CN101612592A - A kind of preparation method of low abrasion microsphere catalyst produced in situ - Google Patents
A kind of preparation method of low abrasion microsphere catalyst produced in situ Download PDFInfo
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Abstract
The present invention relates to a kind of preparation method of low abrasion microsphere catalyst produced in situ, at first by spray drying method for preparation porous carrier microballoon, after 800-1000 ℃ of high-temperature roasting, the modification of phosphorus source are handled, adopt the synthetic method of hydro-thermal, obtain low abrasion microsphere catalyst produced.Compared with prior art, the present invention have abrasion low, catalyst activity is high, raw material sources are extensive, low cost and other advantages.
Description
Technical field
The present invention relates to a kind of catalyst, especially relate to a kind of preparation method of low abrasion microsphere catalyst produced in situ.
Background technology
U.S. Pat 4440871 (UCC, 1984) has been introduced the synthetic of silicoaluminophosphamolecular molecular sieve crystal and has been improved one's methods, and will comprise reactive SiO
2, Al
2O
3And P
2O
5Source and organic formwork agent add in certain sequence, hydrothermal crystallization method obtain the aperture homogeneous, greater than
Micropore sial phosphorus crystal (being designated as SAPO), the anhydrous chemical composition of raw material is when synthetic: mR:(Si
xAl
yP
z) O
2Wherein R is an organic formwork agent, and m is that R is than (Si
xAl
yP
z) O
2Molar fraction, value is 0.02～0.3; X, y and z: the molar fraction that is respectively Si, Al and P, span is (x:0.01-0.99, y:0-0.6, z:0.4-0.99), this patent relates to the determining of synthetic, crystalline phase of micropore SAPO series molecular sieve crystal, the measurement of character (aperture) etc., this patent report the template agent of a large amount of kinds, the actual employing of molecular sieve SAPO-34 among the embodiment.But the SAPO-34 molecular screen primary powder need be shaped to the molecular sieve catalyst with high-wear resistance, just can be suitable for fluidized-bed process.
In methanol-to-olefins (the being called for short MTO) technology, the abrasion height of catalyst is that it realizes one of industrialized technical difficult points at present.The MTO catalyst because inactivation is fast, needs frequent regeneration, is not suitable for fixed-bed process, and the MTO of employing fluidized bed process technology crosses the range request catalyst and has suitable size distribution and higher wearability.At present a large amount of bibliographical informations all adopts spray drying process to prepare the MTO fluid catalyst, and this preparation method is earlier with active component SAPO-34 molecular sieve and bonding agent such as clay, and silicon-aluminum sol etc. are mixed and made into uniform sizing material, and spray-drying makes then.Reported molecular sieve as USP5248647 with SAPO-34, the spray-dired method of the slurry that kaolin and Ludox are made, USP6153552 has reported a kind of microspherical catalyst preparation method of the SAPO of containing molecular sieve, be with the SAPO molecular sieve, inorganic oxide sol, and the phosphorus-containing compound mixing, spray-drying is made; USP6787501 has reported the spray-dried methanol conversion catalyst of making of SAPO-34 molecular sieve, bonding agent and host material; CN01132533A has reported the preparation of abrasion-resisting catalyst, and moulding process is same as described above, and different is to play the effect that improves the catalyst tolerates abrasion by the mass content that reduces molecular sieve in the catalyst.CN1341584A has introduced a kind of method that is used for the abrasion-resisting catalyst of light-olefin production, and described host material comprises inorganic oxide adhesive and filler, the weight of molecular sieve with respect to the weight of catalyst less than 40%.Above-mentioned forming process is owing to be to adopt the molecular sieve active component to mix making beating with compositions such as bonding agent, auxiliary agents, therefore cause the aperture of part molecular sieve to be stopped up inevitably, the part active component can't be brought into play catalytic activity, when the SAPO-34 molecular sieve component is higher in the MTO catalyst, the wearability of catalyst then reduces, and is unsuitable for fluidized-bed process.The present invention's difference is: utilize the carrier through high-temperature process, improve the wearability of catalyst; Adopt in-situ synthetic method, synthetic carrier-SAPO-34 molecular sieve catalyst, it is unimpeded not only to react the duct, and reactivity is good, and the standard abrasion index can directly apply to fluidized-bed reactor less than 1.0%/h.
Kaolin is to be the soft clay of main component with kaolinite subtribe mineral, and molecular formula is Al
4[Si
4O
10] (OH)
8, by [SiO
4] tetrahedral layer and Al[O (OH)]
6Octahedral layer constitutes the layer structure material of compound cellular construction layer, and interlayer is connected by hydrogen bond.Usually the kaolin crystal is hexagon or leg-of-mutton laminated structure.Through after the high-temperature roasting, the hydrogen bond rupture of kaolin interlayer, the kaolinite of originally orderly lamella crystal structure becomes the metakaolinite of disordered structure, and produce highly active aluminium oxide and silica, but its lamellar structure does not change, active silica and aluminium oxide are still with stratiform at interval, it is synthetic that multiple molecular sieve has all adopted roasting kaolin to carry out crystallization as raw material, as the A type, the P type, the X type, the ZSM-5 type, Y type etc., wherein the kaolin spraying is prepared into microballoon, in-situ crystallization growth Y zeolite forms composite catalyst and has obtained practical application in the catalytic cracking field especially.
