CN101628242A - Molecular sieve catalyst for preparing low-carbon olefin and preparation method thereof - Google Patents
Molecular sieve catalyst for preparing low-carbon olefin and preparation method thereof Download PDFInfo
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- CN101628242A CN101628242A CN200910090843A CN200910090843A CN101628242A CN 101628242 A CN101628242 A CN 101628242A CN 200910090843 A CN200910090843 A CN 200910090843A CN 200910090843 A CN200910090843 A CN 200910090843A CN 101628242 A CN101628242 A CN 101628242A
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Abstract
The invention provides a molecular sieve catalyst for preparing low-carbon olefin, and the catalyst comprises the following raw materials by parts by weight: 30-93.7 parts of Na-ZSM-5 zeolite, 5-40 parts of bonding agent, 0.1-10 parts of modifier of mixed elements, 1-15 parts of hole structure regulator and 0.1-5 parts of extrusion assistant, and the modifier of the mixed elements is a soluble substance containing one or a plurality of elements of B, P, La, Ca, Mg, Sr, Zn, Cu, Mn, Cd, Ga and In. The invention further provides a prepration method of the catalyst. The molecular sieve catalyst adopts the extrusion assistant and adds an appropriate amount of hole structure regulator, thereby improving product strength and hole structure, effectively improving diffusion performance of the catalyst and further improving selectivity of the low-carbon olefin. The catalyst has the advantages of appropriate strength, high hydrothermal stability, high activity and high selectivity of propylene.
Description
Technical field
The present invention relates to a kind of molecular sieve catalyst and this Preparation of catalysts method for preparing low-carbon alkene, particularly, the present invention relates to a kind ofly become the molded molecular sieve catalyst and this Preparation of catalysts method of low-carbon alkene, belong to coal chemical technology by methyl alcohol and/or dimethyl ether conversion.
Background technology
Low-carbon alkene is that petrochemical industry is produced basic raw materials, is the basis that produces other chemical products.Produce low-carbon alkene at present and be mainly petroleum path and non-petroleum path.(methanol-to-olefin MTO) is most important non-oil resource technology path by coal or natural gas via methyl alcohol and/or low-carbon alkenes such as dimethyl ether system ethene, propylene.In recent years, because oil price rises steadily and the increasing rapidly of propylene demand, causing with methyl alcohol is that (methanol-to-propylene MTP) has caused more extensive concern for the preparing propylene by methanol transformation technology of raw material.
In the prior art, the ZSM-5 type catalyst in fixed bed MTP technology and this technology is disclosed, however present low, the poor catalyst stability of these catalyst ubiquity propylene selectivity, the shortcoming of degradation deficiency under the propylene selectivity after the moulding.
Therefore need a kind ofly can improve olefin yields, have the catalyst of stability simultaneously.
Summary of the invention
For helping to understand the present invention, some terms have been defined below.The term of this paper definition has the implication of those of ordinary skill in the related art's common sense of the present invention.
Unless otherwise indicated, " precursor " herein refers to by certain operations step or reactions steps to make the precursor of target product.
Unless otherwise indicated, " sodium type ZSM-5 zeolite " herein refers to a kind of artificial synthetic mesopore five-element circular type zeolite with three-D pore structure, it is molecular sieve, be the Powdered porous silicoaluminate crystalline material that a kind of silica alumina ratio can change in a big way, its structure cell is formed can be expressed as Na
nAl
nSi
96-nO
19216H
2O, n＜27.
Unless otherwise indicated, herein " assorted element modifier " refers to the DDGS that contains one or more elements among B, P, La, Ca, Mg, Sr, Zn, Cu, Mn, Cd, Ga and the In, since these above-mentioned elements be in the sodium type ZSM-5 zeolite of catalyst do not have, so it can play the effect that improves catalyst property.
Unless otherwise indicated, " pore structure conditioning agent " herein refers to the material that can improve the catalyst central hole structure.
Unless otherwise indicated, " extrusion aid " herein refers to and helps the catalyst raw material by the needed raw material of forming operation in Preparation of catalysts.
Unless otherwise indicated, " peptizing agent " herein refer in the forming process of catalyst, need to add to increase the interparticle caking property of raw material, reach the material that improves catalyst strength and improve catalyst duct structure.
