CN104549483A - Adhesive-free SAPO-34/ZSM-5 composite molecular sieve and preparation method thereof - Google Patents
Adhesive-free SAPO-34/ZSM-5 composite molecular sieve and preparation method thereof Download PDFInfo
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Abstract
The invention relates to an adhesive-free SAPO-34/ZSM-5 composite molecular sieve and a preparation method thereof, which aim to solve the problems of complex process, high cost, large pollution, low activity of an adhesive-containing catalyst and low strength of an adhesive-free catalyst in preparation of a molecular sieve by a hydro-thermal synthesis method in the prior art. The problems are well solved through the adoption of the technical scheme that the preparation method comprises the following steps: firstly mixing a silicon source, an aluminum source, a phosphorus source and a ZSM-5 molecular sieve with water according to a certain proportion to form gel, crushing the gel into particles in certain sizes after being dried, and then placing the gel in steam containing an organic template agent to be crystallized at 120-220 DEG C for 24-100 hour to obtain the adhesive-free SAPO-34/ZSM-5 composite molecular sieve. The adhesive-free SAPO-34/ZSM-5 composite molecular sieve can be used in a reaction to prepare arene with methyl alcohol or dimethyl ether.
Description
Technical field
The present invention relates to a kind of binder free SAPO-34/ZSM-5 composite molecular screen and preparation method thereof.
Background technology
[0002] aromatic hydrocarbons, particularly such as BTX(benzene,toluene,xylene) light aromatics, be important basic organic chemical industry raw material.Along with global industry in recent years and economic development, the demand of aromatic hydrocarbons constantly increases.At present, the main source of aromatic hydrocarbons is naphtha reforming and pyrolysis gasoline hydrogenation process, and these two processes are all take oil as raw materials for production.But, along with the continuous consumption of petroleum resources and rising steadily of price, be that the aromatics production cost of raw material is unprecedented soaring with oil.Therefore, in the long run, be directly converted from methyl alcohol and prepare aromatic hydrocarbons, a very promising aromatics production route of can yet be regarded as.
The methanol conversion for preparing arene preformed catalyst of current report, is made up of the zeolite molecular sieve of such as ZSM-5, ZSM-11 or MCM-22 etc., binding agent and dehydrogenation active component and modification component usually.But due in moulding process, binding agent has wrapped up molecular sieve, and the effective rate of utilization of molecular sieve is declined, and the duct of moieties sieve is blocked, reactant and resultant diffusion is on a catalyst affected, and finally causes the activity of catalyzer and the selectivity of target product to decline.If the binding agent in catalyzer all or major part change into active principle molecular sieve and can overcome above problem.So-called binder free catalyzer is exactly after molecular sieve based catalyst forming, by crystallization again, added binding agent is changed into active principle molecular sieve, that overall preformed catalyst does not contain or only containing a small amount of binding agent, keeps catalyzer to have the intensity meeting industrial application simultaneously.In general, in Adhesive-free Molecular Sieve catalyzer, the mass content of binding agent is less than or equal to 5%.
ZSM-5 molecular sieve is a kind of micropore sial zeolite molecular sieve of ten-ring pore passage structure, pore diameter range is between 0.52 ~ 0.56nm, and there is larger specific surface, good duct shape selectivity, higher thermostability and hydrothermal stability, be suitable for the reactions such as the aromizing of alkane, isomerization, catalyzed oxidation, catalytic cracking and methanol oxidation hydrocarbon.Silicon aluminium phosphate (SAPO) molecular sieve of a kind of octatomic ring pore passage structure of SAPO-34 molecular sieve, orifice diameter is at about 0.43nm, under normal circumstances, SAPO-34 molecular sieve has the acidity stronger than ZSM-5 and better hydrothermal stability, is widely used in the reaction of preparing light olefins from methanol at present.Due to the respective aperture ratio of two kinds of molecular sieves more single, Acidity is different, is therefore suitable only for better simply reaction process separately, for the reaction system of some complexity, relies on independent a kind of molecular sieve not processed well.If both combinations are obtained a kind of composite molecular screen, then can play its multi-stage artery structure and the adjustable advantage of acidity, thus improve the reactive behavior of complex reaction system.
