CN101468806B - ZSM-5 molecular sieve and process for preparing catalytic cracking catalyst containing the same - Google Patents
ZSM-5 molecular sieve and process for preparing catalytic cracking catalyst containing the same Download PDFInfo
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- CN101468806B CN101468806B CN2007103041094A CN200710304109A CN101468806B CN 101468806 B CN101468806 B CN 101468806B CN 2007103041094 A CN2007103041094 A CN 2007103041094A CN 200710304109 A CN200710304109 A CN 200710304109A CN 101468806 B CN101468806 B CN 101468806B
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Abstract
The invention provides a method for preparing a ZSM-5 molecular sieve and a method for preparing a catalytic cracking catalyst containing the ZSM-5 molecular sieve. The method can effectively utilize mother liquids generated by preparing a titanium-silicon molecular sieve, reduce the pollution to the environment caused by discharging the mother liquids, and reduce the preparing cost of the ZSM-5 molecular sieve simultaneously. In addition, the light oil micro-active reactivity of the catalyzed cracking catalyst obtained by the ZSM-5 molecular sieve is high.
Description
Technical field
The present invention relates to a kind of preparation method of molecular sieve, relate in particular to a kind of preparation method of ZSM-5 molecular sieve and contain the preparation method of the catalytic cracking catalyst of this molecular sieve.
Background technology
The ZSM-5 molecular sieve from 1972 by since the MOBIL company invention, be widely used in a lot of fields of petrochemical complex, its technology of preparing also becomes the emphasis of research.From the employed raw material of preparation ZSM-5 molecular sieve, mainly comprise silicon source, aluminium source, alkali, water etc.
The Production Flow Chart of ZSM-5 molecular sieve at present generally comprises: synthesize → filtration → ammonium exchange → filtration → seven steps of drying → roasting, and then be used for the production of catalytic cracking catalyst as active component.Because molecular sieve is the preparation of carrying out under alkali metal containing (being generally sodium) condition, so it can not be directly used in the preparation of cracking catalyst, must sodium ion be transformed into ammonium ion earlier through the ammonium exchange, just can be further used for the production of catalyzer.Thereby the catalyst process process of preparation is long, the cost height.
HTS is the novel hetero-atom molecular-sieve that early eighties begins to develop.This molecular sieve analog has excellent catalytic activity and selective paraffin oxidation performance to many organic oxidizing reactions.The preparation method of described HTS generally include will contain silicon source, titanium source, organic bases and/or basic oxide reaction mixture in autoclave at 130-200 ℃ of following hydrothermal crystallizing, filter then, wash, dry, roasting.Wherein, described silicon source can be tetraalkyl silicon ester, colloidal state SiO
2Or alkalimetal silicate, the titanium source can be hydrolyzable titanium compound, described organic bases can be a TPAOH.
Wherein, in the preparation process of HTS, after filtering step, can produce a large amount of mother liquors usually, contain not materials such as the silicon source that consumes, organic bases in this mother liquor.If this mother liquor is directly discarded, will cause environmental pollution; And carry out sewage disposal, then can increase the expense of sewage disposal again.In addition, if the direct depleted of the unemployed composition in the mother liquor is talked about, also can correspondingly increase the production cost of molecular sieve.Therefore, effectively utilizing the mother liquor for preparing the HTS generation has great importance to dividing in the suitability for industrialized production of sieve.
Summary of the invention
The objective of the invention is to be difficult to the shortcoming that is directly used in Preparation of catalysts and can't effectively handles, provide a kind of and can be directly used in the preparation method preparation catalyzer and ZSM-5 molecular sieve that can be effectively the mother liquor that produces in the preparation HTS process be utilized the mother liquor that produces in the preparation HTS process in order to overcome ZSM-5 molecular sieve in the prior art.In addition, the present invention also provides the preparation method of the catalytic cracking catalyst that has adopted this molecular sieve.
The invention provides a kind of preparation method of ZSM-5 molecular sieve, this method comprises mixes silicon source, aluminium source, alkali and water, obtain reaction mixture, with this reaction mixture hydrothermal crystallizing, wherein, described silicon source, alkali and water partly or entirely derive from the mother liquor that preparation is produced during HTS and basic metal in the described reaction mixture and SiO
2Mol ratio less than 0.01.