An object of the present invention is to provide a kind of molecular sieve catalyst for preparing low-carbon alkene.This catalyst is used for the reaction of methyl alcohol and/or dimethyl ether production low-carbon alkene, and in this reaction, catalyst has the selectivity of high mechanical properties, high thermal stability and high propylene.
Another object of the present invention also provides this Preparation of catalysts method.
At above purpose, one aspect of the present invention provides a kind of molecular sieve catalyst for preparing low-carbon alkene, in weight portion, described catalyst is made by the raw material that comprises following component: the sodium type ZSM-5 zeolite of 30-93.7 part, the adhesive of 5-40 part, the assorted element modifier of 0.1-10 part, the pore structure conditioning agent of 1-15 part and the extrusion aid of 0.1-5 part, and described assorted element modifier is the DDGS that contains one or more elements among B, P, La, Ca, Mg, Sr, Zn, Cu, Mn, Cd, Ga and the In.
Preferably, in weight portion, each component is in the described raw material: the sodium type ZSM-5 zeolite of 46-87.2 part, the adhesive of 10-30 part, the assorted element modifier of 0.5-5 part, the pore structure conditioning agent of 2-7 part and the extrusion aid of 0.3-2 part.
Preferably, wherein said sodium type ZSM-5 zeolite is that (silica aluminamolar ratio SAR) is the sodium type ZSM-5 zeolite of 20-2000 to silica alumina ratio.
More preferably, wherein said sodium type ZSM-5 zeolite is that particle diameter is that the following silica alumina ratio of 0.1mm is the sodium type ZSM-5 zeolite of 200-1000.
Preferably, to be selected from particle diameter be in 0.1mm following aluminium hydroxide, activated alumina, boehmite, boehmite, Ludox and the clay one or more to wherein said adhesive.
Preferably, wherein said adhesive is selected from one or more in activated alumina, boehmite, Ludox and the clay.
Preferably, wherein said pore structure conditioning agent is selected from one or more in methylcellulose, starch, polyvinyl alcohol, polyethylene glycol, sucrose and the glucose.
Preferably, described pore regulator is selected from one or more in methylcellulose, starch and the sucrose.
Preferably, described extrusion aid is selected from one or more in graphite powder, sesbania powder, oxalic acid, tartaric acid, citric acid, glycerine and the stearic acid.
Preferably, described extrusion aid is that in sesbania powder, citric acid and the glycerine any two kinds are the extrusion aid of forming at 1: 1 by mass ratio.
Preferably, described assorted element modifier is the DDGS that contains one or more elements among P, Mg, La, Mn and the Zn.
The present invention also provides a kind of method for preparing described molecular sieve catalyst on the other hand, and this method may further comprise the steps:
A. sodium type ZSM-5 zeolite, pore structure conditioning agent, extrusion aid, adhesive, assorted element modifier and peptizing agent are mixed;
B. the mixture moulding that step a is obtained, drying obtains the precursor I of catalyst after the calcining;
C. the precursor I of the catalyst that step b is obtained is 1) be selected from one or more solution or 2 in hydrochloric acid, sulfuric acid and the nitric acid) exchange in the inorganic ammonium salt solution, obtain catalyst precursor II after the oven dry;
D. the catalyst precursor II that step c is obtained steam and N
2Mist handle, obtain described catalyst." moulding " among the step b is in make-up machine, the mixture of step a made the preformed catalyst of definite shape and size.
Preferably, in described step a, at first sodium type ZSM-5 zeolite, pore structure conditioning agent and extrusion aid are mixed, obtain mixture, then will mix element modifier and peptizing agent add in the described mixture.The purpose that adds peptizing agent in the inventive method is to make to generate false aluminium colloidal sol in the forming process, and it can get up with dried glue bond, is convenient to moulding.
Preferably, described peptizing agent is selected from one or more in nitric acid, hydrochloric acid, phosphoric acid, sulfuric acid, formic acid, acetate and the malonic acid.
More preferably, described peptizing agent is selected from one or more in nitric acid, acetate and the phosphoric acid.
Preferably, wherein when the adhesive among the described step a was Ludox, described step a was for to mix sodium type ZSM-5 zeolite, pore structure conditioning agent, extrusion aid and assorted element modifier.
Preferably, wherein in described step b, the mixture moulding with step a obtains 50-120 ℃ of drying, 500-700 ℃ of calcining 5-7 hour, obtains the precursor I of catalyst under air atmosphere.