Chinese patent CN101176851A has reported that adopting kaolin is the method for raw material or the synthetic SAPO-34 molecular sieve of matrix, kaolin after this method employing roasting or kaolin microsphere are as aluminium source and/or silicon source, prepared the less molecular sieve catalyst of lamellar structure or particle, the characteristics of this patent are cheap kaolin to have reduced cost of material as the synthetic raw material of SAPO molecular sieve.When adopting 700-850 ℃ of calcination process, kaolin or kaolin microsphere are mainly as the aluminium source, when adopting 900-1100 ℃ of calcination process, kaolin or kaolin microsphere are mainly as the silicon source, add orthophosphoric acid, template agent, deionized water again, hydrothermal crystallizing obtains the kaolin in-situ crystallization catalyst.But as the catalyst that is applied to fluidized-bed reactor, its wearability has certain requirement.It is reaction raw materials that this method stresses with the roasting kaolin, and the wearability of catalyst is not explicitly called for.
Chinese patent CN101157057 has reported silicon source, aluminium source, phosphorus source has been mixed, behind rubber mill glue mill, spray-drying prepares sial phosphorous oxides microballoon, after the high-temperature roasting, add organic amine template and water, hydrothermal crystallizing, grow the SAPO molecular sieve at microsphere surface and internal in-situ, but the microballoon that this method adopts needs three kinds of raw materials to carry out the glue mill, the preparation cost of microballoon is higher, three kinds of raw materials still need to have follow-up crystallization activity in the microballoon, and the sintering temperature of microballoon is subjected to certain limitation, and this method does not have qualification to the rate of wear of catalyst of preparation yet.
At application number is in the patent that awaits the reply of 200910046218.S, and has introduced a kind of method of producing composite silicophosphoaluminamolecular molecular sieve by in situ synthesis, and carrier adopts kaolin microsphere, and means are handled in the sour modification of using in the surface modification treatment, and what reality adopted is hydrochloric acid.In the acid treatment process, the microballoon that employing hydrochloric acid carries out after the modification carries out the synthetic MTO catalyst of original position as carrier, and its selectivity of light olefin is lower than the microballoon original position synthetic catalyst that adopts after the modification processing is carried out in the phosphorus source.Reason is the difference of the carrier surface performance after two kinds of modifications are handled, the hydrochloric acid modification removes a large amount of activated aluminum of carrier surface, surface-active silicon relative scale improves, activated silica in the original position of molecular sieve is synthetic with the adhesion of template agent a little less than, and after the surface modification of carrier process phosphorus source, carrier surface phosphorus hydroxyl adhesion with the template agent in the original position of molecular sieve is synthetic is stronger, and the original position that helps molecular sieve is synthetic.
During the at present existing wear-resistance microspheres shaping of catalyst that is used for oxygen-containing compound conversion to produce olefine, adopt main active component to mix making beating, the attrition of catalyst height that spray shaping obtains with carrier and bonding agent; The main active component that runs into when perhaps adopting in-situ synthetic method is few in the carrier surface increment, and catalyst activity is on the low side.
Summary of the invention
Purpose of the present invention is exactly to provide a kind of preparation method who wears away the low abrasion microsphere catalyst produced in situ low, that catalyst activity is high, raw material sources are extensive, cost is low for the defective that overcomes above-mentioned prior art existence.
Purpose of the present invention can be achieved through the following technical solutions: a kind of preparation method of low abrasion microsphere catalyst produced in situ, it is characterized in that, at first by spray drying method for preparation porous carrier microballoon, after 800-1000 ℃ of high-temperature roasting, the modification of phosphorus source are handled, adopt the synthetic method of hydro-thermal, obtain low abrasion microsphere catalyst produced.
The preparation of described porous carrier microballoon: with kaolin is raw material, carry out the glue mill through rubber mill, make particle diameter all less than 3 μ m, wherein 90% grain diameter is less than 2 μ m, and 70% grain diameter is less than 1 μ m, adds deionized water again and functional component mixes, obtain the slurries that solid content is 25-50wt%, the spray-dried kaolin microsphere that gets, particle diameter is between 20-150 μ m, and average grain diameter is at 60-80 μ m.
Described functional component comprises bonding agent, structural auxiliary agent, and the bonding agent addition is the 5-25% of kaolin quality, and structural promoter addition is the 0.5-10% of kaolin quality.
Described kaolin is soft kaolin, hard Raolinite, kaolinite or gangue; The kaolinite content that particle diameter behind the kaolin glue mill is positioned at 0.5-3.0 μ m is higher than 90wt%, and iron oxide content is lower than 1.5wt%, and sodium oxide molybdena and potassium oxide sum are lower than 0.5wt%.
Described bonding agent is one or more the mixture in Ludox, aluminium colloidal sol, waterglass, the boehmite.
Described structural auxiliary agent comprises one or more the mixture in Sodium Polyacrylate, polyacrylamide, polyvinyl alcohol, polyethylene glycol and starch, carboxymethyl cellulose, graphite powder, the sesbania powder.
It is that the porous carrier microballoon that will obtain through high-temperature roasting is immersed in the phosphorus source solution that concentration is 10-50wt% that the modification of described phosphorus source is handled, and its solvent and solute weight ratio is (3-5): 1, and under 80-100 ℃, backflow 1-12h, washing, drying.
The synthetic method of described hydro-thermal specifically may further comprise the steps:
(a) the porous carrier microballoon after will handling mixes with the template agent of metering, the phosphorus source, silicon source and the aluminium source that add metering again, mix with the template agent and the water of metering, in the stainless steel synthesis reactor of the inner liner polytetrafluoroethylene of packing into, under 150-250 ℃, self-generated pressure, carry out hydrothermal crystallizing 2-150h;
(b) the product screening that step (a) is obtained, deionization washing, 110 ℃ of-120 ℃ of air dryings, in 500-700 ℃ of air roasting 3-8 hour, obtain microspherulite diameter between 20-150 μ m, go out the low abrasion catalyst of sial phosphorus molecular sieve at the surfaces externally and internally growth in situ of microballoon.