The present invention also provides a kind of preparation method of catalytic cracking catalyst of the ZSM-5 of containing molecular sieve, this method comprises and will contain the catalyst slurry spraying drying of molecular sieve, clay, binding agent and water, described molecular sieve contains the ZSM-5 molecular sieve, wherein, described ZSM-5 molecular sieve is prepared by method of the present invention.
The preparation method of ZSM-5 molecular sieve provided by the invention can effectively utilize the mother liquor that the preparation HTS produces, and has reduced because of mother liquor discharging pollution on the environment, makes the preparation cost of ZSM-5 molecular sieve reduce simultaneously.Utilize ZSM-5 molecular sieve of the present invention to prepare the preparation method of catalytic cracking catalyst, make the ZSM-5 molecular sieve need not to carry out the ammonium exchange and promptly can be directly used in Preparation of catalysts, shortened the Preparation of catalysts process, reduced preparation cost.In addition, the little reactive behavior alive of light oil of the catalytic cracking catalyst that the ZSM-5 molecular sieve that employing is made by the present invention obtains only is 62 and adopt the little reactive behavior alive of light oil of the ZSM-5 molecular sieve of prior art more than 65.
Description of drawings
Fig. 1 represents X-ray diffraction (XRD) the crystalline phase figure of the product that embodiment 1 makes.
Embodiment
The preparation method of ZSM-5 molecular sieve of the present invention comprises silicon source, aluminium source, alkali and water is mixed, obtain reaction mixture, with this reaction mixture hydrothermal crystallizing, wherein, described silicon source, alkali and water partly or entirely derive from the mother liquor that preparation is produced during HTS and basic metal in the described reaction mixture and SiO
2Mol ratio less than 0.01.
Mother liquor of the present invention is meant when the preparation HTS, after the reaction raw materials that will prepare HTS carries out hydrothermal crystallizing, by filtering the liquid that produces.Described HTS can be conventional various HTS, for example can be TS-1 HTS, TS-2 HTS or Ti-β HTS, and these HTS and their preparation method are conventionally known to one of skill in the art.
In the reaction mixture of the present invention, the consumption of described silicon source, aluminium source, alkali and water is conventionally known to one of skill in the art.As long as the consumption of described silicon source, aluminium source, alkali and water makes in the described reaction mixture, SiO
2/ Al
2O
3Mol ratio is 20-1000, OH
-/ SiO
2Mol ratio is 0.03-0.5, H
2O/SiO
2Mol ratio is that 5-20 gets final product.
Because when preparing HTS according to diverse ways, raw material consumption and reaction conditions have nothing in common with each other, therefore contained various compositions also are different in the mother liquor that finally obtains.The amount of silicon source, alkali and the water that contains in mother liquor satisfies OH
-/ SiO
2Mol ratio is 0.03-0.5, H
2O/SiO
2When mol ratio is 5-20, then only needs in mother liquor, to add the aluminium source and adjust silica alumina ratio, make reaction mixture satisfy SiO
2/ Al
2O
3Mol ratio is that 20-1000 gets final product.The amount of silicon source, alkali and the water that contains in mother liquor does not satisfy OH
-/ SiO
2Mol ratio is 0.03-0.5, H
2O/SiO
2When mol ratio is 5-20, then can adds silicon source, alkali and water and adjust.In addition, need to prove basicity (OH in mother liquor
-) under the too high situation, also can add acid and regulate described basicity.
Under the preferable case, the mother liquor that described silicon source part is produced when deriving from the preparation HTS, described reaction mixture also contains the silicon source that adds.Under above-mentioned preferable case, can more easily adjust each components in proportions in the reaction mixture, can obtain ZSM-5 molecular sieve of the present invention easilier.In the described reaction mixture, the silicon source of the mother liquor that is produced when deriving from the preparation HTS can change in the larger context with the content that adds the silicon source, under the preferable case, with SiO
2Meter is a benchmark with silicon source weight total in the reaction mixture, and the content in the silicon source of the mother liquor that is produced when deriving from the preparation HTS is 1-50 weight %, and the content that adds the silicon source is 50-99 weight %.
Of the present inventionly add silicon source, aluminium source, alkali as long as satisfy basic metal and the SiO that makes in the described reaction mixture
2Mol ratio get final product less than 0.01 condition.Their kind is conventionally known to one of skill in the art, is the raw material of the routine that is used to prepare ZSM-5.In described reaction mixture, when also needing to add the silicon source the silicon source in mother liquor, this adds the silicon source specifically can be in silica gel, silicon sol and the alumino silica gel one or more; Described aluminium source can be one or more in Tai-Ace S 150, alumino silica gel, phosphate aluminium molecular sieve and the aluminium silicophosphate molecular sieve; Described alkali can be one or more in ammoniacal liquor and the alkaline template, and described alkaline template is the basic cpd in the organic formwork agent.