Methanol/dimethyl ether aromatic hydrocarbons is reacted, its reaction mechanism is divided into two steps, first be methyl alcohol dewater under acidic site effect generate dme, dme generates low-carbon alkene again under the effect of acidic site, and then low-carbon alkene generates aromatic hydrocarbons through complex processes such as oligomerisation, cyclisation, dehydrogenation, alkylation and de-alkyl.For first step, can be understood as reaction for preparing light olefins from methanol, the acidity that this reaction needed is stronger, add reaction raw materials and target product is all small molecules hydro carbons, SAPO-34 has been proved to be the molecular sieve being best suited for this reaction.For second step, can be understood as the aromatization process of low-carbon alkene, because the molecular diameter of aromatic hydrocarbons is larger, the SAPO-34 molecular sieve internal diffusion less in aperture is restricted, therefore SAPO-34 molecular sieve there is no aromatization activity, the duct size of ZSM-5 molecular sieve then just have matched the molecular size of benzene, toluene and dimethylbenzene, is applicable to very much the reaction that aromatization of hydrocarbons prepares aromatic hydrocarbons.SAPO-34 molecular sieve and ZSM-5 molecular sieve are combined, obtained composite molecular screen, then can play its synergy, obtain better reaction effect.
Document CN102372291A reports the preparation method of SAPO-18/SAPO-34 coexisting molecular sieve, solve single, the active not high problem of aperture of porous material of prior art synthesis, in the reaction of preparing light olefins from methanol, the catalyzer adopting this coexisting molecular sieve to prepare have catalyst deactivation speed slow advantage.
Document CN102372290A is also by synthesis condition, and by phosphorus source, aluminium source, silicon source and template mixing, hydrothermal crystallizing has synthesized SAPO-5/SAPO-34 coexisting molecular sieve.
Document CN101279743A then reports in Hydrothermal Synthesis process, add the crystal seed containing β zeolite precursor body, then adjust ratio and the hydrothermal synthesizing condition of various reactant, synthesize the coexisting molecular sieve at least containing ZSM-5 molecular sieve, mordenite and β zeolite three kinds of Symbiont phases.
Document CN102838128A then discloses the preparation method of a kind of mordenite/ZSM-5 coexisting molecular sieve, comprise: mineral alkali, aluminium source, silicon source are added mordenite crystal seed after fully mixing, through aging, crystallization, add silicon source, again crystallization again, products therefrom, through separation, washing, drying, obtains mordenite/ZSM-5 coexisting molecular sieve.
But, yet there are no the report of SAPO-34 and ZSM-5 composite molecular screen.
Summary of the invention
One of technical problem to be solved by this invention is that prior art adopts hydrothermal synthesis method to prepare molecular sieve process complexity, cost is higher, pollute larger, and it is active low and do not contain the problem of binder catalyst intensity difference containing binder catalyst, there is provided a kind of binder free SAPO-34/ZSM-5 composite molecular screen, this molecular sieve responds active high, and preparation process is simple, cost is low, pollutes little feature.
Two of technical problem to be solved by this invention is to provide a kind of preparation method of the binder free SAPO-34/ZSM-5 composite molecular screen corresponding with technical solution problem one.
Three of technical problem to be solved by this invention is to provide a kind of corresponding uses of above-mentioned binder free SAPO-34/ZSM-5 composite molecular screen.
In order to technical solution problem one, the technical solution used in the present invention is as follows: a kind of binder free SAPO-34/ZSM-5 composite molecular sieve catalyst, comprises with weight parts:
(1) 1 ~ 99 part of SAPO-34 molecular sieve;
The ZSM-5 molecular sieve of (2) 1 ~ 99 parts;
The binding agent of (3) 0 ~ 5 parts.
In technique scheme, the intensity of binder free composite molecular screen is greater than 40 Ns/, and wherein the diameter of every catalyzer is 1 ~ 5 millimeter, and length is 5 millimeters, can meet the requirement of industrial application.
