, the appropriate molecular sieve with macropore and/or meso-hole structure is introduced in SAPO-34 molecular sieve, effectively will alleviate reactant and the mass transfer diffusional resistance of product in molecular sieve pore passage, and then, reduce the carbon deposition rate of SAPO-34 molecular sieve, extend the work-ing life of SAPO-34 molecular sieve and catalyzer thereof, even increase the selectivity of low-carbon alkene, such as propylene and butylene.
CN102049294B discloses molecular sieve of a kind of composite structure and its preparation method and application, in fact, it is a kind of AlPO-5/SAPO-34 composite molecular screen, in the preparation process of this composite molecular screen, SAPO-34 molecular sieve is incorporated in the raw material of preparation AlPO-5 molecular sieve and goes, the composite molecular screen that final formation is synthesized by AlPO-5 and SAPO-34.When this composite molecular screen is used for organic oxygen-containing compound reaction for preparing light olefins, because AlPO-5 has macropore and/or the meso-hole structure of some amount, the work-ing life of molecular sieve catalyst is extended to some extent, and adds the selectivity of propylene.But in above-mentioned AlPO-5/SAPO-34 composite molecular screen, AlPO-5 and SAPO-34 is not obviously symbiosis.
CN103011195A discloses a kind of method that a step prepares the multi-stage porous molecular sieve of SAPO-5 and the SAPO-34 symbiosis of Hydrogen.Wherein, except using a kind of template, also use a kind of tensio-active agent, the silicon source of use is tetraethoxy, silicon sol, water glass, white carbon black or their arbitrary mixtures; The aluminium source used is pseudo-boehmite, pseudobochmite, Alumina gel, aluminum isopropylate, aluminate, activated alumina or their arbitrary mixtures, and these materials as raw material are expensive, make the production cost of composite molecular screen higher.
CN102372290A discloses a kind of synthetic method of SAPO-5 and SAPO-34 coexisting molecular sieve.Wherein, the silicon source used also is tetraethoxy, silicon sol, water glass, white carbon black or their arbitrary mixtures, and the aluminium source of use is also pseudo-boehmite, pseudobochmite, Alumina gel, aluminum isopropylate, aluminate, activated alumina or their arbitrary mixtures.Also there is expensive raw material price, problem that composite molecular screen production cost is higher in this synthetic method.
The present invention is devoted to the defect overcoming existing SAPO-34 molecular sieve, and strive developing a kind of preparation method by the composite molecular screen of SAPO-5 and SAPO-34 symbiosis, wherein, the complex body in wide material sources and cheap silicon source and aluminium source is used to replace silicon source costly and aluminium source, to reach the object reducing composite molecular screen production cost, simultaneously, the reaction table of composite molecular screen to organic oxygen-containing compound producing light olefins of SAPO-5 and the SAPO-34 symbiosis prepared by the inventive method reveals good catalytic activity, higher propylene and/or butylene selectivity, with the work-ing life of excellence.
Summary of the invention
According to a first aspect of the invention, provide a kind of preparation method of composite molecular screen of SAPO-5 and SAPO-34 symbiosis, it comprises the following steps successively:
(1) in proportion phosphorus source and water, silicon source and aluminium source complex body and water, template and water are mixed at 5 DEG C of-90 DEG C of temperature, obtain comprising the mixing solutions of phosphorus source, silicon source and aluminium source complex body, water and template, in above-mentioned mixing solutions, P
2o
5: SiO
2: Al
2o
3: H
2o: the mol ratio of template is (0.5-1.5): (0.05-1.5): 1:(30-100): (1-5);
(2) stir above-mentioned mixing solutions until each component disperses is even, subsequently, ageing leaves standstill described mixing solutions 2-24 hour, thus, form mixed gel;
(3) described mixed gel is made to carry out Hydrothermal Synthesis crystallization 24-96 hour at 180 DEG C-220 DEG C, thus, form crystallization liquid;
(4) from described crystallization liquid, be separated the solid crystal thing that crystallization is formed, then at 80 DEG C-120 DEG C dry described solid crystal thing 2-12 hour, obtain the former powder of composite molecular screen of SAPO-5 and SAPO-34 symbiosis;
(5) the former powder 4-10 hour of the above-mentioned composite molecular screen of roasting at 450-650 DEG C, to remove template wherein, thus, obtain the composite molecular screen by SAPO-5 molecular sieve and the symbiosis of SAPO-34 molecular sieve.