More preferably, in described step b, with the mixture moulding that step a obtains, 70-100 ℃ of drying calcined 5-6 hour for 550-650 ℃ under air atmosphere, obtained the precursor I of catalyst.
Most preferably, in described step b,,, under air atmosphere, calcined 5 hours for 600 ℃, obtain the precursor I of catalyst at 80 ℃ of freeze-day with constant temperature with the mixture moulding that step a obtains.
Preferably, wherein in described step c, the precursor I of the catalyst that step b is obtained is 1) the quality percentage composition is one or more solution or 2 in hydrochloric acid, sulfuric acid and the nitric acid of being selected from of 0.1-5%) the quality percentage composition be 0.1-5% be selected from one or more solution in ammonium nitrate, ammonium chloride and the carbonic hydroammonium 20-90 ℃ of exchange 2-5 time, each 1-6 hour, spend the precursor I of the catalyst after deionised water exchanges again, then with the precursor I of catalyst 60-160 ℃ of oven dry, obtain catalyst precursor II.
More preferably, the precursor I of the catalyst that step b is obtained the quality percentage composition be 0.8-4% be selected from one or more solution in hydrochloric acid, sulfuric acid and the nitric acid 40-70 ℃ of exchange 3-4 time, each 2-5 hour, spend the precursor I of the catalyst after deionised water exchanges again, then with the precursor I of catalyst 90-140 ℃ of oven dry, obtain the precursor II of catalyst.
Most preferably, the precursor I of the catalyst that step b is obtained the quality percentage composition be 3% be selected from one or more solution in hydrochloric acid, sulfuric acid and the nitric acid 60 ℃ of exchanges 3 times, each 2 hours, spend the precursor I of the catalyst after deionised water exchanges again, then with the precursor I of catalyst 120 ℃ of oven dry, obtain the precursor II of catalyst.
Preferably, wherein in described steps d, with steam and N
2Mist at 400-700 ℃, handled 5-10 hour, and steam accounts for the 30-70% of mist volume.
More steam and N in described steps d, are used in choosing ground
2Mist at 500-600 ℃, handled 5-8 hour, and steam accounts for the 40-60% of mist volume.
Most preferably, in described steps d, with steam and N
2Mist at 600 ℃, handled 8 hours, and steam accounts for 50% of mist volume.
Catalyst test apparatus of the present invention adopts flow reactor of fixed bed, and each loaded catalyst of estimating is 3.0g, is raw material with methyl alcohol and/or dimethyl ether, and water is diluent, when with CH
3OH or CH
3OCH
3During for raw material, mass ratio CH
3OH: H
2O=2: 1 or CH
3OCH
3: H
2O=2: 1 o'clock; When with CH
3OH and CH
3OCH
3During for raw material, CH
3OH and CH
3OCH
3Ratio can be arbitrarily, but CH
3OH and CH
3OCH
3The mass ratio of quality sum and water still is (CH
3OH+CH
3OHOCH
3): H
2O=2: 1, liquid hourly space velocity (LHSV) is 1h
-1, reaction temperature is 480 ℃, and system's stagnation pressure is less than 0.05MPa, and product is analyzed by flame ionization ditector (FID), and the calculating of selectivity of product is as the criterion with the quality percentage composition of carbon back product.Hetero atoms such as Ca, Mg, Zn, Sr, Cu, Mn, Cd, Ga, In, La, B and P enter and can obviously suppress acidic zeolite behind molecular sieve structure or the surface or produce the difunctional position of Acid-Base at catalyst surface, can improve the anti-coking, life-span of sodium type ZSM-5 zeolite molecular sieve and to the selectivity of light alkene.The conventional method of introducing assorted element modifier is earlier sodium type ZSM-5 zeolite powder to be carried out after the modification reshaping or will earlier shaping of catalyst be carried out modification again, among the present invention, the introducing of assorted element modifier and the moulding of catalyst are synchronous, thereby simplified the production stage of catalyst, reduced the production cost of industrial catalyst effectively.In addition, in the present invention, adopt compound extrusion aid and add an amount of pore structure conditioning agent, not only can make catalyst be easy to the demoulding, can also improve the intensity and the pore structure of product, effectively improve the diffusion of catalyst, thereby improve the selectivity of low-carbon alkene.Catalyst of the present invention has suitable intensity and high hydrothermal stability, shows high active and to the selectivity of propylene in the reaction of methyl alcohol and/or dimethyl ether conversion.