Reaction mixture of the present invention can also contain organic formwork agent Q, and the consumption of described organic formwork agent makes Q/SiO in the described reaction mixture
2Mol ratio be 0.03-0.5, described organic formwork agent Q is that to have quaternary ammonium salt that carbonatoms is the alkyl of 1-4, have carbonatoms be that the quaternary ammonium hydroxide and the general formula of the alkyl of 1-4 is R (NH
2)
nAlkylamine in one or more, wherein R is that carbonatoms is alkyl or the alkylidene group of 1-6, n is 1 or 2.
Under the preferable case, described reaction mixture also comprises the seed molecule sieve.The kind of described seed molecule sieve is conventionally known to one of skill in the art.For example, described seed molecule sieve can be Y zeolite and/or ZSM-5 molecular sieve, and the alkali metal content of described seed molecule sieve is lower than 0.05 weight %; With SiO
2Meter is a benchmark with the gross weight in the silicon source in the reaction mixture, and the content of described seed molecule sieve is below the 5 weight %.
The condition of hydrothermal crystallizing of the present invention generally includes: crystallization temperature is 110-220 ℃, and crystallization time is 6 hours to 10 days.Under the preferable case, described crystallization temperature is 130-220 ℃, and crystallization time is 1-6 days.Further under the preferable case, before carrying out described hydrothermal crystallizing, earlier reaction mixture is carried out ageing, described aged temperature is 20-110 ℃, is preferably 30-100 ℃, and the described aged time is 4-48 hour, is preferably 8-24 hour.
In addition, need to prove that when relating to consumption, silicon of the present invention source is all with SiO
2Meter, described aluminium source is all with Al
2O
3Meter, described alkali is all with OH
-Meter.
The preparation method of the catalytic cracking catalyst of the ZSM-5 of containing molecular sieve of the present invention comprises and will contain the catalyst slurry spraying drying of molecular sieve, clay, binding agent and water, described molecular sieve contains the ZSM-5 molecular sieve, wherein, described ZSM-5 molecular sieve is prepared by the preparation method of ZSM-5 of the present invention.
Utilize ZSM-5 molecular sieve of the present invention to prepare the preparation method of catalytic cracking catalyst, make the ZSM-5 molecular sieve need not to carry out the drying and roasting process after ammonium exchange and the ammonium exchange, promptly can be directly used in Preparation of catalysts, shorten the Preparation of catalysts process, reduce preparation cost.And the ZSM-5 molecular sieve that forms catalyst slurry can directly use the ZSM-5 molecular sieve pulp that produces when described ZSM-5 molecular sieve prepares, promptly need not described ZSM-5 molecular sieve pulp drying, and be directly used in Preparation of catalysts.
In the catalyst slurry of the present invention, the content of molecular sieve, clay, binding agent can be employed content in the conventional preparation catalytic cracking catalyst method.For example, be benchmark with the dry weight of described catalyst slurry, the content of described molecular sieve is 10-50 weight %, and described clay is 10-70 weight %, and the content of described binding agent is 10-45 weight %.In addition, the content of described water can suitably be regulated as required, as long as can carry out spraying drying.The kind of described clay, binding agent is conventionally known to one of skill in the art.
Molecular sieve of the present invention contains the ZSM-5 molecular sieve, and described molecular sieve can all be the ZSM-5 molecular sieve, also can partly be described ZSM-5 molecular sieve.In described molecular sieve, except the ZSM-5 molecular sieve, also contain under the situation of other molecular sieve, described other molecular sieve can be a Y zeolite for example, gross weight with molecular sieve is a benchmark, the content of described ZSM-5 molecular sieve is 5-30 weight %, and the content of described Y zeolite is 70-95 weight %.
In addition, described catalyst slurry is carried out spray-dired method also for conventionally known to one of skill in the art.Described spray-dired condition is conventionally known to one of skill in the art, and for example described spray-dired temperature can be 130-200 ℃.
Further specify method of the present invention below by embodiment.