Usually, in above-mentioned preparation method, described template is tetraethyl ammonium hydroxide, etamon chloride, tetraethylammonium bromide, triethylamine, diethylamine, ammoniacal liquor, n-Butyl Amine 99, morpholine or their arbitrary mixtures; Described silicon source and aluminium source complex body are SiO
2/ Al
2o
3the clay minerals matter of the natural or synthesis of molar ratio range between 0.05-1.5 or their arbitrary mixtures; Described phosphorus source is phosphoric acid, phosphorous acid, phosphoric acid salt and/or phosphorous oxides; Described water is deionized water.
Usually, in above-mentioned preparation method, in step (4), the solid crystal thing that separation crystallization is formed refers to: the solid crystal thing that centrifuging is formed, to remove the crystallisate mother liquor that Hydrothermal Synthesis crystallization produces, with solid crystal thing described in deionized water wash at least one times, then solid crystal thing described in centrifuging is at least one times.
Preferably, in above-mentioned preparation method, by controlling phosphorus source, the relative usage of silicon source and aluminium source complex body, template and water, hybrid mode and/or feeding sequence, and then control pore passage structure and the acidity of described composite molecular screen.
Preferably, in above-mentioned preparation method, described mixing solutions is prepared by the following method:
(1) silicon source and aluminium source complex body and phosphorus source are mixed with water respectively, form silicon source and aluminium source complex solution and phosphorus source solution;
(2) lentamente phosphorus source solution be added drop-wise in silicon source and aluminium source complex solution or silicon source and aluminium source complex solution are added drop-wise in the solution of phosphorus source, forming the mixing solutions of phosphorus source, silicon source and aluminium source complex body;
(3) in the mixing solutions of described phosphorus source, silicon source and aluminium source complex body, described template is added again, thus, form the mixing solutions comprising phosphorus source, silicon source, aluminium source, water and template.
Preferably, in above-mentioned preparation method, described silicon source and aluminium source complex body are kaolin, diatomite, illiteracy holder soil, talcum, wilkinite, one of aluminium vanadine or their arbitrary mixtures, and affiliated silicon source and aluminium source complex body require to reach SiO
2/ Al
2o
3molar ratio range between 0.05-1.5, or has specific SiO
2/ Al
2o
3mol ratio, such as SiO
2/ Al
2o
3the SiO of molar ratio range between 0.05-1.5
2and Al
2o
3synthetic mixture.
According to a second aspect of the invention, provide a kind of catalyzer of organic oxygen-containing compound producing light olefins, the catalytic active component of described catalyzer is the composite molecular screen of SAPO-5 and the SAPO-34 symbiosis prepared by aforesaid method.
Preferably, described organic oxygen-containing compound is methyl alcohol and/or dme; Described low-carbon alkene is ethene, propylene and/or butylene.
Accompanying drawing explanation
Fig. 1 is the X-ray diffracting spectrum of SAPO-5/SAPO-34 composite molecular screen of the present invention.
Embodiment
By being further explained in detail the present invention below with reference to the description of embodiment and accompanying drawing, but below describe only for enabling general technical staff of the technical field of the invention clearly understand principle of the present invention and marrow, and do not mean that any type of restriction is carried out to the present invention.
Preferably, the present invention by SAPO-5 molecular sieve and the symbiosis of SAPO-34 molecular sieve the preparation method of composite molecular screen, comprise the following steps successively:
(1) in proportion phosphorus source and water, silicon source and aluminium source complex body and water, template and water are mixed at 5 DEG C of-90 DEG C of temperature, obtain comprising the mixing solutions of phosphorus source, silicon source and aluminium source complex body, water and template, in above-mentioned mixing solutions, P
2o
5: SiO
2: Al
2o
3: H
2o: the mol ratio of template is (0.5-1.5): (0.05-1.5): 1:(30-100): (1-5);
(2) stir above-mentioned mixing solutions until each component disperses is even, subsequently, ageing leaves standstill described mixing solutions 2-24 hour, thus, form mixed gel;
(3) described mixed gel is made to carry out Hydrothermal Synthesis crystallization 24-96 hour at 180 DEG C-220 DEG C, thus, form crystallization liquid;
(4) from described crystallization liquid, be separated the solid crystal thing that crystallization is formed, then at 80 DEG C-120 DEG C dry described solid crystal thing 2-12 hour, obtain the former powder of composite molecular screen of SAPO-5 and SAPO-34 symbiosis;
(5) the former powder 4-10 hour of the above-mentioned composite molecular screen of roasting at 450-650 DEG C, to remove template wherein, thus, obtain the composite molecular screen by SAPO-5 molecular sieve and the symbiosis of SAPO-34 molecular sieve.
