CN102294262B - Silicoaluminophosphate molecular sieve catalyst, preparation method, and use thereof - Google Patents
Silicoaluminophosphate molecular sieve catalyst, preparation method, and use thereof Download PDFInfo
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Abstract
The invention relates to a silicoaluminophosphate molecular sieve catalyst, a preparation method, and a use thereof. The invention relates to a preparation method for a silicoaluminophosphate molecular sieve catalyst. The method comprises the following steps: (a) preparing a mixed solution containing a template agent, silicon source, aluminum source, phosphorus source, and a matrix material; (b) optionally, aging the mixed solution; (c) carrying out crystallization for the optionally-aged mixed solution through a hydrothermal crystallization method; (d) optionally, mixing the crystallized mixed solution and a peptizing agent to form a uniform slurry; (e) carrying out a forming treatment for the crystallized mixed solution from the step (c) or the uniform slurry from the step (d) to obtain the formed product; (f) baking the formed product to obtain the silicoaluminophosphate molecular sieve catalyst. The invention further relates to the silicoaluminophosphate molecular sieve catalyst prepared through the method, the use of the silicoaluminophosphate molecular sieve catalyst as a catalyst for preparation of methanol through olefin, and a method for preparing methanol through olefin. The method provided by the present invention has characteristics of environmental friendliness and low cost.
Description
Technical field
The invention provides a kind of silicoaluminophosphamolecular molecular sieves catalyst especially SAPO-34 molecular sieve catalyst, its preparation method, purposes.
Background technology
Novel SAPO series molecular sieve (US4440871, US 4499327)-SAPO-n molecular sieve that U.S. combinating carbide company (UCC) researched and developed out in 1984, be be the template agent with the organic amine, be aluminium source, phosphorus source and silicon source with hydrated alumina, phosphoric acid, Ludox respectively, at first obtain having the organic amine/aluminum phosphate/silicon complex of micropore phase by hydrothermal crystallization method, remove by roasting then that template agent (organic amine) obtains.The SAPO-34 molecular sieve is wherein a kind of, and the similar chabasie of its structure has the three dimensional intersection duct, and the aperture is about 0.38nm, belongs to cubic system.Because it has suitable proton acidity, suitable pore passage structure, bigger specific area, absorption property and heat endurance and hydrothermal stability etc. preferably preferably, makes it present catalytic activity and selective preferably in as the methanol to olefins reaction catalyst.
The catalyst strength that adopts pure molecular sieve to make is lower, and cost is also than higher.And industrial catalyst not only requires good reaction activity, selectively reaches outside good stable, the suitable pore structure (specific area, void volume, aperture etc.), also need to have long service life, necessary strength (crushing strength, tear strength) and proper physical structural design (shape, size etc.), above-mentioned every catalyst serviceability, outside the Pass having with the catalyst intrinsic performance, relevant with its forming process to a certain extent.Therefore, industrial molecular sieve catalyst all needs the suitable auxiliary agent of molecular sieve and other to adopt that the method for forming waits to prepare in suitable forming method such as compression forming method, extrusion moulding, rotational forming method, spray shaping method, the oil usually.
The methanol-to-olefins catalyst is based on the acidic catalyst characteristics of aperture SAPO molecular sieve, owing to utilized the acidity of this molecular sieve and the shape selective effect of small apertures diameter, can highly selective be ethene, propylene with methanol conversion, existence and the acid catalysed intrinsic property of " cage " in the SAPO molecular sieve structure also make this catalyst very fast because of the coking inactivation simultaneously.Under the condition of higher reaction temperatures and higher space velocity, the one way life-span is shorter, must be to the frequent charcoal regeneration of decaying catalyst.Therefore select the circulating fluid bed reactor of successive reaction-regeneration for use, and the catalyst repeated regeneration require catalyst except have preferably active and selectively also should have higher intensity.With catalyst several pieces of patent reports are arranged at methanol-to-olefins, as the molecular sieve catalyst preparation method of CN1535177 according to routine, molecular sieve, binding agent and matrix material are mixed the formation slurry according to suitable proportioning, spray-dried technology obtains molecular sieve catalyst, this catalyst has wear resistence preferably, as have preferably ethene when the oxygen raw material is produced the catalyst of alkene to contain, propylene is selective; The CN1207097C report utilizes catalyst particle and part SAPO-34 molecular sieve, bonding agent, carrier, the peptizing agent of the abrasion of the ciculation fluidized reaction recovery of part to be mixed into even mixed serum, spray-dried technology prepares the methanol to olefins reaction catalyst then, be of value to by the abrasion recovery of particle and application waste is minimized, thereby reduce the problem of relevant environment and economic constraints; CN100446859C adopts does not have the molecular sieve of bone dry to mix the catalyst that spray-dried technology obtains having better wear resistence with binding agent, matrix material, and in MTO reacts, show good ethene, propylene is selective.
