CN103771437A - Phosphorate-containing modified beta-molecular sieve - Google Patents
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- CN103771437A CN103771437A CN201210417720.9A CN201210417720A CN103771437A CN 103771437 A CN103771437 A CN 103771437A CN 201210417720 A CN201210417720 A CN 201210417720A CN 103771437 A CN103771437 A CN 103771437A
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Abstract
The invention provides a phosphorate-containing modified beta-molecular sieve which is characterized in that the content of phosphorus accounts for 3-10 w% of P2O5, in the <27>Al MAS NMR of the molecular sieve, the value of ratio of a resonance signal peak area with the chemical shift of 37-43 ppm to a resonance signal peak area with the chemical shift of 51-57 ppm is not less than 1. In the molecular sieve, phosphorus is in full coordination with framework aluminum, the framework aluminum is fully protected, and the phosphorate-containing modified beta-molecular sieve has excellent hydrothermal stability and better product selectivity.
Description
Technical field
The invention relates to a kind of molecular sieve and preparation method thereof, further say about a kind of phosphorous modified beta molecular sieve and preparation method thereof.
Background technology
First the Wadlinger of Mobile company in 1967 uses sodium aluminate, silica gel, tetraethyl ammonium hydroxide (TEAOH) and water mixed crystal to be combined to beta-molecular sieve, beta-molecular sieve has the characteristic of high silica alumina ratio, and silica alumina ratio can be tens to modulation in the scope of hundreds of.Martens etc. utilize decane to disclose the skeleton structure of 12 yuan of annular distances of beta-molecular sieve for probe reaction; 1988, the employing tectonic models such as Newsam and Higgins, simulation powdery diffractometry were determined the Stacking Fault Structure of beta-molecular sieve first.Beta-molecular sieve has twelve-ring intersection pore passage structure, and 12 yuan of annular apertures that are parallel to the one-dimensional channels of (001) crystal face are 0.75～0.57nm, and 12 yuan of annular apertures in another two-dimentional duct parallel with (100) crystal face are 0.65～0.56nm.Beta-molecular sieve is the high-silica zeolite of unique a kind of macropore three-dimensional structure of finding up to now, due to the singularity of its structure, have acid catalysis characteristic and structure selectivity concurrently, and there is very high thermostability (lattice damage temperature is greater than 1200 ℃), hydrothermal stability and wear resisting property.Due to unique constitutional features, in a series of catalyzed reactions, beta-molecular sieve has good heat and hydrothermal stability, acid resistance, anti-coking and catalytic activity, show good performance at the aspect such as catalysis, absorption, therefore be with a wide range of applications, developed rapidly in recent years and become a kind of novel catalytic material.After modification or some metal constituent element of load, can be used in the refining of petroleum such as hydrocracking, hydro-isomerization, olefin hydration and petrochemical process.
In many catalyzed chemical reaction processes, need to there is the molecular sieve of metal or metal ion (as Ni, Co, Cu, Ag, Zn, Fe, Mn, Cr, Zr, Mo, W, alkaline-earth metal, rare earth metal etc.) as the active ingredient of catalyzer with load or exchange, or utilize hydrogenation, the dehydrogenation functionality of this metal, or utilize this metal and the synergy at acidic zeolite center to reach the specific desired specific purposes of reacting.
CN1098028A discloses a kind of beta-molecular sieve catalyzer for toluene disproportionation and transalkylation reaction, this catalyzer is made up of the beta-molecular sieve of 10～90 % by weight, the binding agent of 5～90 % by weight, the metal that is selected from Ni, Co, Cu, Ag, Sn, Ga etc. of 0.05～5 % by weight, and metal wherein adopts pickling process load.
USP5,453,553 disclose a kind of benzene reacts the processing method of preparing dodecylbenzene with laurylene, wherein use catalyzer be by X, Y, M, ZSM-12 or beta-molecular sieve carrying transition metal Fe, Ni, Co, Pt, Ir one or more and obtain, these metals are to load in the hole of molecular sieve by dipping method, this catalyzer can obviously improve the stability of the synthetic used catalyst of dodecylbenzene, but must just can reach the object that improves activity stability facing reaction under nitrogen atmosphere.
It is on the one hand in the process that removes its template, easily to make its structure suffer damage that beta-molecular sieve subject matter is in use embodied in, be on the other hand in reaction process easily dealuminzation thereby activity stability poor.
In USP 4,605,637, having proposed a kind of method, is with crystallite state AlPO in liquid phase water system
4the molecular sieve that-5 aluminum phosphate materials such as grade are processed low acidity for example containing the ZSM-5 of B, containing beta-molecular sieve, the high silica ZSM-5 molecular sieve etc. of B, Al nuclear power is moved in the skeleton of molecular sieve, thereby improves the acidity of molecular sieve, increase lytic activity.