The composite molecular screen of SAPO-5 and the SAPO-34 symbiosis prepared by above-mentioned preparation method can be used as the catalytic active component of the catalyzer of organic oxygen-containing compound producing light olefins.
The composite molecular screen of SAPO-5 and SAPO-34 prepared by the inventive method and the preferred working conditions of catalyzer as follows: temperature of reaction: 300-500 DEG C, preferred 400-500 DEG C; Reaction pressure: 0-0.5MPa; Methanol quality air speed: 1.0-5.0/ hour; Under this working conditions, methanol conversion is close to 100%; Ethene+propylene+butylene yield > 75%; Propylene+butylene yield > 52%; SAPO-5/SAPO-34 composite molecular screen work-ing life, SAPO-5/SAPO-34 composite molecular sieve catalyst work-ing life was more than 2 hours more than 200 minutes.
Embodiment
Embodiment 1: the SAPO-5/SAPO-34 composite molecular screen of preparation symbiosis
Choose amorphous silicon aluminium powder purchased from German Sa Suo factory as the complex body in silicon source and aluminium source, its trade name is SIRAL40, SiO
2/ Al
2o
3weight ratio is 2:3, and its mol ratio is 1.13, and specific surface area is 500m
2/ g.
By 12 grams of above-mentioned amorphous silicon aluminium powder (SIRAL40) and 64.5 grams of deionized water mix and blends, form the slurries of silicon source and aluminium source complex body, slowly drip the phosphoric acid that 20 grams of concentration are 85 % by weight wherein again, uniform stirring 1.5 hours, forms the mixed serum in silicon source and aluminium source complex body and phosphorus source.
Then, in above-mentioned mixed serum, add 14.5 grams of triethylamines (template), ageing 2 hours under whipped state, thus form mixed gel.
In above-mentioned mixed serum, P
2o
5: SiO
2: Al
2o
3: H
2o: the mol ratio of template is 1.24:1.13:1:51.4:2.
It is in the stainless steel cauldron of tetrafluoroethylene (teflon) that above-mentioned mixed gel is loaded inner bag, carries out Hydrothermal Synthesis crystallization 48 hours at 200 DEG C, forms crystallization liquid.
After the cooling of crystallization still, separate solid crystallized product from crystallization liquid, solid crystallized product is again through deionized water wash and centrifuging, until the specific conductivity of scavenging solution is at 200 below μ S/cm, then at 120 DEG C by dry for body crystallized product 8 hours, thus the former powder of the composite molecular screen obtaining SAPO-5 and SAPO-34 symbiosis.
Subsequently, in air atmosphere and at 650 DEG C, the former powder of roasting above-mentioned SAPO-5 and SAPO-34 composite molecular screen 5 hours, obtains SAPO-5 and SAPO-34 composite molecular screen.
Comparative example 1: the SAPO-5/SAPO-34 composite molecular screen of preparation symbiosis
Except 12 grams of above-mentioned amorphous silicon aluminium powder (SIRAL40) being used the silicon sol (silicon source) of equimolar amount and pseudo-boehmite (aluminium source) and replace, repeat the process of embodiment 1, obtain SAPO-5 and SAPO-34 composite molecular screen.
Embodiment 2: the SAPO-5/SAPO-34 composite molecular screen of preparation symbiosis
Adopt the purity that is purchased be more than 99% kaolin and aluminium vanadine be mixed with SiO
2/ Al
2o
3mol ratio is the kaolin of 43% and the mixed powder of aluminium vanadine as the complex body in silicon source and aluminium source, and its specific surface area is 550m
2/ g.
By the mixed powder of 15 grams of above-mentioned kaolin and aluminium vanadine and 85 grams of deionized water mix and blends, form the slurries of silicon source and aluminium source complex body, slowly drip the phosphoric acid that 25 grams of concentration are 85 % by weight wherein again, uniform stirring 1.5 hours, form the mixed serum in silicon source and aluminium source complex body and phosphorus source.