Below among each embodiment, the relative crystallinity of product is that X-ray diffraction separately (XRD) spectrogram with this product and standard specimen is that the ratio of the peak height sum of five the XRD diffraction peaks (being commonly called as Five Fingers Peak) between 22.5-25.0 ° is represented at 2 θ angles.The sample of standard specimen wherein for making as follows is defined as 100% with its degree of crystallinity.
The preparation of standard specimen: 0.56 gram NaOH (chemical pure) is dissolved in the 28 gram deionized waters, under agitation adds 1.34 gram Al
2(SO
4)
318H
2O and 1.46 gram n-Butyl Amine 99s (chemical pure) add 12 gram 40-120 purpose silica gel (Haiyang Chemical Plant, Qingdao's product) again, obtain mixture.This mixture is placed the stainless steel sealed reactor,, obtains product after the cooling 170 ℃ of following hydrothermal crystallizings 24 hours, with this product after filtration, washing, ammonium exchange, filter, washing, dry, roasting obtain standard specimen.Wherein, the method for described ammonium exchange be by weight mixing in 1: 1: 10,90 ℃ of stirring reactions 1 hour with molecular sieve, ammonium nitrate and chemical water; Described roasting is to heat 30 minutes down at 550 ℃.This standard specimen by XRD analysis, is determined that its crystal phase structure is the ZSM-5 molecular sieve.
The mother liquor that is produced during the described preparation HTS used in the various embodiments of the present invention in addition, is the mother liquor that following method obtains:
Method according to the embodiment 1 of US 4410501 is prepared: under whipped state, 15 gram tetraethyl titanates are added in the 455 gram tetraethyl orthosilicates, and then be added dropwise to 800 the gram 25 weight % the tetrapropyl oxyammonia aqueous solution, stirred 1 hour, being heated to 80-90 ℃ then kept 5 hours, adding deionized water then makes cumulative volume reach 1.5 liters, this liquid is transferred in the autoclave, under agitation 175 ℃ of following crystallization 10 days, be cooled to room temperature, filter, promptly obtain needed HTS, the filtrate that filtration is obtained is used for the preparation of following each embodiment ZSM-5 molecular sieve as mother liquor.The analysis showed that (Chen Biyou compiles.Factory's analytical chemistry handbook.National Defense Industry Press.1992:261), SiO in this mother liquor
2Content is 5 weight %, and OH content is 3 weight %, and the pH value is 13.
Comparative Examples 1
5.6 gram NaOH (chemical pure) are dissolved in the 280 gram deionized waters, under agitation add 13.4 gram Al
2(SO
4)
318H
2O and 14.6 gram n-Butyl Amine 99s (chemical pure) add 120 gram silica gel (Qingdao silica gel factory) again.This mixture is placed the stainless steel sealed reactor, in 170 ℃ of crystallization 24 hours, the cooling after product after filtration → washing → ammonium exchange → filtration → washing → drying → roasting, obtain ZSM-5 molecular sieve (degree of crystallinity is 100%).The method of described ammonium exchange be by weight mixing in 1: 1: 10,90 ℃ of stirring reactions 1 hour with molecular sieve, ammonium nitrate and chemical water; Described roasting is to heat 30 minutes down at 550 ℃.
Present embodiment illustrates the preparation method of ZSM-5 molecular sieve of the present invention.
Alumino silica gel (Qingdao silica gel factory, mol ratio SiO with 125 grams
2/ Al
2O
3=100) join in the mother liquor of the 200 described preparation HTS that restrain, stir, obtain reaction mixture.In this reaction mixture, mol ratio SiO
2/ Al
2O
3=106, OH
-/ SiO
2=0.17, H
2O/SiO
2=5.With SiO
2Meter is a benchmark with silicon source weight total in the reaction mixture, is 7.5 weight % from the content in the silicon source of mother liquor.Basic metal in the described reaction mixture and SiO
2Mol ratio be 0.007.
The reaction mixture that obtains is placed the stainless steel sealed reactor, earlier 110 ℃ of ageings 5 hours, again 165 ℃ of following hydrothermal crystallizings 30 hours, be cooled to room temperature, filtration → washing then → filtration obtains molecular sieve pulp, will obtain product after this molecular sieve pulp drying.The XRD crystalline phase figure of this product shows that this product is the ZSM-5 molecular sieve as shown in Figure 1, and degree of crystallinity is 97%.
Embodiment 2
Present embodiment illustrates the preparation method of ZSM-5 molecular sieve of the present invention.