The weight ratio of described template agent and porous carrier microballoon is 0.3-3: 1; The weight ratio of described phosphorus source and porous carrier microballoon is 0.3-3: 1, the weight ratio of described silicon source and porous carrier microballoon is 0.1-1: 1, the weight ratio of described aluminium source and porous carrier microballoon is 0.2-3: 1, and the volume ratio of described water and template agent is 0-2: 1.
After liquid-solid separation, the solid material adds the moulding preparation that participates in porous carrier in the kaolin as one of spray-drying raw material to the mother liquor after step (a) screening, and organic amine template agent distillation is recycled in the liquid.
Described silicon source is a kind of or any several mixture in Ludox, active silica, ethyl orthosilicate or the kaolin; Described aluminium source is the one or any several mixture in aluminium salt, activated alumina, aluminum alkoxide, false boehmite, boehmite or the kaolin; Described template agent is the nitrogen-containing organic compound that is used for hydro-thermal synthesizing Si-Al phosphorus molecular sieve, comprise diethylamine, triethylamine, n-propylamine, isopropylamine, Tri-n-Propylamine, tri-isopropyl amine, di-n-propylamine, diisopropylamine, TMAH, tetraethyl ammonium hydroxide, TPAOH, 1,6-hexamethylene diamine, cyclohexylamine, morpholine, monoethanolamine, diethanol amine, triethanolamine a kind of or any several mixture wherein.
Described phosphorus source is a kind of or any several mixture in orthophosphoric acid, ammonium hydrogen phosphate, ammonium dihydrogen phosphate (ADP), organic phosphorus compound or the phosphorous oxides.
Described sial phosphorus molecular sieve is SAPO-5, SAPO-11, SAPO-17, SAPO-18, SAPO-31, SAPO-34, SAPO-35, SAPO-37, SAPO-40, SAPO-41, SAPO-42, SAPO-44, SAPO-56.
The described low abrasion microsphere catalyst produced multi-stage artery structure that has, its standard abrasion index is less than 1.0%/h.
The described low abrasion microsphere catalyst produced oxygen-containing compound conversion to produce olefine reaction that is used for, this catalyst preferably uses fluidized-bed reactor.
The present invention utilizes direct synthesis technique, utilize the support modification of phosphorus source with high-temperature roasting, directly add as raw material in the mother liquor of synthesizing Si-Al phosphorus (SAPO) molecular sieve, after the hydrothermal crystallizing reaction, cooling, screening, washing, calcination activation promptly obtain being suitable for the MTO catalyst of fluidized-bed process.
The synthetic SAPO molecular sieve of the carrier situ that the present invention adopts, difference from prior art is to have adopted the phosphorus source to carry out surface treatment.The cellular construction of SAPO-34 molecular sieve is divided into SiO
2, AlO
2 -, PO
2 +In the experimental design of the synthetic SAPO-34 of carrier situ, for reaching the strong connectivity of SAPO-34 and carrier, comparatively feasible method is at first with the carrier high-temperature roasting, improves the wear-resisting property of catalyst, on this basis, based on one of above-mentioned three kinds of cellular constructions of SAPO-34 molecular sieve, utilize the effect of template agent to make the SAPO-34 molecular sieve around the carrier growth, calcination activation obtains carrier-SAPO-34 composite behind the hydrothermal crystallizing, is the MTO catalyst.Prior art adopts HCl or NaOH that carrier surface is handled usually, and part remains with the activated silica or the activated aluminum of certain reactivity.Find by above-mentioned analysis, the binding ability of carrier surface template agent relatively a little less than, the molecular sieve amount of carrier surface growth in situ is relatively low, and is on the low side as the selectivity of light olefin of MTO catalyst.Anatomize three kinds of cellular constructions of SAPO-34 molecular sieve, they have on chemical characteristic than big-difference: SiO
2Come from SiOH, chemical property is near neutral; AlO
2 -Come from AlOH, chemical property is in the soda acid both sexes; PO
2 +Come from POH, chemical property is in acidity, the synthetic organic amine of the employing usually template agent of SAPO-34 molecular sieve, this class template agent has strong basicity, from point of chemical reaction, when adopting the modification of phosphorus source, if POH appears in carrier surface, have acidity, combine with the template agent easily, utilized PO during original position is synthetic
2 +Cellular construction has on the one hand guaranteed being connected of SAPO-34 molecular sieve and carrier chemistry, utilizes the guidance quality of template agent on the other hand, can improve the increment of carrier surface SAPO-34 molecular sieve.
For achieving the above object, technical solution of the present invention is the microballoon that at first prepares porous carrier by spray-drying, after the surface modification of phosphorus source, adopts the synthetic method of hydro-thermal, goes out the SAPO molecular sieve at the surfaces externally and internally growth in situ of microballoon.For reducing discharging, improve utilization rate of active components, in actual application, after synthetic at every turn mother liquor sieved out the catalyst finished product, remaining carry out liquid-solid separation, solid constituent adds in the raw material of preparation carrier and participates in mist projection granulating, and the agent of organic amine template is recycled in the liquid, reduces catalyst production cost.
Compared with prior art, it is that raw material carries out the glue mill that the present invention adopts kaolin, and support material is cheap and easy to get, and with kaolin and bonding agent process spray shaping, after the high-temperature roasting, the inert carrier in only synthesizing as catalyst is used to improve the wearability of catalyst; Wear-resisting kaolin support surface is carried out the phosphorus source and is handled, adopt in-situ synthetic method, utilizing surperficial phosphorus hydroxyl to strengthen carrier is connected with chemical bond between the SAPO-34 molecular sieve, improve the load capacity of main active component, synthetic carrier-SAPO-34 molecular sieve catalyst, it is unimpeded not only to react the duct, reactivity is good, under the prerequisite that guarantees higher catalytic activity, obtain being suitable for the MTO catalyst of the standard abrasion index of fluidized-bed process operation, can directly apply to fluidized-bed reactor less than 1.0%/h.