The specific embodiment
Below in conjunction with specific embodiment, further set forth the present invention, but these embodiment only limit to explain the present invention, and be not used in restriction the present invention.The experimental technique of not marked concrete experiment condition among the following embodiment, usually according to normal condition, or the condition of advising according to manufacturer, the variation of technical scheme is all in protection scope of the present invention in following examples.
Embodiment 1
Get ZSM-5 zeolite powder 100g (SAR=200), to wherein adding 25g aluminium oxide, 2g methylcellulose and 3g sesbania powder, after above-mentioned raw materials mixed, with liquid-solid ratio be the quality percentage composition of 1.5mL nitric acid/2g zeolite be 20% salpeter solution as peptizing agent, add 3.4gLa (NO again
3)
36H
2The assorted element modifier of O.Other preparation process is identical with comparative example 1, and the catalyst that obtains is labeled as S-1, and this catalyst contains 1% La in the quality percentage composition.S-1 is carried out fragmentation, sieve out 20～40 purpose particles and be used for activity rating, reaction is with first alcohol and water mixed feeding (mass ratio CH
3OH: H
2O=2: 1), the activity of such catalysts evaluation result is as shown in table 1.The activity of such catalysts evaluation result is as shown in table 1.
As shown in table 1, under the condition of identical methanol conversion, the La modification of ZSM-5 zeolite helps improving the selectivity of target product propylene.Compare with the introducing method of general assorted element modifier (promptly earlier former powder is carried out after the modification reshaping or will earlier shaping of catalyst be carried out modification again), adopt the assorted element modified catalyst preparation technology of carrying out synchronously of the present invention, catalyst strength and the selectivity of propylene obviously improved with forming technique.
The intensity of the catalyst of table 1 comparative example 1-3 and embodiment 1 and reaction result
*Be 1-butylene, 2-butylene and isobutene sum
Embodiment 2-11
Take by weighing 100g SAR respectively and be 300,400,500,600 and 700 sodium type ZSM-5 zeolite and carry out moulding, add one or more different adhesives and pore structure conditioning agent, add peptizing agent and assorted element modifier again.Peptizing agent is difference nitric acid, sulfuric acid, hydrochloric acid, phosphoric acid, formic acid, acetate or malonic acid, its addition feeds intake by liquid-solid ratio 1.5mL/2g zeolite, the kind and concentration, water vapor concentration and the processing time that are used for the acid of ion-exchange specifically list at table 2, assorted element modifier is one or more of solubility precursor that contain Mg, P, In, Zn, Cu, Mn, Ga, Sr and Ca, concrete raw material proportioning is as shown in table 2, and other preparation process of preformed catalyst is identical with embodiment 1.Reaction is with dimethyl ether and water mixed feeding (mass ratio CH
3OCH
3: H
2O=2: 1), the activity of such catalysts evaluation result is as shown in table 2.
Raw material proportioning and the preparation condition of table 2 embodiment 2-11
| Number | Volumn concentration) | |||||||||
| ??2 | ??300 | Aluminium hydroxide 15g | Starch 3.0g | Sesbania powder 4.0g | ??Mg(NO 3) 2·6H 2O ??3.1g | ??HNO 3??20％ | ??HCl | ?4％ | ??70％ | ??10h |
| ??3 | ??400 | Activated alumina 30g | Polyvinyl alcohol 5.0g | Lemon 1.0g and sesbania powder 1.0g | ??H 3PO 4??1.8g | ??HCl ??20％ | ??HNO 3 | ?3％ | ??60％ | ??8h |