Alumino silica gel (Qingdao silica gel factory, mol ratio SiO with 160 grams
2/ Al
2O
3=40) and 100 gram chemical water join in the mother liquor of described preparation HTS of 150 grams, stir, obtain reaction mixture.In this reaction mixture, mol ratio SiO
2/ Al
2O
3=42, OH
-/ SiO
2=0.06, H
2O/SiO
2=5.With SiO
2Meter is a benchmark with silicon source weight total in the reaction mixture, is 4.6 weight % from the content in the silicon source of mother liquor.Basic metal in the described reaction mixture and SiO
2Mol ratio be 0.008.
The reaction mixture that obtains is placed the stainless steel sealed reactor, earlier 120 ℃ of ageings 7 hours, again 170 ℃ of following hydrothermal crystallizings 24 hours, be cooled to room temperature, filtration → washing then → filtration obtains molecular sieve pulp, will obtain product after this molecular sieve pulp drying.The product that the XRD crystalline phase figure of this product and embodiment 1 make is similar, shows that this product is the ZSM-5 molecular sieve, and degree of crystallinity is 105%.
Embodiment 3
Present embodiment illustrates the preparation method of ZSM-5 molecular sieve of the present invention.
Alumino silica gel (Qingdao silica gel factory, mol ratio SiO with 500 grams
2/ Al
2O
3=200), 60 the gram n-Butyl Amine 99s and 785 the gram water join 500 the gram described preparation HTS mother liquor in, stir, obtain reaction mixture.In this reaction mixture, mol ratio SiO
2/ Al
2O
3=208, OH
-/ SiO
2=0.1, n-Butyl Amine 99/SiO
2=0.1, H
2O/SiO
2=8.With SiO
2Meter is a benchmark with silicon source weight total in the reaction mixture, is 4.7 weight % from the content in the silicon source of mother liquor.Basic metal in the described reaction mixture and SiO
2Mol ratio be 0.006.
The reaction mixture that obtains is placed the stainless steel sealed reactor, earlier 120 ℃ of ageings 7 hours, again 170 ℃ of following hydrothermal crystallizings 30 hours, be cooled to room temperature, filtration → washing then → filtration obtains molecular sieve pulp, will obtain product after this molecular sieve pulp drying.The product that the XRD crystalline phase figure of this product and embodiment 1 make is similar, shows that this product is the ZSM-5 molecular sieve, and degree of crystallinity is 99%.
Embodiment 4
Present embodiment illustrates the preparation method of ZSM-5 molecular sieve of the present invention.
With 500 gram silica gel (Qingdao silica gel factory, mol ratio SiO
2/ Al
2O
3=600), 640 gram water join in the mother liquor of described preparation HTS of 700 grams, stir, and obtain reaction mixture.In this reaction mixture, mol ratio SiO
2/ Al
2O
3=610, OH
-/ SiO
2=0.15, H
2O/SiO
2=10.With SiO
2Meter is a benchmark with silicon source weight total in the reaction mixture, is 6.5 weight % from the content in the silicon source of mother liquor.Basic metal in the described reaction mixture and SiO
2Mol ratio be 0.007.
The reaction mixture that obtains is placed the stainless steel sealed reactor, earlier 90 ℃ of ageings 11 hours, again 165 ℃ of following hydrothermal crystallizings 30 hours, be cooled to room temperature, filtration → washing then → filtration obtains molecular sieve pulp, will obtain product after this molecular sieve pulp drying.The product that the XRD crystalline phase figure of this product and embodiment 1 make is similar, shows that this product is the ZSM-5 molecular sieve, and degree of crystallinity is 101%.
Embodiment 5
Present embodiment illustrates the preparation method of ZSM-5 molecular sieve of the present invention.
Method according to embodiment 4 prepares the ZSM-5 molecular sieve, and different is that also adding in the described reaction mixture has the seed molecule of 18 grams sieve (ZSM-5 molecular sieve, the production of Shandong catalyst plant, SiO
2/ Al
2O
3=50, the alkali metal content of described seed molecule sieve is lower than 0.05 weight %).Obtain in the reaction mixture mol ratio SiO
2/ Al
2O
3=610, OH
-/ SiO
2=0.15, H
2O/SiO
2=10.With SiO
2Meter is a benchmark with the gross weight in the silicon source in the reaction mixture, and the content of described seed molecule sieve is 3.4 weight %.With SiO
2Meter is a benchmark with silicon source weight total in the reaction mixture, is 6.5 weight % from the content in the silicon source of mother liquor.Basic metal in the described reaction mixture and SiO
2Mol ratio be 0.008.