Above-mentioned patent report all is at first to make molecular sieve, is combined with binding agent, matrix material by molecular sieve then, and spray-dried technology forms molecular sieve catalyst.Owing to can produce a large amount of crystallized residual liquids in the hydrothermal crystallizing synthesis of molecular sieve process, these crystallized residual liquids are owing to contain the harmful components of organic amine, phosphorus and can not directly discharge, and handling these raffinates, can to consume more financial resources, man power and material, environmental protection pressure bigger.In addition, can produce a large amount of waste liquids equally in molecular sieve washing and filtering process, these waste liquids also can bring pollution to environment, and some molecular sieves are run off, and the molecular sieve yield reduces, the corresponding increase of cost.
Therefore, need a kind of environmental friendliness, SAPO-34 molecular sieve catalyst preparation method that cost is low.
Summary of the invention
One aspect of the present invention relates to a kind of silicoaluminophosphamolecular molecular sieves Preparation of catalysts method, may further comprise the steps:
(a) provide the mixed liquor that contains template agent, silicon source, aluminium source, phosphorus source and matrix material;
(b) alternatively, with the mixed liquor ageing;
(c) adopt hydrothermal crystallization method that the mixed liquor of optional ageing is carried out crystallization;
(d) alternatively, the mixed liquor after the crystallization is mixed with peptizing agent, form homogeneous slurry;
(e) homogeneous slurry that obtains of the mixed liquor after the crystallization that step (c) is obtained or step (d) carries out forming processes, obtains mold compound;
(f) mold compound is carried out roasting, obtain the silicoaluminophosphamolecular molecular sieves catalyst.
Preferably, the silicoaluminophosphamolecular molecular sieves catalyst is the SAPO molecular sieve catalyst, preferred SAPO-34 molecular sieve catalyst.
Preferably, the template agent is tetraethyl ammonium hydroxide, triethylamine, diethylamine, morpholine, aniline, isopropylamine, di-n-propylamine or their mixture for the template agent, be preferably tetraethyl ammonium hydroxide, triethylamine, diethylamine, morpholine or their mixture, more preferably triethylamine.
Preferably, the silicon source is Ludox, silicic acid, silica, white carbon, waterglass, ethyl orthosilicate or their mixture, preferred Ludox, and preferably, the concentration of Ludox is 40 weight %.
Preferably, the phosphorus source is phosphoric acid, phosphate or phosphite or their mixture, preferably phosphoric acid.
Preferably, the aluminium source is boehmite, aluminium isopropoxide, aluminium oxide, aluminium hydroxide or their mixture, preferred boehmite.
Preferably, matrix material is diatomite, kaolin, imvite or their mixture, preferred kaolin.
Preferably, peptizing agent is inorganic acid such as nitric acid or organic acid such as acetic acid, preferred rare nitric acid.
Preferably, in step (a), form the mixed liquor in template agent and silicon source, aluminium source, phosphorus source earlier, and then mix with matrix material.
The invention still further relates to the silicoaluminophosphamolecular molecular sieves catalyst that method of the present invention obtains.