| ??4 | ??500 | Boehmite 20g | Methylcellulose 2.0 | Oxalic acid 2.6g | ??In(NO 3) 2??2.6g | ??H 3PO 4??10％ | ??H 2SO 4 | ?1％ | ??50％ | ??7h |
| ??5 | ??600 | Boehmite 15g | Methylcellulose 7.0g | Tartaric acid 1.5g | ??Zn(NO 3) 2·6H 2O ??10.7g | ??HCOOH ??40％ | ??HNO 3And HCl | Contain 2% HNO 3With 1% HCl | ??50％ | ??6h |
| ??6 | ??600 | Aluminium hydroxide 10g and activated alumina 10g | Starch 5.0g | Glycerine 2.0g | ??Cu(NO 3) 2·3H 2O ??2.9g | ??HCH 3OOH ??30％ | ??HNO 3 | ?1％ | ??50％ | ??6h |
| ??7 | ??600 | Activated alumina 30g and boehmite 15g | Sucrose 2.0g and starch 3.0 g | Stearic acid 1.0g | ??Mn(NO 3) 20.8g and Cu (NO 3) 2·3H 2O ??2.9g | ??HNO 3??20％ | ??HNO 3 | ?1％ | ??50％ | ??6h |
| ??8 | ??700 | Boehmite 10g, aluminium hydroxide 10g and activated alumina 10g | Polyethylene glycol 5.0 g, polyvinyl alcohol 5.0 g and sucrose 2.0g | Graphite powder 3.0g and sesbania powder 1.0g | ??Ga(NO 3) 2·9H 2O ??3.3g | ??HNO 3??20％ | ??HNO 3、 ??H 2SO 4And HCl | Contain 1% HNO 3??、1％ ??H 2SO 4With 1% HCl | ??45％ | ??5h |
| ??9 | ??700 | Aluminium hydroxide 20g | Starch 5.0g | Sesbania powder 1.0g and glycerine 1.0g | ??Sr(NO 3) 20.4g、 ??Ca(NO 3) 2·4H 2O 0.7g and H 3PO 4??1.8g | ??HNO 3??20％ | ??HNO 3 | ??1％ | ??45％ | ??5h |
| ??10 | ??700 | Boehmite 30g | Glucose 10.0 g | Citric acid 1.8g | ??Mg(NO 3) 2·6H 2O ??1.5g | ??HCl ??20％ | ??HNO 3 | ??1％ | ??45％ | ??5h |
| ??11 | ??800 | Clay 20g | Sucrose 7.0g | Oxalic acid 3.5g | ??Ca(NO 3) 2·4H 2O ??0.7g | Malonic acid 30% | ??HCl | ??0.8％ | ??40％ | ??5h |
Embodiment 12
Get the former powder 100g of ZSM-5 na-pretreated zeolite (SAR=1000),, above-mentioned raw materials is mixed, form mixture to wherein adding 2.0g sesbania powder and 2.0g starch.With 3.4g La (NO
3)
36H
2It is to form mixed liquor in 33.3% the silicon sol solution that O is dissolved in 75g quality percentage composition.This mixed liquor is slowly added in the said mixture, mix, be extruded into Φ 2 * 5mm strip, under 80 ℃, freeze-day with constant temperature 12h under air atmosphere, 600 ℃ of calcining 5h.By liquid-solid ratio is the consumption of 10mLHCl/1g zeolite, is that 4% HCl solution exchanges 3 times at 60 ℃ with the quality percentage composition, each 2h.Spend deionised water,, obtain the H-ZSM-5 zeolite in 120 ℃ of oven dry down.With above-mentioned h-type zeolite H
2The O volumn concentration is 40% H
2O/N
2Gas is handled 8h under 600 ℃, the catalyst that gets carries out fragmentation, and reaction is with dimethyl ether and water mixed feeding (mass ratio CH
3OCH
3: H
2O=2: 1), sieve out 20～40 purpose particles and be used for activity rating, the activity of such catalysts evaluation result is as shown in table 3.
Embodiment 13
With 2.0g sesbania powder in the 2.0g glycerine alternate embodiment 12, as the pore structure conditioning agent, remaining preparation condition is identical with example 12 with 2g starch in the 2.0g methylcellulose alternate embodiment 12.Reaction is with dimethyl ether and water mixed feeding (mass ratio CH
3OCH
3: H
2O=2: 1), the activity of such catalysts evaluation result is as shown in table 3.
Embodiment 14
With the quality percentage composition be 2% ammonium nitrate solution to replace quality percentage composition among the embodiment 1 be 2% HCl solution solution in return, all the other preparation conditions are identical with example 1.Reaction is with dimethyl ether and water mixed feeding (mass ratio CH
3OCH
3: H
2O=2: 1), the activity of such catalysts evaluation result is as shown in table 3.