The invention has the advantages that:
(1) utilizes the synthetic method of original position, greatly improve reaction raw materials and the product diffusion-restricted in course of reaction, improve the utilization rate of main active component.
(2) adopting kaolin is carrier, and raw material sources are wide, and are cheap and easy to get, and spray shaping has guaranteed the wearability of carrier after high-temperature roasting.
(3) by carrier surface is carried out the modification of phosphorus source, greatly having strengthened the SAPO molecular sieve is connected with chemistry between the carrier, effectively improved the increment of the synthetic middle SAPO molecular sieve of original position, when satisfying the low abrasion of catalyst, guaranteed the high activity of catalyst again at carrier surface.
(4) screening promptly obtains finished product to the present invention's mother liquor that in-situ crystallization is synthetic through a step, remains in solid phase composition in the mother liquor after liquid-solid separation, and solid and support material mix carries out mist projection granulating, has improved main active component utilization rate.
(5) performance of carrier and SAPO molecular sieve is regulated respectively, helps production control.
The moulding process of catalyst is simple, and the rate of wear of catalyst is low, adapts to the fluidized-bed process operation, is fit to suitability for industrialized production.
Description of drawings
Fig. 1 for the present invention in the kaolin microsphere superficial growth XRD figure spectrum of SAPO-34 molecular sieve;
Fig. 2 is the SEM picture of the present invention at the most of embedding of the SAPO-34 zeolite crystal carrier surface of kaolin microsphere surface in situ growth;
Fig. 3 is the SEM picture of the present invention at the most of embedding of the SAPO-34 zeolite crystal carrier surface of kaolin microsphere surface in situ growth.
The specific embodiment
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment only to be used to the present invention is described and be not used in and limit the scope of the invention.The experimental technique of unreceipted actual conditions in the following example usually according to normal condition, or carries out according to the condition that manufacturer advises.Unless otherwise indicated, otherwise all umbers are weight portion, and all percentages are weight percentage.
Unless otherwise defined or explanation, the meaning that all specialties used herein are familiar with scientific words and those skilled in the art is identical, and any in addition method similar or impartial to described content and material all can be applicable in the inventive method.
Embodiment 1
(1) preparation of kaolin microsphere
At first kaolin 3000g, Ludox 1200g (solid content 25%) and deionized water 1560g are mixed into uniform sizing material, add 12g polyvinyl alcohol, 10g polyethylene glycol again and carry out the glue mill by rubber mill, make particle diameter all less than 3 μ m, wherein 90% grain diameter is less than 2 μ m, and 70% grain diameter is less than 1 μ m; Then the spray-dried method of mixed slurry is made kaolin microsphere, particle diameter is between 20-150 μ m, and average grain diameter is at 60 μ m, 800 ℃ of roasting 1-4h, bioassay standard abrasion index 0.9%/h.
(2) modification of kaolin microsphere
The kaolin microsphere that above-mentioned steps (1) makes is got 30g, add 60g 10%H
3PO
4In the solution, at 80 ℃ of backflow 4h, washing, filtration, 100-150 ℃ dry 1h.
(3) low abrasion microsphere catalyst produced preparation
7.8g boehmite (content 65%) is mixed stirring 30 minutes with the 30g deionized water, to wherein slowly adding 11.5g phosphoric acid (content 85%), stir the back to wherein adding 3.6g Ludox (content 25%), continue to stir adding 10g triethylamine, add deionized water 20g again, after at room temperature stirring 1.5 hours, get the modified kaolin microballoon 10g that step (2) makes, add the 5g triethylamine, add again in the above-mentioned colloidal sol, continued stir about 2 hours, gained colloidal sol is moved into to be had in the teflon-lined autoclave, 200 ℃ of following crystallization 24 hours; Product is through screening, washing, in 110 ℃ of dryings 12 hours, and 600 ℃ of following roastings 10 hours, the synthetic molecular sieve of XRD test shows original position is the SAPO-34 molecular sieve, the abrasion index of kaolin microsphere-SAPO molecular sieves compound material is 0.9%/h.
As shown in Figure 1, the XRD figure spectrum SAPO-34 molecular sieve that has been presented at the kaolin microsphere superficial growth.
Shown in Fig. 2-3, the SEM picture is presented at the most of carrier surface that embeds of SAPO-34 zeolite crystal of kaolin microsphere surface in situ growth.
Original position is synthesized the determination of activity of kaolin microsphere-SAPO molecular sieve
The resulting catalyst of above-mentioned steps is carried out methanol-to-olefins reaction (MTO) reaction evaluating.
Appreciation condition: take by weighing the 1.35g catalyst sample fixed bed reactors of packing into, sample at first 520 ℃ down logical nitrogen (nitrogen flows: 40mL/min) activation is 30 minutes, is cooled to 450 ℃ then and reacts.Stop logical nitrogen, use the micro pump charging, methyl alcohol: water=1: 3 (volume ratio), weight space velocity WHSV are 1h
-1, product is analyzed by online gas-chromatography, the results are shown in Table 1.