Finally obtain product.The product that the XRD crystalline phase figure of this product and embodiment 1 make is similar, shows that this product is the ZSM-5 molecular sieve, and degree of crystallinity is 103%.
Comparative Examples 2
Catalytic cracking catalyst of this Comparative Examples explanation prior art and preparation method thereof.
ZSM-5 molecular sieve and 20 gram pseudo-boehmites (solid content 35 weight %, Shandong Aluminum Plant produces), 10 gram aluminium colloidal sols that 25 gram REUSY molecular sieves (Qilu Petrochemical company catalyst plant produces, Y zeolite), 8 gram Comparative Examples 1 are made (contain 21 weight %Al
2O
3, Qilu Petrochemical company catalyst plant produces) and 35 gram kaolin (solid content is 85 heavy %, and China Kaolin Co., Ltd's industry is produced) mix and pulled an oar 30 minutes, spraying drying obtains catalyst A 550 ℃ of following roastings again.
Embodiment 6
Present embodiment illustrates catalytic cracking catalyst of the present invention and preparation method thereof.
(Qilu Petrochemical company catalyst plant produces with 25 gram REUSY molecular sieves, Y zeolite), the 20 ZSM-5 molecular sieve pulps that make of gram embodiment 1 (contain ZSM-5 molecular sieve 8 grams, solid content is 40 heavy %) (contain 21 weight %Al with 20 gram pseudo-boehmites (solid content 35 weight %, Shandong Aluminum Plant produces), 10 gram aluminium colloidal sols
2O
3, Qilu Petrochemical company catalyst plant produces) and 35 gram clays (kaolin, solid content are 85 heavy %, and China Kaolin Co., Ltd's industry is produced) mix to pull an oar and obtained catalyst slurry in 30 minutes.Then with this catalyst slurry 180 ℃ of following spraying dryings, obtain catalyst B 1 550 ℃ of following roastings again.
Dry weight with described catalyst slurry is a benchmark, and the content of described molecular sieve is 46 weight %, and the content of described binding agent is 12 weight %, and the content of described clay is 42 weight %.Total amount with molecular sieve is a benchmark, and the content of described ZSM-5 molecular sieve is 24 weight %, and the content of described Y zeolite is 76 weight %.
Embodiment 7
Present embodiment illustrates catalytic cracking catalyst of the present invention and preparation method thereof.
(Qilu Petrochemical company catalyst plant produces with 25 gram REUSY molecular sieves, Y zeolite), the 11 ZSM-5 molecular sieve pulps that make of gram embodiment 2 (contain ZSM-5 molecular sieve 4 grams, solid content is 35 heavy %) (contain 21 weight %Al with 20 gram pseudo-boehmites (solid content 35 weight %, Shandong Aluminum Plant produces), 10 gram aluminium colloidal sols
2O
3, Qilu Petrochemical company catalyst plant produces) and 35 gram clays (kaolin, solid content are 85 heavy %, and China Kaolin Co., Ltd's industry is produced) mix to pull an oar and obtained catalyst slurry in 30 minutes.Then with this catalyst slurry 180 ℃ of following spraying dryings, obtain catalyst B 2 550 ℃ of following roastings again.
Dry weight with described catalyst slurry is a benchmark, and the content of described molecular sieve is 42 weight %, and the content of described binding agent is 14 weight %, and the content of described clay is 44 weight %.Total amount with molecular sieve is a benchmark, and the content of described ZSM-5 molecular sieve is 14 weight %, and the content of described Y zeolite is 86 weight %.
Comparative Examples 3
The activity of this Comparative Examples explanation catalyst A.
Catalyst A 800 ℃ of following hydrothermal agings 4 hours, is carried out the little reactive behavior evaluation alive of light oil as follows, and the result is as shown in table 1.
Concrete evaluation method: 5 gram catalyzer are put into fixed-bed reactor, be heated to 460 ℃, feed 1.56 gram reactions then with oily, reaction times is 70 seconds, use ice-cold method to collect product, the oil product of collecting is analyzed, and then calculate little work (MA) of catalyzer with chromatographic instrument.
Embodiment 7
According to the method evaluate catalysts B1 of Comparative Examples 2 and the activity of B2.The result is as shown in table 1.