Embodiment 15
With contain the quality percentage composition be the solution of the carbonic hydroammonium of 2% ammonium chloride and 1% to replace quality percentage composition among the embodiment 14 be 2% ammonium nitrate solution solution in return, all the other preparation conditions are identical with example 14.Reaction is with dimethyl ether and water mixed feeding (mass ratio CH
3OCH
3: H
2O=2: 1), the activity of such catalysts evaluation result is as shown in table 3.
Catalyst strength and the reaction result of table 3 embodiment 2-13
| ??2 | ??86 | ??5.6 | ??44.9 | ??14.0 | ??100 |
| ??3 | ??106 | ??11.5 | ??42.1 | ??13.2 | ??99.6 |
| ??4 | ??82 | ??6.6 | ??43.4 | ??14.6 | ??100 |
| ??5 | ??70 | ??6.4 | ??43.2 | ??15.8 | ??100 |
| ??6 | ??62 | ??8.6 | ??40.4 | ??14.7 | ??98.9 |
| ??7 | ??74 | ??6.6 | ??44.7 | ??15.8 | ??100 |
| ??8 | ??88 | ??5.7 | ??44.4 | ??13.8 | ??100 |
| ??9 | ??62 | ??8.2 | ??42.7 | ??15.2 | ??99.8 |
| ??10 | ??64 | ??3.9 | ??40.3 | ??14.3 | ??97.5 |
| ??11 | ??98 | ??8.1 | ??43.1 | ??12.3 | ??100 |
| ??12 | ??48 | ??9.5 | ??45.4 | ??10.4 | ??99.8 |
| ??13 | ??54 | ??9.4 | ??42.0 | ??8.5 | ??100 |
| ??14 | ??67 | ??6.9 | ??44.0 | ??9.9 | ??100 |
| ??15 | ??71 | ??8.4 | ??43.9 | ??12.6 | ??100 |
*Be 1-butylene, 2-butylene and isobutene sum
Embodiment 16
Comparative example 2,3 and embodiment 1,7,8,12 are made catalyst be used for reaction with methyl alcohol, dimethyl ether and water three mixed feeding, wherein the mass ratio of methyl alcohol, dimethyl ether, water is 1: 1: 1, and evaluation result is as shown in table 4.
Table 4 methyl alcohol and dimethyl ether conversion are the reaction result of low-carbon alkene
| Catalyst | Ethylene selectivity (%) | Propylene selectivity (%) | ??C 4 ＝Selectivity *??(％) | Methanol conversion (%) when reacting 200 hours | Dimethyl ether conversion rate (%) when reacting 200 hours |
| Comparative example 2 | ??7.2 | ??40.5 | ??16.3 | ??99.5 | ??99.9 |
| Comparative example 3 | ??6.8 | ??42.5 | ??13.4 | ??99.0 | ??99.2 |
| Embodiment 1 | ??5.8 | ??43.5 | ??15.3 | ??100 | ??100 |
| Embodiment 7 | ??7.5 | ??41.7 | ??14.7 | ??100 | ??100 |
| Embodiment 8 | ??8.4 | ??44.1 | ??15.0 | ??100 | ??100 |
| Embodiment 12 | ??9.4 | ??42.8 | ??13.4 | ??99.1 | ??99.4 |
*Be 1-butylene, 2-butylene and isobutene sum
Comparative example 1
Get ZSM-5 zeolite powder 100g (SAR=200), to wherein adding the 25g aluminium oxide, 2g methylcellulose and 3g sesbania powder, after above-mentioned raw materials mixed, with liquid-solid ratio is that the quality percentage composition of 1.5mL nitric acid/2g zeolite is 20% salpeter solution, slowly join in the above-mentioned mixed material, mix, be extruded into φ 2 * 5mm strip, in 80 ℃ of following freeze-day with constant temperature 12h, air atmosphere is calcined 5h for following 600 ℃, obtains the precursor of catalyst, is the consumption of 10mL HCl/1g zeolite by liquid-solid ratio, the precursor that with the quality percentage composition is 2% HCl solution and catalyst is at 60 ℃ of exchanges 3 times down, each 2h.Spend deionised water,, obtain the H-ZSM-5 zeolite in 120 ℃ of oven dry down.With above-mentioned h-type zeolite H
2The O volumn concentration is 50% H
2O/N
2Mist handle down 8h in 550 ℃, catalyst be labeled as B-1.B-1 is carried out fragmentation, sieve out 20-40 purpose particle and be used for activity rating, reaction is with first alcohol and water mixed feeding (mass ratio CH
3OH: H
2O=2: 1), the activity of such catalysts evaluation result is as shown in table 1.