Table 1 reaction for preparing light olefins from methanol result
Embodiment 2
(1) preparation of kaolin microsphere
At first kaolin is carried out the glue mill by rubber mill, make particle diameter all less than 2 μ m, wherein 90% grain diameter is less than 2 μ m, and 70% grain diameter is less than 1 μ m; Get gained kaolin 3000g, aluminium colloidal sol 1200g (solid content 25%) and deionized water 1560g then and be mixed into uniform sizing material, spray-dried method makes kaolin microsphere, particle diameter is between 20-150 μ m, average grain diameter is at 80 μ m, 850 ℃ of roasting 1-4h, bioassay standard abrasion index 0.9%/h.
(2) modification of kaolin microsphere
The kaolin microsphere that step (1) makes is got 30g, add 90g 20%H
3PO
4In the solution, at 80 ℃ of backflow 10h, washing, filtration, 100-150 ℃ dry 2h.
(3) low abrasion microsphere catalyst produced preparation
7.8g boehmite (content 65%) is mixed stirring 30 minutes with the 30g deionized water, to wherein slowly adding 11.5g phosphoric acid (content 85%), stir the back to wherein adding 3.6g Ludox (content 25%), continue to stir adding 15g triethylamine, add deionized water 20g again, after at room temperature stirring 1.5 hours, get the modified kaolin microballoon 10g that step (2) makes, add the 5g triethylamine, add again in the above-mentioned colloidal sol, continued stir about 2 hours, gained colloidal sol is moved into to be had in the teflon-lined autoclave, 200 ℃ of following crystallization 24 hours; Product is through screening, washing, in 110 ℃ of dryings 12 hours, and 600 ℃ of following roastings 10 hours, the synthetic molecular sieve of XRD test shows original position is the SAPO-34 molecular sieve, the abrasion index of kaolin microsphere-SAPO molecular sieves compound material is 0.9%/h.
Embodiment 3
(1) preparation of kaolin microsphere
At first kaolin is carried out the glue mill by rubber mill, make particle diameter all less than 2 μ m, wherein 90% grain diameter is less than 2 μ m, and 70% grain diameter is less than 1 μ m; Get gained kaolin 3000g, Ludox 1200g (solid content 25%) then, deionized water 1560g is mixed into uniform sizing material, spray-dried method makes kaolin microsphere, particle diameter is between 20-150 μ m, average grain diameter is at 60 μ m, 900 ℃ of roasting 1-4h, bioassay standard abrasion index 0.8%/h.
(2) modification of kaolin microsphere
The kaolin microsphere that step (1) makes is got 30g, add 60g 50%H
3PO
4In the solution, at 80 ℃ of backflow 4h, washing, filtration, 100-150 ℃ dry 4h.
(3) low abrasion microsphere catalyst produced preparation
7.8g boehmite (content 65%) is mixed stirring 30 minutes with the 30g deionized water, to wherein slowly adding 11.5g phosphoric acid (content 85%), stir the back to wherein adding 3.6g Ludox (content 25%), continue to stir adding 10g triethylamine, add deionized water 20g again, after at room temperature stirring 1.5 hours, get the modified kaolin microballoon 10g that step (2) makes, add the 5g triethylamine, add again in the above-mentioned colloidal sol, continued stir about 2 hours, gained colloidal sol is moved into to be had in the teflon-lined autoclave, 200 ℃ of following crystallization 24 hours; Product is through screening, washing, in 110 ℃ of dryings 12 hours, and 600 ℃ of following roastings 10 hours, the synthetic molecular sieve of XRD test shows original position is the SAPO-34 molecular sieve, the abrasion index of kaolin microsphere-SAPO molecular sieves compound material is 0.8%/h.
Embodiment 4
(1) preparation of kaolin microsphere
At first kaolin is carried out the glue mill by rubber mill, make particle diameter all less than 2 μ m, wherein 90% grain diameter is less than 2 μ m, and 70% grain diameter is less than 1 μ m; Get gained kaolin 3000g, aluminium colloidal sol 1200g (solid content 25%) then, 20g not the SAPO-34 of removed template method and particle diameter all less than 2 μ m polyacrylamides, deionized water 1560g is mixed into uniform sizing material, spray-dried method makes kaolin microsphere, particle diameter is between 20-150 μ m, average grain diameter is at 90 μ m, 1000 ℃ of roasting 1-4h, bioassay standard abrasion index 0.8%/h.
(2) modification of kaolin microsphere
The kaolin microsphere that step (1) makes is got 30g, add 60g 20% (CH
3)
3PO
4In the solution, at 80 ℃ of backflow 8h, washing, filtration, 100-150 ℃ dry 4h.
(3) low abrasion microsphere catalyst produced preparation
7.8g boehmite (content 65%) is mixed stirring 30 minutes with the 30g deionized water, to wherein slowly adding 11.5g phosphoric acid (content 85%), stir the back to wherein adding 1.0g Ludox (content 25%), continue to stir adding 10g triethylamine, add deionized water 20g again, after at room temperature stirring 1.5 hours, get the kaolin microsphere 10g that embodiment 8 makes, add the 5g triethylamine, add again in the above-mentioned colloidal sol, continued stir about 2 hours, gained colloidal sol is moved into to be had in the teflon-lined autoclave, 200 ℃ of following crystallization 24 hours; Product is through screening, washing, in 110 ℃ of dryings 12 hours, and 600 ℃ of following roastings 10 hours, the synthetic molecular sieve of XRD test shows original position is the SAPO-34 molecular sieve, the abrasion index of kaolin microsphere-SAPO molecular sieves compound material is 0.8%/h.
Comparative Examples 1
(1) modification of kaolin microsphere
The kaolin microsphere that embodiment 3 steps (1) make is got 30g, add in the 60g 2N HCl solution, at 95 ℃ of backflow 8h, washing, filtration, 100-150 ℃ dry 4h.