In order to technical solution problem two, the technical solution used in the present invention is as follows: the preparation method of binder free SAPO-34/ZSM-5 composite molecular screen, comprises following step:
(1) silicon source, aluminium source, phosphorus source, ZSM-5 molecular sieve are mixed to form gel with water according to a certain percentage, in the butt of each material, mol ratio is: Al
2o
3: P
2o
5: SiO
2: ZSM-5=1:0.8 ~ 2.0:0.3 ~ 2.0:0.5 ~ 30.0;
(2), after gel drying, the particle be applicable to needed for reaction is broken into;
(3) particle of fragmentation is placed in the steam containing organic formwork agent, in 120 ~ 220 DEG C of crystallization 24 ~ 100h;
(4) product washing crystallization obtained, drying, roasting obtain binder free SAPO-34/ZSM-5 composite molecular screen.
In technique scheme, before step (1), first can modify ZSM-5 molecular sieve with metallic element, modifying method can be ion exchange method, also pickling process can be used, the form that ZSM-5 molecular sieve makes modified metal be converted into framework metal ion or metal oxide through super-dry, roasting is subsequently carried on ZSM-5 molecular sieve, and pickling process also can be adopted after step (4) at APO-34/ZSM-5 composite molecular screen load modified metal.Described metal-modified element is selected from least one in the periodic table of elements I B to VIII B and III A, at least one in preferred La, Ti, V, Cr, Mo, Mn, Fe, Co, Ni, Cu, Ag, Zn, Ga.Preparation process silicon source used is selected from least one in silicon sol, water glass, active silica, organosilicon.Aluminium source is selected from least one in pseudo-boehmite, aluminum isopropylate, activated alumina, aluminium salt.Phosphorus source is selected from least one in ortho-phosphoric acid, phosphorous acid, phosphoric acid salt.ZSM-5 molecular sieve can be H type ZSM-5, Na type ZSM-5, also can be at least one in the ZSM-5 after metallic element is modified, if select Na type ZSM-5, before catalyzer is used for reaction, it need be made to be transformed into H type ZSM-5 by ion-exchange.Organic formwork agent is selected from least one in tetraethyl ammonium hydroxide, triethylamine, morpholine.Prepare various raw material used, with the dry basis of each material, ratio is: Al
2o
3: P
2o
5: SiO
2: ZSM-5=1:0.8 ~ 1.6:0.3 ~ 1.0:0.5 ~ 20.0.
In order to technical solution problem three, the technical solution used in the present invention is as follows: a kind of method of methanol/dimethyl ether conversion aromatic hydrocarbons, and taking methanol aqueous solution as raw material, is 400 ~ 600 DEG C in temperature of reaction, reaction pressure is 0.01 ~ 5MPa, and methanol weight air speed is 0.5 ~ 15 h
-1, the mass ratio of water and methyl alcohol is under the condition of 0.1 ~ 5:1, and raw material is by beds, and the binder free SAPO-34/ZSM-5 composite molecular screen obtained with the present invention contacts, and generates aromatic hydrocarbons.
The present invention is by being first mixed to form gel with water according to a certain percentage by silicon source, aluminium source, phosphorus source, ZSM-5 molecular sieve, be placed on after gel drying in the steam containing organic formwork agent and carry out gas-solid inversion of phases, amorphous silicon in gel, aluminium and phosphorous oxides are changed into effective constituent molecular sieve, thus improve the content of catalyzer Middle molecule sieve, improve reactive behavior.Simultaneously, the SAPO-34/ZSM-5 composite molecular screen obtained, has multi-stage artery structure and the adjustable advantage of acidity, is more suitable for complicated reaction system than adopting separately a kind of molecular sieve, particularly methanol/dimethyl ether aromatic hydrocarbons reaction process, thus the reactive behavior improving complex reaction system.
Accompanying drawing explanation
Fig. 1 is the XRD diffracting spectrum of the composite molecular screen of synthesis,
Fig. 2 is the SEM picture of the composite molecular screen of synthesis.
Below by embodiment, the present invention is further elaborated, but the present invention is not limited in these embodiments.