Comparative example 2
With 0.343g La (NO
3)
36H
2O is dissolved in the 10mL deionized water and is made into maceration extract.Comparative example 1 made under the B-1 catalyst 10g room temperature flood 12h, in 80 ℃ of following freeze-day with constant temperature 12h, 600 ℃ of calcining 5h.With above-mentioned h-type zeolite H
2The O volumn concentration is 50% H
2O/N
2Gas is handled 8h down in 550 ℃.So make catalyst and contain 1% La in the quality percentage composition, catalyst is labeled as B-2, and B-2 is carried out fragmentation, sieves out 20-40 purpose particle and is used for activity rating, and reaction is with first alcohol and water mixed feeding (mass ratio CH
3OH: H
2O=2: 1), the activity of such catalysts evaluation result is as shown in table 1.
Comparative example 3
Getting ZSM-5 zeolite powder 100g (SAR=200), by the consumption of liquid-solid ratio 10mLHCl/1g zeolite, is 2% HCl solution exchange 3 times, 2h at every turn with the quality percentage composition.Spend deionised water,, get catalyst precursor I in 120 ℃ of oven dry down.With 3.4g La (NO
3)
36H
2O is dissolved in the 100mL deionized water and is made into maceration extract.To flood 12h under the catalyst precursor I room temperature, in 80 ℃ of following freeze-day with constant temperature 12h, 600 ℃ of calcining 5h make the catalyst precursor II of La modification; Then catalyst precursor II is used for moulding, its step is as follows: add 25g aluminium oxide, 2g methylcellulose and 3g sesbania powder in catalyst precursor II, after above-mentioned raw materials mixed, by liquid-solid ratio is 1.5mL nitric acid/2g zeolite, slowly adding quality percentage composition is 20% salpeter solution, mix, be extruded into
2 * 5mm strip, in 80 ℃ of following freeze-day with constant temperature 12h, 600 ℃ of calcining 5h get catalyst precursor III; With catalyst precursor III H
2The O volumn concentration is 50% H
2O/N
2Gas is handled 8h down in 550 ℃.The catalyst that obtains is designated as B-3, and this catalyst contains 1% La in the quality percentage composition.B-3 is carried out fragmentation, sieve out 20～40 purpose particles and be used for activity rating, reaction is with first alcohol and water mixed feeding (mass ratio CH
3OH: H
2O=2: 1), the activity of such catalysts evaluation result is as shown in table 1.The activity of such catalysts evaluation result is as shown in table 1.
Claims (12)
1. molecular sieve catalyst for preparing low-carbon alkene, in weight portion, described catalyst is made by the raw material that comprises following component: the sodium type ZSM-5 zeolite of 30-93.7 part, the adhesive of 5-40 part, 0.1-10 the assorted element modifier of part, pore structure conditioning agent of 1-15 part and the extrusion aid of 0.1-5 part, and described assorted element modifier is for containing B, P, La, Ca, Mg, Sr, Zn, Cu, Mn, Cd, the DDGS of one or more elements among Ga and the In, preferably, in weight portion, each component is in the described raw material: the sodium type ZSM-5 zeolite of 46-87.2 part, the adhesive of 10-30 part, 0.5-5 the assorted element modifier of part, pore structure conditioning agent of 2-7 part and the extrusion aid of 0.3-2 part.
2. molecular sieve catalyst according to claim 1, wherein said sodium type ZSM-5 zeolite are that silica alumina ratio is the sodium type ZSM-5 zeolite of 20-2000, and preferable particle size is below the 0.1mm and silica alumina ratio is the sodium type ZSM-5 zeolite of 200-1000.
3. molecular sieve catalyst according to claim 1 and 2, wherein said adhesive is that particle diameter is one or more in 0.1mm following aluminium hydroxide, activated alumina, boehmite, boehmite, Ludox and the clay, is preferably in activated alumina, boehmite, Ludox and the clay one or more.
4. according to each described molecular sieve catalyst among the claim 1-3, wherein said pore structure conditioning agent is selected from one or more in methylcellulose, starch, polyvinyl alcohol, polyethylene glycol, sucrose and the glucose, preferably, described pore structure conditioning agent is selected from one or more in methylcellulose, starch and the sucrose.