The invention still further relates to silicoaluminophosphamolecular molecular sieves catalyst of the present invention purposes as catalyst in by methanol to olefins reaction.
The invention still further relates to the method by methanol-to-olefins of the present invention, wherein, adopt silicoaluminophosphamolecular molecular sieves catalyst of the present invention as catalyst.
The method according to this invention environmental friendliness, cost are low.
Description of drawings
Fig. 1 is embodiment 1,2,3 process chart;
Fig. 2 is the process chart of embodiment 4;
Fig. 3 is the synthetic process chart of SAPO-34 molecular sieve catalyst;
Fig. 4 is the process chart of Comparative Examples 1;
Fig. 5 is the process chart of Comparative Examples 2;
Fig. 6 is X-ray diffraction (XRD) figure (curve a: the embodiment 1 of embodiment 1-7, Comparative Examples 1-2 products obtained therefrom; Curve b: embodiment 2; Curve c: embodiment 3; Curve d: embodiment 4; Curve e: embodiment 5; Curve f: embodiment 6; Curve g: embodiment 7; Curve h: Comparative Examples 1; Curve i: Comparative Examples 2).
The specific embodiment
In the present invention, under the situation of not contradiction or conflict, all embodiment of the present invention, embodiment and feature can make up mutually.
In the present invention, all reagent, unit, parts etc. both can be purchased, also can be according to content self-control disclosed by the invention.
In the present invention, for outstanding emphasis of the present invention, the omission that operation and unit, the parts of some routines are carried out, or only do simple the description.
Term " template agent ", " silicon source ", " aluminium source " and " phosphorus source " are illustrated in the compound that can form the template agent/SAPO complex with micropore in the hydrothermal crystallization process in the present invention.Wherein, the template agent can be removed by roasting.
In the present invention, term " SAPO-34 molecular sieve " refers to be numbered in the US Patent No. 4440871 molecular sieve of SAPO-34.SAPO-34 molecular sieve of the present invention is silicoaluminophosphamolecular molecular sieves, and it preferably has basically as the X-ray diffractogram shown among Fig. 6 a-d any.
One aspect of the present invention relates to silicoaluminophosphamolecular molecular sieves catalyst, the preparation method of SAPO-34 molecular sieve catalyst especially.The present invention especially provides a kind of method of directly utilizing crystallization liquid in the molecular sieve water heat crystallization process to prepare molecular sieve catalyst.
Method of the present invention may further comprise the steps:
(a) provide the mixed liquor that contains template agent, silicon source, aluminium source, phosphorus source and matrix material;
(b) alternatively, with the mixed liquor ageing;
(c) mixed liquor with optional ageing carries out crystallization;
(d) alternatively, the mixed liquor after the crystallization is mixed with peptizing agent, form uniform slurries;
(e) with uniform slurries moulding;
(f) product with moulding carries out roasting, obtains molecular sieve catalyst.
A kind of preferred embodiment in, method of the present invention comprises the steps:
(a) the template agent is mixed according to sequencing with silicon source, aluminium source, phosphorus source form mixed liquor earlier, and then add matrix material and mix, stirring mixed in 1-10 hour under 25-80 ℃;
(b) mixed solution was carried out under 25-80 ℃ ageing 1-24 hour;
(c) mixed solution after the ageing is packed into crystallizing kettle airtightly is heated to crystallization temperature 150-250 ℃, carries out under constant crystallization temperature then crystallization 10-120 hour;
(d) mixed liquor after the crystallization is added peptizing agent and be mixed into uniform slurries, wherein the peptizing agent consumption is according to the 0-20% of crystallization liquid quality;
(e) slurry that mixes is entered carry out spray shaping in the spray dryer, spray-drying condition: inlet temperature: 250-400 ℃, outlet temperature: 150-180 ℃;
(f) with the sample behind the spray shaping at 450-650 ℃ of following roasting 4-8 hour, obtain molecular sieve catalyst.