Embodiment
[embodiment 1]
Take 10g HZSM-5 to mix with appropriate water, violent stirring forms slurries A1.Take 8g pseudo-boehmite, 13g ortho-phosphoric acid (85% wt), 12g silicon sol (40% wt) and appropriate water are mixed to form uniform gel B1.A1 and B1 mixed and stirs, being then placed in the baking oven evaporate to dryness of 120 DEG C.The solid crushing of evaporate to dryness is become 10 ~ 20 object particles, and be placed in the upper layer bracket of autoclave, then place the mixed solution of 10g water and 10g tetraethyl ammonium hydroxide in the lower floor of autoclave.Through 180 DEG C of crystallization 48h after airtight, product is through washing, drying, and 550 DEG C of roasting 4h remove a small amount of template and obtain binder free SAPO-34/ZSM-5 composite molecular screen.Adopting equi-volume impregnating, take zinc nitrate aqueous solution as steeping fluid, SAPO-34/ZSM-5 composite molecular screen floods the Zn element of 3%, makes catalyzer through super-dry, roasting.
Get the catalyzer that 9g above-mentioned binder free SAPO-34/ZSM-5 composite molecular screen makes and be placed in stainless steel fixed-bed reactor, be warmed up to 460 DEG C, methanol weight air speed 2h
-1, the mass ratio of water and methyl alcohol is 0.5:1, reaction pressure 0.02MPa, is then squeezed in reactor to contact with catalyzer by methanol aqueous solution with ram pump to react, and product obtains aromatic hydrocarbons through condensation separation, and reaction result lists in table 1.
[embodiment 2]
Compared with embodiment 1, the 10g HZSM-5 used instead in the ZSM-5 molecular sieve alternate embodiment 1 of 20g Zn ion-exchange obtains binder free SAPO-34/ZSM-5 composite molecular screen, thus omit the step of follow-up incipient impregnation weight content 3% Zn, all the other steps are identical with embodiment 1, and reaction result lists in table 1.
[embodiment 3]
Take 200g NaZSM-5 to mix with appropriate water, violent stirring forms slurries A3.Take 35g aluminum isopropylate, 25g ortho-phosphoric acid, 8g aluminium dihydrogen phosphate, 50g silicon sol and appropriate water are mixed to form uniform gel B3.A3 and B3 is mixed, under 80 DEG C of conditions, heats evaporate to dryness while stirring, and then put into 150 DEG C of oven drying 6h.Dried solid crushing is become 10 ~ 20 object particles.Get the above-mentioned particle of 100g and be placed in the upper layer bracket of autoclave, the mixed solution of 30g tetraethyl ammonium hydroxide, 30g triethylamine and 30g water is placed by lower floor.Through 200 DEG C of crystallization 48h after airtight, product is through washing, drying, and 550 DEG C of roasting 4h remove a small amount of template.Use the ammonium nitrate solution of 10% to exchange 2h under 90 DEG C of conditions the solid after roasting, washing, to filter, after repeating 2 times, by after washing, filtration, the solid that obtains is through super-dry, and 500 roasting 4h obtain binder free SAPO-34/ZSM-5 composite molecular screen.Take 10g binder free SAPO-34/ZSM-5 composite molecular screen, adopt equi-volume impregnating, take zinc nitrate aqueous solution as steeping fluid, SAPO-34/ZSM-5 composite molecular screen floods the Zn element of 3%, obtains binder free SAPO-34/ZSM-5 composite molecular sieve catalyst through super-dry, roasting.
The reactivity worth of catalyzer characterizes the method adopting embodiment 1, the results are shown in table 1.
[embodiment 4]
take 10 ~ 20 object solid particulates that 30g embodiment 3 obtains, the liquid that lower floor places is made into the mixed solution of 10g tetraethyl ammonium hydroxide, 10g morpholine and 10g water, all the other steps obtain binder free SAPO-34/ZSM-5 composite molecular screen with embodiment 3, and make catalyzer by the method for embodiment 3.
The reactivity worth of catalyzer characterizes the method adopting embodiment 1, the results are shown in table 1.