Then, in above-mentioned mixing solutions, add 16.5 grams of triethylamines (template), ageing 2 hours under whipped state, thus form mixed gel.
In above-mentioned mixing solutions, P
2o
5: SiO
2: Al
2o
3: H
2o: the mol ratio of template is 0.61:0.43:1:33.7:1.16.
It is in the stainless steel cauldron of tetrafluoroethylene (teflon) that above-mentioned mixed gel is loaded inner bag, carries out Hydrothermal Synthesis crystallization 48 hours at 200 DEG C, forms crystallization liquid.
After the cooling of crystallization still, separate solid crystallized product from crystallization liquid, solid crystallized product is again through deionized water wash and centrifuging, until the specific conductivity of scavenging solution is at 200 below μ S/cm, then at 120 DEG C by dry for body crystallized product 8 hours, thus the former powder of the composite molecular screen obtaining SAPO-5 and SAPO-34 symbiosis.
Subsequently, in air atmosphere and at 600 DEG C, the former powder of roasting above-mentioned SAPO-5 and SAPO-34 composite molecular screen 6 hours, obtains SAPO-5 and SAPO-34 composite molecular screen.
Test case
The X-ray diffraction (XRD) of test case 1:SAPO-5 and SAPO-34 composite molecular screen is analyzed
X-ray diffraction (XRD) analysis is carried out to SAPO-5 and the SAPO-34 composite molecular screen obtained in embodiment 1, obtain Fig. 1, can find from Fig. 1: the XRD characteristic diffraction peak simultaneously having occurred SAPO-5 and SAPO-34 molecular sieve in the XRD spectra of the SAPO-5/SAPO-34 composite molecular screen obtained in embodiment 1, the chemically composited structure defining two kinds of molecular sieves is described.
The catalytic activity assessment of test case 2:SAPO-5 and SAPO-34 composite molecular screen
Adopt fixed bed catalyst evaluating apparatus, catalytic activity, selectivity of product and test in work-ing life are carried out to the molecular sieve obtained in embodiment 1-2 and comparative example 1.
After above-mentioned molecular sieve is carried out compressing tablet and fragmentation, it is that 20-40 object part is stand-by as sieve sample that sieve gets granularity.
Take 1.0 grams of above-mentioned sieve samples respectively, and respectively they are put into reactor, in 500 DEG C of downhill reaction devices, pass into nitrogen, activate above-mentioned molecular sieve 1 hour, then, temperature of reactor is down to 450 DEG C, methanol solution as raw material after flow metering pump, mix with carrier gas, and entering in preheating oven under nitrogen-carrier gas is carried, methyl alcohol is vaporized into gas in preheating oven, then, enter in reactor, under the katalysis of above-mentioned molecular sieve, carry out reaction for preparing light olefins from methanol.
In above process, nitrogen flow rate: 150 ml/min, methanol weight air speed: 3.0/ hour, reaction product adopts off-line gas-chromatography to carry out composition analysis, wherein, when occurring alcohol and ether in gas chromatogram, illustrate that methanol conversion has not been 100%, now, stop test, start to the time now as molecular sieve work-ing life to react.
Measure the reaction product composition of each experiment, and calculate each reaction product selectivity, and the transformation efficiency of ethene, propylene and butylene, they are represented in the following Table 1.
Table 1
As can be seen from Table 1: compared with existing SAPO-34 molecular sieve (comparative example 1), the SAPO-5/SAPO-34 composite molecular screen (embodiment 1) of symbiosis prepared by the inventive method equally also has excellent catalytic activity, and in methanol to olefins reaction, show good propylene and butylene selectivity.Particularly, along with the carrying out of reaction, the overall selectivity that the SAPO-5/SAPO-34 composite molecular screen of symbiosis prepared by the inventive method has more and more higher butylene selectivity and propylene and butylene also increases gradually.
The term that this specification sheets is used and form of presentation are only used as descriptive and nonrestrictive term and form of presentation, are not intended to by any equivalents thereof exclude of the feature that represents and describe or its integral part outside when using these terms and form of presentation.