Preferably, in step (a), form the mixed liquor in template agent and silicon source, aluminium source, phosphorus source earlier, and then mix with matrix material.A kind of preferred embodiment in, at first the template agent is mixed with the silicon source, mix with aluminium source, phosphorus source successively then, mix with matrix material at last.That is to say, the template agent is mixed forming mixed liquor earlier with silicon source, aluminium source, phosphorus source according to sequencing, and then mix with matrix material.
In another embodiment, the charging sequence in the step (a) is: the mixture of phosphorus source and water is added in the mixture of aluminium source and water, obtain phosphorus source-aluminium source mixed liquor; Mixture with silicon source and water joins in phosphorus source-aluminium source mixed liquor again, obtains phosphorus source-aluminium source-silicon source mixed liquor; The template agent is joined in phosphorus source-aluminium source-silicon source mixed liquor then.
Preferably, the template agent is organic amine.Organic amine can be alkylamine, arylamine or nitrogenous heteroatomic heterocycle.Alkylamine can be C
1-C
8Alkylamine, more preferably C
1-C
6Alkylamine, further preferred C
1-C
4Alkylamine, most preferably C
1-C
3Alkylamine.Arylamine can be C
6-C
10Arylamine, more preferably C
6-C
8Arylamine.The example of alkylamine is triethylamine, diethylamine.
Preferably, the template agent is tetraethyl ammonium hydroxide, triethylamine, diethylamine, morpholine, aniline, isopropylamine, di-n-propylamine or their mixture, be preferably tetraethyl ammonium hydroxide, triethylamine, diethylamine, morpholine or their mixture, more preferably triethylamine.
Preferably, the silicon source is Ludox, silicic acid, silica, white carbon, waterglass, ethyl orthosilicate or they mixture arbitrarily, preferred Ludox.Preferably, the concentration of Ludox is 40 weight %.
Preferably, the phosphorus source is phosphoric acid, phosphate or phosphite or they mixture arbitrarily.
Preferably, the phosphorus source is phosphoric acid, and it is 85% orthophosphoric acid by weight that preferably phosphoric acid contains.
Preferably, the aluminium source is boehmite, aluminium isopropoxide, aluminium oxide, aluminium hydroxide or they mixture arbitrarily, preferred boehmite.
Preferably, matrix material is diatomite, kaolin, imvite or they mixture arbitrarily, preferred kaolin.
Preferably, peptizing agent is inorganic acid such as nitric acid or organic acid such as acetic acid, preferred rare nitric acid.
Preferably, in step (a), stirring mixed in 1-10 hour under 25-80 ℃.
Preferably, in step (b), the ageing temperature is 25～80 ℃, preferred 25～60 ℃, and more preferably 25～50 ℃, most preferably 25～40 ℃.Preferably, in step (b), digestion time is 1-24h, preferred 1-16h, more preferably 1-10h, most preferably 2-10h, for example 4h.
Preferably, in step (c), crystallization is undertaken by hydrothermal crystallization method.
Preferably, in step (c), crystallization temperature is 150-250 ℃, preferred 150-220 ℃, and more preferably 180-220 ℃, most preferably 190-210 ℃, for example, 200 ℃.Preferably, in step (c), crystallization time is 10-120h, preferred 10-100h, more preferably 20-100h, most preferably 30-80h, for example 48h, 50h.
Preferably, in step (d), based on the crystallization liquid quality, the peptizing agent consumption is 0-20%, preferred 0.1%-20%, more preferably 1%-20%, further preferred 2%-15%, most preferably 2%-5%.
Preferably, in step (e), forming processes can be spray shaping, for example by carrying out spray shaping in the spray dryer.For example, the spray-drying condition is inlet temperature 250-400 ℃, outlet temperature 150-180 ℃.Preferably, before forming processes, carry out static ageing.
Preferably, in step (f), sintering temperature is 450-800 ℃, preferred 450-700 ℃, and 450-650 most preferably.Preferably, in step (f), roasting time is 3-12h, preferred 3-10h, more preferably 4-8h, most preferably 5-8h.
Another aspect of the present invention relates to the molecular sieve catalyst by method preparation of the present invention.