[embodiment 5]
Similar to embodiment 4, the mixed solution of 20g triethylamine, 10g morpholine and 10g water is adopted to replace the mixed solution of 10g tetraethyl ammonium hydroxide, 10g morpholine and 10g water, all the other steps are identical, obtain binder free SAPO-34/ZSM-5 composite molecular screen, and obtain catalyzer further.
The reactivity worth of catalyzer characterizes the method adopting embodiment 1, the results are shown in table 1.
[embodiment 6 ~ 13]
Take the binder free SAPO-34/ZSM-5 composite molecular screen that 10g embodiment 3 prepares, adopt equi-volume impregnating, respectively load weight content 1.0% La, 1.0% Ti, 1.0% V, 1.0% Cr, Co, the Mo of 1.0% of 1.0%, the Ag of the Mn of 1.0% and 0.5%, obtain binder free SAPO-34/ZSM-5 composite molecular sieve catalyst through super-dry, roasting.
The reactivity worth of catalyzer characterizes the method adopting embodiment 1, the results are shown in table 1.
[comparative example 1]
Take 16g pseudo-boehmite, 25g ortho-phosphoric acid (85% wt), 24g silicon sol (40% wt), 20g tetraethyl ammonium hydroxide mixes with appropriate water.Transfer in airtight high pressure crystallizing kettle after stirring, through washing, drying after 180 DEG C of crystallization 48h, 550 DEG C of roasting 4h remove a small amount of template, and product is accredited as pure phase SAPO-34 molecular sieve through X-ray diffraction.
Molecular sieve is adopted equi-volume impregnating, take zinc nitrate aqueous solution as the Zn of steeping fluid, load 3%, then through super-dry, roasting.Powder after roasting is obtained 10 ~ 20 object binder free SAPO-34 molecular sieve catalysts through compressing tablet, fragmentation, adopts the method for embodiment 1 to characterize its catalytic activity, the results are shown in table 1.
[comparative example 2]
the ZSM-5 molecular sieve of the Zn ion-exchange used in Example 2 obtains 10 ~ 20 object binder free SAPO-34 molecular sieve catalysts through compressing tablet, fragmentation, adopts the method for embodiment 1 to characterize its catalytic activity, the results are shown in table 1.
[comparative example 3]
take 10g SAPO-34,10g ZSM-5,8g pseudo-boehmite, 1g sesbania powder mix with appropriate dust technology all with, adopt the mode of extrusion shaping, after dry, roasting, be broken into 10 ~ 20 object particles.Adopt equi-volume impregnating, be steeping fluid with zinc nitrate aqueous solution, the Zn of load weight content 3% on particle, then obtains the agent of Methanol arenes catalytic through super-dry, roasting, and the reactivity worth evaluation of catalyzer adopts the method for embodiment 1, the results are shown in table 1.
Table 1
As can be seen from the table, in comparative example 1, the catalyzer that independent employing SAPO-34 molecular sieve obtains almost does not have aromatization activity, the catalyst activity adopting ZSM-5 molecular sieve to obtain separately in comparative example 2 is not high, BTX yield only has 36.5%, and in comparative example 3, adopt the SAPO-34 containing binding agent and ZSM-5 molecular sieve mixed molecular sieve catalyst, although aromatization activity increases than independent ZSM-5 molecular sieve, but the yield of BTX is still not high, and BTX accounts for the catalyzer of ratio not as adopting soap-free emulsion polymeization formulation SAPO-34/ZSM-5 composite molecular screen obtained of total aromatic hydrocarbons.This illustrates that technical scheme of the present invention achieves good technique effect.
Claims (10)
1. a binder free SAPO-34/ZSM-5 composite molecular screen, in composite molecular screen, with weight parts, comprises following component:
(1) 1 ~ 99 part of SAPO-34 molecular sieve;
The ZSM-5 molecular sieve of (2) 1 ~ 99 parts;
The binding agent of (3) 0 ~ 5 parts.