Although show and described several embodiment of the present invention, the present invention has not been restricted to described embodiment.On the contrary; those skilled in the art should recognize can carry out any accommodation and improvement to these embodiments when not departing from principle of the present invention and spirit, and protection scope of the present invention determined by appended claim and equivalent thereof.
Claims (8)
1. a preparation method for the composite molecular screen of SAPO-5 and SAPO-34 symbiosis, it comprises the following steps successively:
(1) in proportion phosphorus source and water, silicon source and aluminium source complex body and water, template and water are mixed at 5 DEG C of-90 DEG C of temperature, obtain comprising the mixing solutions of phosphorus source, silicon source and aluminium source complex body, water and template, in above-mentioned mixing solutions, P
2o
5: SiO
2: Al
2o
3: H
2o: the mol ratio of template is (0.5-1.5): (0.05-1.5): 1:(30-100): (1-5);
(2) stir above-mentioned mixing solutions until each component disperses is even, subsequently, ageing leaves standstill described mixing solutions 2-24 hour, thus, form mixed gel;
(3) described mixed gel is made to carry out Hydrothermal Synthesis crystallization 24-96 hour at 180 DEG C-220 DEG C, thus, form crystallization liquid;
(4) from described crystallization liquid, be separated the solid crystal thing that crystallization is formed, then at 80 DEG C-120 DEG C dry described solid crystal thing 2-12 hour, obtain the former powder of composite molecular screen of SAPO-5 and SAPO-34 symbiosis;
(5) the former powder 4-10 hour of the above-mentioned composite molecular screen of roasting at 450-650 DEG C, to remove template wherein, thus, obtain the composite molecular screen by SAPO-5 molecular sieve and the symbiosis of SAPO-34 molecular sieve.
2. preparation method according to claim 1, wherein, described template is tetraethyl ammonium hydroxide, etamon chloride, tetraethylammonium bromide, triethylamine, diethylamine, ammoniacal liquor, n-Butyl Amine 99, morpholine or their arbitrary mixtures; Described silicon source and aluminium source complex body are SiO
2/ Al
2o
3the clay minerals matter of the natural or synthesis of molar ratio range between 0.05-1.5 or their arbitrary mixtures; Described phosphorus source is phosphoric acid, phosphorous acid, phosphoric acid salt and/or phosphorous oxides; Described water is deionized water.
3. preparation method according to claim 1, wherein, in step (4), the solid crystal thing that separation crystallization is formed refers to: the solid crystal thing that centrifuging is formed, to remove the crystallisate mother liquor that Hydrothermal Synthesis crystallization produces, with solid crystal thing described in deionized water wash at least one times, then solid crystal thing described in centrifuging is at least one times.
4. preparation method according to claim 1, wherein, by controlling phosphorus source, the relative usage of silicon source and aluminium source complex body, template and water, hybrid mode and/or feeding sequence, and then controls pore passage structure and the acidity of described composite molecular screen.
5. preparation method according to claim 1, wherein, described mixing solutions is prepared by the following method:
(1) silicon source and aluminium source complex body and phosphorus source are mixed with water respectively, form silicon source and aluminium source complex solution and phosphorus source solution;
(2) lentamente phosphorus source solution be added drop-wise in silicon source and aluminium source complex solution or silicon source and aluminium source complex solution are added drop-wise in the solution of phosphorus source, forming the mixing solutions of phosphorus source, silicon source and aluminium source complex body;
(3) in the mixing solutions of described phosphorus source, silicon source and aluminium source complex body, described template is added again, thus, form the mixing solutions comprising phosphorus source, silicon source, aluminium source, water and template.
6., according to one of any described preparation method of claim 1-5, wherein, described silicon source and aluminium source complex body are kaolin, diatomite, illiteracy holder soil, talcum, wilkinite, one of aluminium vanadine or their arbitrary mixtures, or have specific SiO
2/ Al
2o
3the SiO of mol ratio
2and Al
2o
3synthesising complex.
7. a catalyzer for organic oxygen-containing compound producing light olefins, the active ingredient of described catalyzer is by the composite molecular screen of SAPO-5 and the SAPO-34 symbiosis prepared according to one of any described method of claim 1-6.
8. catalyzer according to claim 7, wherein, described organic oxygen-containing compound is methyl alcohol and/or dme; Described low-carbon alkene is ethene, propylene and/or butylene.
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