Another aspect of the present invention relates to molecular sieve catalyst of the present invention purposes as catalyst in by methanol to olefins reaction.
Another aspect of the present invention relates to the method by methanol-to-olefins, wherein, adopts molecular sieve catalyst of the present invention.
The present invention is with the template agent, the silicon source, the aluminium source, the phosphorus source, binding agent, matrix carrier is in the lump according to suitable proportioning, suitable addition manner mixes the uniform mixed liquor of formation, then through aging, hydrothermal crystallizing, in crystallization liquid, add an amount of adhesive and form uniform slurry, spray-dried technology forms pressed powder, obtain molecular sieve catalyst finally by roasting, this method is except having above-mentioned environmental protection effect, owing to reduced operation and correspondingly reduced cost, compare with the molecular screen primary powder that prior art makes, the molecular sieve catalyst that the inventive method makes has higher intensity, when being used for methanol to olefins reaction as catalyst, when reaction temperature is 300～500 ℃, reaction pressure is 0～0.5MPa, preferable reaction temperature is 400～500 ℃, the mass space velocity of methyl alcohol is 1.0～5.0 o'clock, and feed stock conversion can reach 100%, ethene+propene yield＞80%.
Embodiment
Now further specify the present invention by following examples, comparative example, but the present invention is not limited to this.
Embodiment 1:
With 85% phosphoric acid of 443g, the boehmite of 780g, 40% Ludox of 171g, the triethylamine of 582g, the deionized water of 1784g, 400g kaolin carries out according to operation shown in Figure 1, and wherein aging condition is: temperature: 25 ℃, and the time: 4 hours; Crystallization condition is: temperature: 200 ℃, and the time: 48 hours; Obtain adding in the crystallization liquid the rare nitric acid of 120g (20%) and mix mixed liquor ageing condition: temperature: 25 ℃, the time: 2 hours; Slurry carries out spray shaping after the ageing.Spray-drying condition: inlet temperature: 260 ℃, outlet temperature: 170 ℃.The sample that obtains carries out roasting, roasting condition at horse still stove: temperature: 550 ℃, and the time: 7 hours.
Embodiment 2:
With 85% phosphoric acid of 400g, the boehmite of 800g, 40% Ludox of 180g, the triethylamine of 600g, the deionized water of 2000g, 400g kaolin carries out according to operation shown in Figure 1, and wherein aging condition is: temperature: 25 ℃, and the time: 2 hours; Crystallization condition is: temperature: 200 ℃, and the time: 50 hours; Obtain adding in the crystallization liquid the rare nitric acid of 150g (20%) and mix mixed liquor ageing condition: temperature: 25 ℃, the time: 2 hours; Slurry carries out spray shaping after the ageing.Spray-drying: inlet temperature: 250 ℃, outlet temperature: 160 ℃.The sample that obtains carries out roasting, roasting condition at horse still stove: temperature: 600 ℃, and the time: 6 hours.
Embodiment 3:
With 85% phosphoric acid of 400g, the boehmite of 850g, 40% Ludox of 200g, the triethylamine of 600g, the deionized water of 2000g, 400g kaolin carries out according to operation shown in Figure 1, and wherein aging condition is: temperature: 25 ℃, and the time: 2 hours; Crystallization condition is: temperature: 200 ℃, and the time: 50 hours; Obtain adding in the crystallization liquid the rare nitric acid of 100g (20%) and mix mixed liquor ageing condition: temperature: 25 ℃, the time: 2 hours; Slurry carries out spray shaping after the ageing.Spray-drying: inlet temperature: 250 ℃, outlet temperature: 160 ℃.The sample that obtains carries out roasting, roasting condition at horse still stove: temperature: 600 ℃, and the time: 6 hours.