Table 1
| The catalyzer numbering | A | B1 | B2 |
| MA | 62 | 65 | 66 |
As can be seen from Table 1, adopting the little reactive behavior alive of light oil of the catalytic cracking catalyst of the ZSM-5 molecular sieve acquisition that is made by the present invention is more than 65, is higher than the activity of such catalysts of employing by the ZSM-5 molecular sieve of existing method preparation.
Claims (14)
1. the preparation method of a ZSM-5 molecular sieve, this method comprises mixes silicon source, aluminium source, alkali and water, obtain reaction mixture, with this reaction mixture hydrothermal crystallizing, it is characterized in that, described silicon source, alkali and water partly or entirely derive from the mother liquor that preparation is produced during HTS and basic metal in the described reaction mixture and SiO
2Mol ratio less than 0.01.
2. method according to claim 1, wherein, the mother liquor that described silicon source part is produced when deriving from the preparation HTS, described reaction mixture also contains the silicon source that adds.
3. method according to claim 1, wherein, with SiO
2Meter is a benchmark with silicon source weight total in the reaction mixture, and the content in the silicon source of the mother liquor that is produced when deriving from the preparation HTS is 1-50 weight %, and the content that adds the silicon source is 50-99 weight %.
4. according to claim 2 or 3 described methods, wherein, the described silicon source that adds is in silicon sol, silicon gel and the alumino silica gel one or more.
5. method according to claim 1, wherein, SiO
2/ Al
2O
3Mol ratio is 20-1000, OH
-/ SiO
2Mol ratio is 0.03-0.5, H
2O/SiO
2Mol ratio is 5-20.
6. according to claim 1,2,3 or 5 described methods, wherein, described reaction mixture also contains organic formwork agent Q, and the consumption of described organic formwork agent makes Q/SiO in the described reaction mixture
2Mol ratio be 0.03-0.5, described organic formwork agent Q is that to have quaternary ammonium salt that carbonatoms is the alkyl of 1-4, have carbonatoms be that the quaternary ammonium hydroxide and the general formula of the alkyl of 1-4 is R (NH
2)
nAlkylamine in one or more, wherein R is that carbonatoms is alkyl or the alkylidene group of 1-6, n is 1 or 2.
7. according to claim 1,2,3 or 5 described methods, wherein, described reaction mixture also contains the seed molecule sieve, and the alkali metal content of described seed molecule sieve is lower than 0.05 weight %; With SiO
2Meter is a benchmark with the gross weight in the silicon source in the reaction mixture, and the content of described seed molecule sieve is below the 5 weight %.
8. method according to claim 7, wherein, described seed molecule sieve is Y zeolite and/or ZSM-5 molecular sieve.
9. method according to claim 1, wherein, the condition of described hydrothermal crystallizing comprises: crystallization temperature is 110-220 ℃, crystallization time is 6 hours to 10 days.
10. method according to claim 1, wherein, described aluminium source is one or more in Tai-Ace S 150, sodium aluminate and the alumino silica gel.
11. method according to claim 1, wherein, described alkali is ammoniacal liquor or alkaline template.
12. preparation method who contains the catalytic cracking catalyst of ZSM-5 molecular sieve, this method comprises and will contain the catalyst slurry spraying drying of molecular sieve, clay, binding agent and water, described molecular sieve contains the ZSM-5 molecular sieve, it is characterized in that described ZSM-5 molecular sieve is prepared by any described method among the claim 1-11.
13. the preparation method of catalytic cracking catalyst according to claim 12, wherein, be benchmark with the dry weight of described catalyst slurry, the content of described molecular sieve is 10-50 weight %, described clay is 10-70 weight %, and the content of described binding agent is 10-45 weight %.
14. the preparation method of catalytic cracking catalyst according to claim 12, wherein, described molecular sieve also contains Y zeolite, and is benchmark with the gross weight of molecular sieve, the content of described ZSM-5 molecular sieve is 5-30 weight %, and the content of described Y zeolite is 70-95 weight %.
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| CN103418425B (en) * | 2012-05-16 | 2016-12-14 | 中国石油化工股份有限公司 | Catalyst of preparing propylene by methanol transformation and preparation method thereof |
| CN104107713B (en) * | 2013-04-16 | 2017-07-14 | 中国石油化工股份有限公司 | C 4 olefin cracks catalyst of propylene processed and its production and use |
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