2. binder free SAPO-34/ZSM-5 composite molecular screen according to claim 1, is characterized in that the intensity of binder free composite molecular screen is greater than 40 Ns/, and wherein the diameter of every catalyzer is 1 ~ 5 millimeter, and length is 5 millimeters.
3. the preparation method of binder free SAPO-34/ZSM-5 composite molecular screen according to claim 1, comprises following step:
(1) silicon source, aluminium source, phosphorus source, ZSM-5 molecular sieve are mixed to form gel with water according to a certain percentage, in the butt of each material, mol ratio is: Al
2o
3: P
2o
5: SiO
2: ZSM-5=1:0.8 ~ 2.0:0.3 ~ 2.0:0.5 ~ 30.0;
(2), after gel drying, the particle be applicable to needed for reaction is broken into;
(3) particle of fragmentation is placed in the steam containing organic formwork agent, in 120 ~ 220 DEG C of crystallization 24 ~ 100h;
(4) product washing crystallization obtained, drying, roasting obtain binder free SAPO-34/ZSM-5 composite molecular screen.
4. the preparation method of binder free SAPO-34/ZSM-5 composite molecular screen according to claim 3, is characterized in that described silicon source is selected from least one in silicon sol, water glass, active silica, organosilicon; Aluminium source is selected from least one in pseudo-boehmite, aluminum isopropylate, activated alumina, aluminium salt; Phosphorus source is selected from least one in ortho-phosphoric acid, phosphorous acid, phosphoric acid salt; ZSM-5 molecular sieve is H type ZSM-5, Na type ZSM-5, or metallic element modify after ZSM-5 at least one; Organic formwork agent is selected from least one in tetraethyl ammonium hydroxide, triethylamine, morpholine.
5. the preparation method of binder free SAPO-34/ZSM-5 composite molecular screen according to claim 3, is characterized in that, in described step (1), in the wgt dry basis by total of each material, ratio is: Al
2o
3: P
2o
5: SiO
2: ZSM-5=1:0.8 ~ 1.6:0.3 ~ 1.0:0.5 ~ 20.0.
6. the preparation method of binder free SAPO-34/ZSM-5 composite molecular screen according to claim 3, is characterized in that, before step (1), first modifying ZSM-5 molecular sieve with metallic element.
7. the preparation method of binder free SAPO-34/ZSM-5 composite molecular screen according to claim 3, is characterized in that after step (4), modifies obtain binder free SAPO-34/ZSM-5 composite molecular screen with metallic element.
8. the preparation method of the binder free SAPO-34/ZSM-5 composite molecular screen according to claim 6 or 7, is characterized in that described metal-modified element is selected from least one in the periodic table of elements I B to VIII B and III A.
9. the preparation method of binder free SAPO-34/ZSM-5 composite molecular screen according to claim 8, is characterized in that described metal-modified element is selected from least one in La, Ti, V, Cr, Mo, Mn, Fe, Co, Ni, Cu, Ag, Zn, Ga.
10. a method for methanol/dimethyl ether conversion aromatic hydrocarbons, taking methanol aqueous solution as raw material, is 400 ~ 600 DEG C in temperature of reaction, and reaction pressure is 0.01 ~ 5MPa, and methanol weight air speed is 0.5 ~ 15 h
-1, the mass ratio of water and methyl alcohol is under the condition of 0.1 ~ 5:1, and raw material, by beds, with any one catalyst exposure of claim 1 ~ 2, generates aromatic hydrocarbons.
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| CN108014842A (en) * | 2016-11-04 | 2018-05-11 | 中国石油化工股份有限公司 | Cu-SSZ-13/ZSM-5 composite molecular sieves catalyst, preparation method and applications |
| CN108014842B (en) * | 2016-11-04 | 2019-11-08 | 中国石油化工股份有限公司 | Cu-SSZ-13/ZSM-5 composite molecular sieves catalyst, preparation method and applications |
| CN108927204A (en) * | 2018-07-09 | 2018-12-04 | 中国科学院山西煤炭化学研究所 | The catalyst and its preparation method of coal tar hydrogenating processing distillate selective hydrogenation cracking light aromatic hydrocarbons and application |
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