Embodiment 4:
With 85% phosphoric acid of 442g, the boehmite of 780g, 40% Ludox of 171g, the triethylamine of 580g, the deionized water of 1800g, 400g kaolin carries out according to operation shown in Figure 2, and wherein aging condition is: temperature: 25 ℃, and the time: 4 hours; Crystallization condition is: temperature: 200 ℃, and the time: 48 hours; Obtain crystallization liquid and carry out spray shaping.Spray-drying: inlet temperature: 260 ℃, outlet temperature: 170 ℃.The sample that obtains carries out roasting, roasting condition at horse still stove: temperature: 650 ℃, and the time: 5 hours.
With 85% phosphoric acid of 443g, the boehmite of 780g, 40% Ludox of 171g, the tetraethyl ammonium hydroxide (30wt%) of 131g, the triethylamine of 380g, the deionized water of 1784g, 400g kaolin carries out according to operation shown in Figure 1, wherein aging condition is: temperature: 25 ℃, and the time: 4 hours; Crystallization condition is: temperature: 200 ℃, and the time: 48 hours; Obtain adding in the crystallization liquid the rare nitric acid of 120g (20%) and mix mixed liquor ageing condition: temperature: 25 ℃, the time: 2 hours; Slurry carries out spray shaping after the ageing.Spray-drying condition: inlet temperature: 260 ℃, outlet temperature: 170 ℃.The sample that obtains carries out roasting, roasting condition at horse still stove: temperature: 550 ℃, and the time: 7 hours.
Embodiment 6
With the deionized water of 40% Ludox of the boehmite of 85% phosphoric acid of 443g, 780g, 171g, 275g diethylamine, 1784g, 400g kaolin carries out according to operation shown in Figure 1, and wherein aging condition is: temperature: 25 ℃, and the time: 4 hours; Crystallization condition is: temperature: 200 ℃, and the time: 48 hours; Obtain adding in the crystallization liquid the rare nitric acid of 120g (20%) and mix mixed liquor ageing condition: temperature: 25 ℃, the time: 2 hours; Slurry carries out spray shaping after the ageing.Spray-drying condition: inlet temperature: 260 ℃, outlet temperature: 170 ℃.The sample that obtains carries out roasting, roasting condition at horse still stove: temperature: 550 ℃, and the time: 7 hours.
Embodiment 7
With 85% phosphoric acid of 443g, the boehmite of 780g, 40% Ludox of 171g, the morpholine of 330g, the deionized water of 1784g, 400g kaolin carries out according to operation shown in Figure 1, and wherein aging condition is: temperature: 25 ℃, and the time: 4 hours; Crystallization condition is: temperature: 200 ℃, and the time: 48 hours; Obtain adding in the crystallization liquid the rare nitric acid of 120g (20%) and mix mixed liquor ageing condition: temperature: 25 ℃, the time: 2 hours; Slurry carries out spray shaping after the ageing.Spray-drying condition: inlet temperature: 260 ℃, outlet temperature: 170 ℃.The sample that obtains carries out roasting, roasting condition at horse still stove: temperature: 550 ℃, and the time: 7 hours.
Comparative Examples 1:
With 85% phosphoric acid of 443g, the boehmite of 315g, 40% Ludox of 171g, the triethylamine of 581.76g, the deionized water of 1784g, synthesize the SAPO-34 molecular sieve according to operation shown in Figure 3, wherein ageing condition is: temperature: 25 ℃, and the time: 4 hours; Crystallization condition is: temperature: 200 ℃, and the time: 48 hours; Roasting condition: temperature: 550 ℃, the time: 7 hours; Get product SAPO-34 molecular sieve at last.Take out the 400gSAPO-34 molecular sieve then and mix mixed liquor ageing condition: temperature with 310g boehmite, 400g kaolin, the rare nitric acid of 150g (20%) and 3000g deionized water respectively according to operation shown in Figure 4: 25 ℃, the time: 2 hours; Slurry carries out spray shaping after the ageing.Spray-drying: inlet temperature: 260 ℃, outlet temperature: 170 ℃.The sample that obtains carries out roasting, roasting condition at horse still stove: temperature: 550 ℃, and the time: 7 hours.