5. according to each described molecular sieve catalyst among the claim 1-4, wherein said extrusion aid is selected from one or more in graphite powder, sesbania powder, oxalic acid, tartaric acid, citric acid, glycerine and the stearic acid, and any two kinds in preferred sesbania powder, citric acid and the glycerine is the extrusion aid of forming at 1: 1 by mass ratio.
6. according to each described molecular sieve catalyst among the claim 1-5, wherein said assorted element modifier is the DDGS that contains one or more elements among P, Mg, La, Mn and the Zn.
7. method for preparing each described molecular sieve catalyst among the claim 1-6, this method may further comprise the steps:
A. sodium type ZSM-5 zeolite, pore structure conditioning agent, extrusion aid, adhesive, assorted element modifier and peptizing agent are mixed;
B. the mixture moulding that step a is obtained, drying obtains the precursor I of catalyst after the calcining;
C. the precursor I of the catalyst that step b is obtained is 1) be selected from one or more solution or 2 in hydrochloric acid, sulfuric acid and the nitric acid) exchange in the inorganic ammonium salt solution, obtain catalyst precursor II after the oven dry;
D. the catalyst precursor II that step c is obtained steam and N
2Mist handle, obtain described catalyst, preferably, in described step a, at first sodium type ZSM-5 zeolite, pore structure conditioning agent and extrusion aid are mixed, obtain mixture, then will mix element modifier and peptizing agent add in the described mixture.
8. method according to claim 7, wherein the peptizing agent described in the step a is selected from one or more in nitric acid, hydrochloric acid, phosphoric acid, sulfuric acid, formic acid, acetate and the malonic acid, preferably, described peptizing agent is selected from one or more in nitric acid, acetate and the phosphoric acid.
9. according to claim 7 or 8 described methods, wherein when the adhesive among the described step a was Ludox, described step a was for to mix sodium type ZSM-5 zeolite, pore structure conditioning agent, extrusion aid and assorted element modifier.
10. according to each described method among the claim 7-9, wherein in described step b, the mixture moulding that step a is obtained, 50-120 ℃ of drying, under air atmosphere, calcined 5-7 hour for 500-700 ℃, obtain the precursor I of catalyst, preferably, 70-100 ℃ of drying, under air atmosphere, calcined 5-6 hour for 550-650 ℃, more preferably, at 80 ℃ of freeze-day with constant temperature, under air atmosphere, calcined 5 hours for 600 ℃, obtain the precursor I of catalyst.
11. according to each described method among the claim 7-10, wherein in described step c, the precursor I of the catalyst that step b is obtained is 1) the quality percentage composition is the hydrochloric acid that is selected from of 0.1-5%, one or more solution or 2 in sulfuric acid and the nitric acid) the quality percentage composition is the ammonium nitrate that is selected from of 0.1-5%, one or more solution in ammonium chloride and the carbonic hydroammonium are 20-90 ℃ of exchange 2-5 time, each 1-6 hour, spend the precursor I of the catalyst after deionised water exchanges again, then with the precursor I of catalyst 60-160 ℃ of oven dry, obtain catalyst precursor II; Preferably, the precursor I of the catalyst that step b is obtained the quality percentage composition be 0.8-4% be selected from one or more solution in hydrochloric acid, sulfuric acid and the nitric acid 40-70 ℃ of exchange 3-4 time, each 2-5 hour, spend the precursor I of the catalyst after deionised water exchanges again, then with the precursor I of catalyst 90-140 ℃ of oven dry, obtain catalyst precursor II; More preferably, the precursor I of the catalyst that step b is obtained the quality percentage composition be 3% be selected from one or more solution in hydrochloric acid, sulfuric acid and the nitric acid 60 ℃ of exchanges 3 times, each 2 hours, spend the precursor I of the catalyst after deionised water exchanges again, then with the precursor I of catalyst 120 ℃ of oven dry, obtain catalyst precursor II.
12. according to each described method among the claim 7-11, wherein in described steps d, with steam and N
2Mist at 400-700 ℃, handled 5-10 hour, and steam accounts for the 30-70% of mist volume, preferably, in described steps d, with steam and N
2Mist at 500-600 ℃, handled 5-8 hour, and steam accounts for the 40-60% of mist volume, more preferably, in described steps d, with steam and N
2Mist at 600 ℃, handled 8 hours, and steam accounts for 50% of mist volume.
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