(2) 7.8g boehmite (content 65%) is mixed stirring 30 minutes with the 30g deionized water, to wherein slowly adding 11.5g phosphoric acid (content 85%), stir the back to wherein adding 3.6g Ludox (content 25%), continue to stir adding 10g triethylamine, add deionized water 20g again, after at room temperature stirring 1.5 hours, get the modified kaolin microballoon 10g that step (1) makes, add the 5g triethylamine, add again in the above-mentioned colloidal sol, continued stir about 2 hours, gained colloidal sol is moved into to be had in the teflon-lined autoclave, 200 ℃ of following crystallization 24 hours; Product is through screening, washing, in 110 ℃ of dryings 12 hours, and 600 ℃ of following roastings 10 hours, the synthetic molecular sieve of XRD test shows original position is the SAPO-34 molecular sieve, the abrasion index of kaolin microsphere-SAPO molecular sieves compound material is 0.9%/h.
Original position is synthesized the determination of activity of kaolin microsphere-SAPO molecular sieve
The resulting catalyst of above-mentioned steps is carried out methanol-to-olefins reaction (MTO) reaction evaluating.
Appreciation condition: take by weighing the 1.35g catalyst sample fixed bed reactors of packing into, sample at first 520 ℃ down logical nitrogen (nitrogen flows: 40mL/min) activation is 30 minutes, is cooled to 450 ℃ then and reacts.Stop logical nitrogen, use the micro pump charging, methyl alcohol: water=1: 3 (volume ratio), weight space velocity WHSV are 1h
-1, product is analyzed by online gas-chromatography, the time dependent table 1 that the results are shown in of product distribution.Catalyst is after reaction 6 hours, and the coke content of measuring catalyst by infrared carbon sulfur analyzer (CS-106) is 8.03%.
Table 2 reaction for preparing light olefins from methanol result
Embodiment 1 shows that with the comparative result of Comparative Examples 1 carrier of phosphorus source modification has significantly improved the synthetic kaolin microsphere of original position-SAPO molecular sieve and has been applied to the catalytic activity of methanol-to-olefins reaction (MTO) reaction.
Embodiment 5
(1) preparation of porous carrier microballoon
With the kaolinite is raw material, carry out the glue mill through rubber mill, make particle diameter all less than 3 μ m, wherein 90% grain diameter is less than 2 μ m, 70% grain diameter is less than 1 μ m, iron oxide content is lower than 1.5%, sodium oxide molybdena and potassium oxide sum are lower than 0.5%, add deionized water again, Ludox, Sodium Polyacrylate and starch mix, and the Ludox addition is 5% of a kaolinite quality, Sodium Polyacrylate and starch addition are 10% of kaolinite quality, obtain solid content and be 25% slurries, spray-dried porous carrier microballoon, particle diameter is between 20-150 μ m, average grain diameter is at 60-80 μ m, through 800 ℃ of high-temperature roastings;
(2) modification of the preparation of porous carrier microballoon
It is that its solvent and solute weight ratio is 3: 1 in 10% the orthophosphoric acid solution that the kaolinite microballoon that step (1) is made is immersed in concentration, under 80 ℃, and backflow 1h, washing, drying.
(3) low abrasion microsphere catalyst produced preparation
(a) the kaolinite microballoon that step (2) is obtained mixes with diethylamine, the orthophosphoric acid, ethyl orthosilicate, the aluminum alkoxide that add metering again, mix with the diethylamine of metering, in the stainless steel synthesis reactor of the inner liner polytetrafluoroethylene of packing into, under 150 ℃, self-generated pressure, carry out hydrothermal crystallizing 150h; The weight ratio of described diethylamine and kaolinite microballoon is 0.3: 1, and the weight ratio of orthophosphoric acid and kaolinite microballoon is 3: 1; The weight ratio of described ethyl orthosilicate and kaolinite microballoon is 0.1: 1, and the weight ratio of described aluminum alkoxide and kaolinite microballoon is 0.2: 1.
(b) the product screening that step (a) is obtained, the deionization washing is 120 ℃ of air dryings, roasting is 8 hours in 500 ℃ of air, obtain microspherulite diameter between 20-150 μ m, the low abrasion catalyst of surface in situ growth sial phosphorus molecular sieve, the sial phosphorus molecular sieve is SAPO-5;
(c) with the mother liquor after step (a) screening after liquid-solid separation, the solid material adds the moulding preparation that participates in porous carrier in the kaolinite as one of spray-drying raw material to, organic amine template agent distillation is recycled in the liquid.
Embodiment 6
(1) preparation of porous carrier microballoon
With the gangue is raw material, carry out the glue mill through rubber mill, make particle diameter all less than 3 μ m, wherein 90% grain diameter is less than 2 μ m, 70% grain diameter is less than 1 μ m, iron oxide content is lower than 1.5%, sodium oxide molybdena and potassium oxide sum are lower than 0.5%, add deionized water again, aluminium colloidal sol, polyvinyl alcohol and graphite powder mix, and aluminium colloidal sol addition is 25% of a gangue quality, polyvinyl alcohol and graphite powder addition are 0.5% of gangue quality, obtain solid content and be 50% slurries, spray-dried porous carrier microballoon, particle diameter is between 20-150 μ m, average grain diameter is at 60-80 μ m, through 1000 ℃ of high-temperature roastings;
(2) modification of the preparation of porous carrier microballoon
It is that its solvent and solute weight ratio is 5: 1 in 50% the ammonium dihydrogen phosphate that the porous carrier microballoon that step (1) is made is immersed in concentration, under 100 ℃, and backflow 12h, washing, drying.