Comparative Examples 2:
With 85% phosphoric acid of 443g, the boehmite of 315g, 40% Ludox of 171g, the triethylamine of 582g, the deionized water of 1784g, obtain molecular screen primary powder (not carrying out roasting) according to operation shown in Figure 5, wherein ageing condition is: temperature: 25 ℃, and the time: 4 hours; Crystallization condition is: temperature: 200 ℃, and the time: 48 hours; The molecular screen primary powder that obtains, mix with 384g kaolin, 465g boehmite, the rare nitric acid of 120g (20%) according to Fig. 5 operation, mixed liquor ageing a period of time forms slurry, carries out spray shaping behind the ageing slurry.Wherein ageing condition: temperature: 25 ℃, the time: 2 hours; Spray-drying condition: inlet temperature: 260 ℃, outlet temperature: 170 ℃.The sample that obtains carries out roasting, roasting condition at horse still stove: temperature: 550 ℃, and the time: 7 hours.
Can find that from Fig. 6 it is SAPO-34 that Comparative Examples 1, Comparative Examples 2 and embodiment 1-4 all manifest the catalyst that obtains, and all can be used as the catalyst of methanol to olefins reaction.
The molecular sieve catalyst examination:
Adopt the fixed bed catalyst evaluating apparatus, the embodiment 1-4, Comparative Examples 1, the Comparative Examples 2 that obtain are carried out catalyst examination experiment, experiment condition: loaded catalyst 1.0 grams, 450 ℃ of reaction temperatures, air speed are 3h
-1, the results are shown in following table 1.
Table 1 methanol conversion alkene appraisal result processed
As can be seen from Table 1, especially when adopting same template agent (embodiment 1-4), adopt the sub-sieve catalyst method of molecular sieve catalyst simultaneous interpretation controlling back-up (Comparative Examples 1 and Comparative Examples 2) of the inventive method preparation to compare to show good ethene and propylene selective.
Each embodiment of table 2, Comparative Examples gained molecular sieve catalyst intensity
| Sample | Wear rate/% |
| Embodiment 1 | 1.07 |
| Embodiment 2 | 0.88 |
| Embodiment 3 | 0.96 |
| Embodiment 4 | 1.03 |
| |
1.24 |
| Embodiment 6 | 1.45 |
| Embodiment 7 | 1.68 |
| Comparative Examples 1 | 1.72 |
| Comparative Examples 2 | 2.58 |
Annotate: the molecular sieve catalyst tear strength adopts two-tube abrasion index analyzer to measure.
Wear rate=[(W
1-W
0)/W
S]/4; W
S=W
2+ W
1-W
0
W wherein
0The empty bag of expression collecting bag weight, unit: g; W
1Expression wearing and tearing collecting bag gross weight after 4 hours, unit: g; W
2Catalyst weight in the developmental tube after expression was worn and torn 4 hours, unit: g; W
S4 hours rear catalyst gross weights of expression wearing and tearing, unit: g.
As can be seen from Table 2, especially when adopting same template agent (embodiment 1-4), the sub-sieve catalyst method of molecular sieve catalyst simultaneous interpretation controlling back-up (Comparative Examples 1 and Comparative Examples 2) that adopts the inventive method to prepare is compared has higher intensity.
Therefore, result of the test can illustrate and adopt the molecular sieve catalyst of the inventive method preparation to have higher intensity in table 1 and the table 2, and in methanol to olefins reaction, show good ethene and propylene selective.
Certainly, the present invention also can have other specific embodiment, and the above is preferred embodiment of the present invention only, is not to limit protection scope of the present invention; Without departing from the spirit of the invention, those of ordinary skills are every to make various corresponding variations and modification according to content of the present invention, all belongs to the protection domain of claim of the present invention.