(3) low abrasion microsphere catalyst produced preparation
(a) the modified porous carrier microballoons that step (2) is obtained mixes with TMAH, the ammonium dihydrogen phosphate (ADP), ethyl orthosilicate, the alum that add metering again, mix with the TMAH and the water of metering, pack in the stainless steel synthesis reactor of inner liner polytetrafluoroethylene, under 250 ℃, self-generated pressure, carry out hydrothermal crystallizing 2h; The weight ratio of described TMAH and modified porous carrier microballoons is 3: 1, the weight ratio of ammonium dihydrogen phosphate (ADP) and modified porous carrier microballoons is 0.3: 1, the weight ratio of described ethyl orthosilicate and modified porous carrier microballoons is 1: 1, the weight ratio of described alum and modified porous carrier microballoons is 3: 1, and the volume ratio of water and TMAH is 2: 1;
(b) the product screening that step (a) is obtained, the deionization washing is 120 ℃ of air dryings, roasting is 3 hours in 700 ℃ of air, obtain microspherulite diameter between 20-150 μ m, the low abrasion catalyst of surface in situ growth sial phosphorus molecular sieve, the sial phosphorus molecular sieve is SAPO-56;
(c) with the mother liquor after step (a) screening after liquid-solid separation, the solid material adds the moulding preparation that participates in porous carrier in the kaolin as one of spray-drying raw material to, organic amine template agent distillation is recycled in the liquid.
The sial phosphorus molecular sieve also comprises SAPO-11, SAPO-17, SAPO-18, SAPO-31, SAPO-34, SAPO-35, SAPO-37, SAPO-40, SAPO-41, SAPO-42, SAPO-44.
The described low abrasion microsphere catalyst produced multi-stage artery structure that has, its standard abrasion index is less than 1.0%/h.The described low abrasion microsphere catalyst produced oxygen-containing compound conversion to produce olefine reaction that is used for, this catalyst preferably uses fluidized-bed reactor.
This method of the present invention utilizes cheap kaolin to be raw material, add deionized water and functional component, by with roasting at high temperature behind the kaolin spray shaping as attrition-resistant support, carrier after the roasting is handled through the phosphorus source, mix with the agent of organic amine template again, the silicon source that adds synthesizing silicon aluminum orthophosphate molecular sieve as raw material, in the colloidal sol that aluminium source and phosphorus source form, hydrothermal crystallizing, product is through washing, dry, carry out calcination activation after the screening, promptly obtain the catalyst that is applied to converting oxygen-containing compound to low-carbon olefins that is suitable for fluidized-bed reactor of low abrasion, mother liquor in the building-up process is through liquid-solid separation, the organic amine recycling, solid portion adds kaolin and carries out spray shaping, has improved utilization ratio of raw materials, is fit to suitability for industrialized production.
Described kaolin is soft kaolin, hard Raolinite, kaolinite or gangue; The kaolinite content that particle diameter behind the kaolin glue mill is positioned at 0.5-3.0 μ m is higher than 90%, and iron oxide content is lower than 1.5%, and sodium oxide molybdena and potassium oxide sum are lower than 0.5%.Described functional component comprises bonding agent, structural auxiliary agent, and the bonding agent addition is the 5-25% of kaolin quality, and structural promoter addition is the 0.5-10% of kaolin quality; Described bonding agent is one or more the mixture in Ludox, aluminium colloidal sol, waterglass, the boehmite.Described structural auxiliary agent comprises one or more the mixture in Sodium Polyacrylate, polyacrylamide, polyvinyl alcohol, polyethylene glycol and starch, carboxymethyl cellulose, graphite powder, the sesbania powder.
Described silicon source is a kind of or any several mixture in Ludox, active silica, ethyl orthosilicate or the kaolin; Described aluminium source is the one or any several mixture in aluminium salt, activated alumina, aluminum alkoxide, false boehmite, boehmite or the kaolin; Described phosphorus source is a kind of or any several mixture in orthophosphoric acid, ammonium hydrogen phosphate, ammonium dihydrogen phosphate (ADP), organic phosphorus compound or the phosphorous oxides; Described template agent is the nitrogen-containing organic compound of the hydro-thermal synthesizing Si-Al phosphorus molecular sieve that is useful on, comprise diethylamine, triethylamine, n-propylamine, isopropylamine, Tri-n-Propylamine, tri-isopropyl amine, di-n-propylamine, diisopropylamine, TMAH, tetraethyl ammonium hydroxide, TPAOH, 1,6-hexamethylene diamine, cyclohexylamine, morpholine, monoethanolamine, diethanol amine, triethanolamine a kind of or any several mixture wherein.
Claims (15)
1. the preparation method of a low abrasion microsphere catalyst produced in situ, it is characterized in that, at first by spray drying method for preparation porous carrier microballoon, after 800-1000 ℃ of high-temperature roasting, the modification of phosphorus source are handled, adopt the synthetic method of hydro-thermal, obtain low abrasion microsphere catalyst produced.
2. the preparation method of a kind of low abrasion microsphere catalyst produced in situ according to claim 1, it is characterized in that, the preparation of described porous carrier microballoon: with kaolin is raw material, carry out the glue mill through rubber mill, make particle diameter all less than 3 μ m, wherein 90% grain diameter is less than 2 μ m, 70% grain diameter is less than 1 μ m, add deionized water again and functional component mixes, obtain the slurries that solid content is 25-50wt%, the spray-dried kaolin microsphere that gets, particle diameter is between 20-150 μ m, and average grain diameter is at 60-80 μ m.
3. the preparation method of a kind of low abrasion microsphere catalyst produced in situ according to claim 2, it is characterized in that, described functional component comprises bonding agent, structural auxiliary agent, the bonding agent addition is the 5-25% of kaolin quality, and structural promoter addition is the 0.5-10% of kaolin quality.
4. according to the preparation method of claim 2 or 3 described a kind of low abrasion microsphere catalyst produced in situ, it is characterized in that described kaolin is soft kaolin, hard Raolinite, kaolinite or gangue; The kaolinite content that particle diameter behind the kaolin glue mill is positioned at 0.5-3.0 μ m is higher than 90wt%, and iron oxide content is lower than 1.5wt%, and sodium oxide molybdena and potassium oxide sum are lower than 0.5wt%.
5. the preparation method of a kind of low abrasion microsphere catalyst produced in situ according to claim 3 is characterized in that, described bonding agent is one or more the mixture in Ludox, aluminium colloidal sol, waterglass, the boehmite.
6. the preparation method of a kind of low abrasion microsphere catalyst produced in situ according to claim 3, it is characterized in that described structural auxiliary agent comprises one or more the mixture in Sodium Polyacrylate, polyacrylamide, polyvinyl alcohol, polyethylene glycol and starch, carboxymethyl cellulose, graphite powder, the sesbania powder.
7. the preparation method of a kind of low abrasion microsphere catalyst produced in situ according to claim 1, it is characterized in that, it is that the porous carrier microballoon that will obtain through high-temperature roasting is immersed in the phosphorus source solution that concentration is 10-50wt% that the modification of described phosphorus source is handled, its solvent and solute weight ratio is (3-5): 1, under 80-100 ℃, backflow 1-12h, washing, drying.
8. the preparation method of a kind of low abrasion microsphere catalyst produced in situ according to claim 1 is characterized in that, the synthetic method of described hydro-thermal specifically may further comprise the steps:
(a) the porous carrier microballoon after will handling mixes with the template agent of metering, the phosphorus source, silicon source and the aluminium source that add metering again, mix with the template agent and the water of metering, in the stainless steel synthesis reactor of the inner liner polytetrafluoroethylene of packing into, under 150-250 ℃, self-generated pressure, carry out hydrothermal crystallizing 2-150h;
(b) the product screening that step (a) is obtained, deionization washing, 110 ℃ of-120 ℃ of air dryings, in 500-700 ℃ of air roasting 3-8 hour, obtain microspherulite diameter between 20-150 μ m, go out the low abrasion catalyst of sial phosphorus molecular sieve at the surfaces externally and internally growth in situ of microballoon.
9. the preparation method of a kind of low abrasion microsphere catalyst produced in situ according to claim 8 is characterized in that, the weight ratio of described template agent and porous carrier microballoon is 0.3-3: 1; The weight ratio of described phosphorus source and porous carrier microballoon is 0.3-3: 1, the weight ratio of described silicon source and porous carrier microballoon is 0.1-1: 1, the weight ratio of described aluminium source and porous carrier microballoon is 0.2-3: 1, and the volume ratio of described water and template agent is 0-2: 1.
10. the preparation method of a kind of low abrasion microsphere catalyst produced in situ according to claim 8, it is characterized in that, with the mother liquor after step (a) screening after liquid-solid separation, the solid material adds the moulding preparation that participates in porous carrier in the kaolin as one of spray-drying raw material to, and organic amine template agent distillation is recycled in the liquid.
11. the preparation method of a kind of low abrasion microsphere catalyst produced in situ according to claim 8 is characterized in that, described silicon source is a kind of or any several mixture in Ludox, active silica, ethyl orthosilicate or the kaolin; Described aluminium source is the one or any several mixture in aluminium salt, activated alumina, aluminum alkoxide, false boehmite, boehmite or the kaolin; Described template agent is the nitrogen-containing organic compound that is used for hydro-thermal synthesizing Si-Al phosphorus molecular sieve, comprise diethylamine, triethylamine, n-propylamine, isopropylamine, Tri-n-Propylamine, tri-isopropyl amine, di-n-propylamine, diisopropylamine, TMAH, tetraethyl ammonium hydroxide, TPAOH, 1,6-hexamethylene diamine, cyclohexylamine, morpholine, monoethanolamine, diethanol amine, triethanolamine a kind of or any several mixture wherein.
12. preparation method according to claim 1 or 7 or 8 described a kind of low abrasion microsphere catalyst produced in situ, it is characterized in that described phosphorus source is a kind of or any several mixture in orthophosphoric acid, ammonium hydrogen phosphate, ammonium dihydrogen phosphate (ADP), organic phosphorus compound or the phosphorous oxides.
13. the preparation method according to claim 1 or 8 described a kind of low abrasion microsphere catalyst produced in situ is characterized in that, described sial phosphorus molecular sieve is SAPO-5, SAPO-11, SAPO-17, SAPO-18, SAPO-31, SAPO-34, SAPO-35, SAPO-37, SAPO-40, SAPO-41, SAPO-42, SAPO-44, SAPO-56.
14. the preparation method of a kind of low abrasion microsphere catalyst produced in situ according to claim 1 is characterized in that, the described low abrasion microsphere catalyst produced multi-stage artery structure that has, and its standard abrasion index is less than 1.0%/h.
15. the preparation method of a kind of low abrasion microsphere catalyst produced in situ according to claim 1 is characterized in that, the described low abrasion microsphere catalyst produced oxygen-containing compound conversion to produce olefine reaction that is used for, and this catalyst preferably uses fluidized-bed reactor.
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Address after: 200062 Shanghai city Putuo District Yunling Road No. 345 Co-patentee after: Shanghai Luqiang New Materials Co., Ltd. Patentee after: Shanghai Chemical Research Institute Co., Ltd. Address before: 200062 Shanghai city Putuo District Yunling Road No. 345 Co-patentee before: Shanghai Luqiang New Materials Co., Ltd. Patentee before: Shanghai Research Institute of Chemical Industry |