Claims (19)
1. silicoaluminophosphamolecular molecular sieves Preparation of catalysts method may further comprise the steps:
(a) provide the mixed liquor that contains template agent, silicon source, aluminium source, phosphorus source and matrix material, wherein form the mixed liquor in described template agent and described silicon source, aluminium source, phosphorus source earlier, and then mix with described matrix material;
(b) alternatively, with the mixed liquor ageing;
(c) adopt hydrothermal crystallization method that the mixed liquor of optional ageing is carried out crystallization;
(d) mixed liquor after the crystallization is mixed with peptizing agent, form homogeneous slurry;
(e) homogeneous slurry that step (d) is obtained carries out forming processes, obtains mold compound;
(f) described mold compound is carried out roasting, obtain the silicoaluminophosphamolecular molecular sieves catalyst;
Wherein, described matrix material is kaolin.
2. method according to claim 1, wherein, described silicoaluminophosphamolecular molecular sieves catalyst is the SAPO molecular sieve catalyst.
3. method according to claim 1, wherein, described silicoaluminophosphamolecular molecular sieves catalyst is the SAPO-34 molecular sieve catalyst.
4. according to each described method of claim 1 to 3, wherein, described template agent is tetraethyl ammonium hydroxide, triethylamine, diethylamine, morpholine, aniline, isopropylamine, di-n-propylamine or their mixture.
5. according to each described method of claim 1 to 3, wherein, described template agent is tetraethyl ammonium hydroxide, triethylamine, diethylamine, morpholine or their mixture.
6. according to each described method of claim 1 to 3, wherein, described template agent is triethylamine.
7. according to each described method of claim 1 to 3, wherein, described silicon source is Ludox, silicic acid, silica, white carbon, waterglass, ethyl orthosilicate or their mixture.
8. according to each described method of claim 1 to 3, wherein, described silicon source is Ludox.
9. method according to claim 8, wherein, the concentration of described Ludox is 40 weight %.
10. according to each described method of claim 1 to 3, wherein, described phosphorus source is phosphoric acid, phosphate or phosphite or their mixture.
11. according to each described method of claim 1 to 3, wherein, described phosphorus source is phosphoric acid.
12. according to each described method of claim 1 to 3, wherein, described aluminium source is boehmite, aluminium isopropoxide, aluminium oxide, aluminium hydroxide or their mixture.
13. according to each described method of claim 1 to 3, wherein, described aluminium source is boehmite.
14. according to each described method of claim 1 to 3, wherein, described peptizing agent is inorganic acid or organic acid.
15. according to each described method of claim 1 to 3, wherein, described peptizing agent is nitric acid or acetic acid.
16. according to each described method of claim 1 to 3, wherein, described peptizing agent is nitric acid.
17. the silicoaluminophosphamolecular molecular sieves catalyst that obtains according to each described method of claim 1 to 16.
18. silicoaluminophosphamolecular molecular sieves catalyst according to claim 17 in by methanol to olefins reaction as the purposes of catalyst.
19. by the method for methanol-to-olefins, wherein, adopt silicoaluminophosphamolecular molecular sieves catalyst according to claim 17 as catalyst.
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| CN103058223B (en) * | 2013-01-28 | 2015-04-01 | 神华集团有限责任公司 | Molecular sieve catalyst and preparation method thereof |
| CN104923284B (en) * | 2014-03-18 | 2019-09-17 | 中国石油天然气股份有限公司 | A kind of molded molecular sieve catalyst and its preparation method and application |
| CN105271302B (en) * | 2014-06-30 | 2018-04-13 | 神华集团有限责任公司 | A kind of 18 molecular sieves of SAPO and its synthetic method and a kind of method of methanol-to-olefins |
| CN106430229B (en) * | 2016-09-12 | 2018-06-26 | 中国华能集团公司 | The method that multilevel hierarchy molecular sieve is prepared using mesoporous material as indirect template agent |
| CN108371955B (en) * | 2018-01-23 | 2020-05-22 | 中国石油大学(北京) | SAPO-34/ZSM-5@ kaolin microsphere composite catalytic material, and preparation and application thereof |
| CN111659463B (en) * | 2020-06-10 | 2023-08-29 | 江苏扬农化工集团有限公司 | Preparation method of silicon-aluminum-phosphorus molecular sieve catalyst for synthesizing hexamethylenediamine key intermediate and application of catalyst |
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