A kind of method of modifying of beta-molecular sieve is proposed in CN 1043450A, the method is that Na beta-molecular sieve is pumped to part framework aluminum with acid after roasting, then carrying out potassium exchange, to make molecular sieve potassium content be 0.5～2.5 heavy %, after drying, roasting, at room temperature soak 4～10 hours with microcosmic salt buffered soln including potassium hydrogen phosphate-potassium primary phosphate, Hypophosporous Acid, 50-potassium hypophosphite, phosphorous acid-potassium phosphite, nearly neutrality, take the circumstances into consideration washing or do not wash that to make on molecular sieve phosphorus content be 0.01～0.5 heavy %, then dry, roasting; Beta-molecular sieve after the method modification is applicable to as the hydrocarbon processing catalyzer that relates to hydroisomerization reaction.
A kind of method of modifying of beta-molecular sieve has been proposed in CN 1179994A, the method by Na beta-molecular sieve by ammonium ion exchange to the Na on molecular sieve
2o content is less than 0.1 heavy %; Then the beta-molecular sieve of above-mentioned ammonium exchange is pumped to part framework aluminum with acid treatment, make its silica alumina ratio be greater than 50; Beta-molecular sieve after above-mentioned dealuminzation is mixed to post-drying with phosphoric acid or phosphoric acid salt, make P on gained molecular sieve
2o
5amount be 2～5 heavy %; Finally under water vapour atmosphere with 450～650 ℃ of hydrothermal calcines 0.5～4 hour.Can obtain higher alkene, the especially productive rate of isomeric olefine and lower coke yield by the beta-molecular sieve after the method modification when the cracking reaction for hydro carbons.
In CN1205249A, proposed a kind of method of modifying of beta-molecular sieve, the method comprises former the beta-molecular sieve synthesizing powder and contains Al
2o
3source, P
2o
5source, SiO
2source, H
2o
2and the mixture of water is according to beta-molecular sieve: Al
2o
3: P
2o
5: SiO
2: H
2o
2: H
2o=1:(0.001～0.02): (0.01～0.30): (0～0.05): (0～0.10): the weight ratio of (1.0～3.0) mixes, after drying, be warming up to again 400～650 ℃ of roastings 1～5 hour, and then by ordinary method through ammonium ion exchange to its Na
2o content is less than 0.1 heavy %, and the method can make the activity stability of beta-molecular sieve be significantly improved, and also can make its crystallization reservation degree be improved simultaneously.
Summary of the invention
Contriver is surprised to find that after by a large amount of modified tests for beta-molecular sieve and materialization phenetic analysis, a kind of modified beta molecular sieve through phosphorus and transition metal, its
27in Al MAS NMR, chemical shift is that the feature of 40 ± 3ppm and 54ppm ± 3ppm aluminium species resonance signal is but different from prior art.
Therefore.One of object of the present invention is to provide a kind of a kind of phosphorous modified beta molecular sieve that is different from prior art feature, and two of object is to provide the preparation method of this molecular sieve.
Phosphorous modified beta molecular sieve provided by the invention, is characterized in that, with P
2o
5meter phosphorus content accounts for the heavy % of 3-10, this molecular sieve
27in Al MAS NMR, chemical shift is that 40 ± 3ppm resonance signal peak area and chemical shift are that the ratio of 54ppm ± 3ppm resonance signal peak area is more than or equal to 1.
The present invention also provides the preparation method of above-mentioned phosphorous modified beta molecular sieve, it is characterized in that comprising that the former powder of beta-molecular sieve is in the temperature range of 200 ℃ to 800 ℃, the step of carrying out again phosphorus modification after at least two non-overlapping temperature ranges are from low to high processed with removed template method.More specifically, comprise the steps:
(1) sodium type beta-molecular sieve is made to the Na on molecular sieve through ammonium exchange
2o content is less than 0.2 heavy %;
(2) after drying, calcination process at least 0.5 hour at 200-400 ℃, then being warmed up at least 0.5 hour removed template method of calcination process at 500-800 ℃ in 2 hours at the most for molecular sieve step (1) being obtained;
(3) introduce P contained compound molecular sieve is carried out to modification;
(4) calcination process at least 0.5 hour at 400～800 ℃.
Phosphorous modified beta molecular sieve provided by the invention, can be applied in catalytic cracking or Deep Catalytic Cracking process, as the active ingredient of catalyzer or auxiliary agent.In modified beta molecular sieve provided by the invention, phosphorus and framework aluminum coordination be abundant, and framework aluminum is adequately protected, and has excellent hydrothermal stability and better product selectivity.
Embodiment
The beta-molecular sieve of phosphorous modification provided by the invention, is characterized in that, with P
2o
5meter phosphorus content accounts for the heavy % of 3-10, this molecular sieve
27in Al MAS NMR, chemical shift is that 40 ± 3ppm resonance signal peak area and chemical shift are that the ratio of 54ppm ± 3ppm resonance signal peak area is more than or equal to 1.
Phosphorous modified beta molecular sieve provided by the invention, with P
2o
5meter phosphorus content accounts for the heavy % of 3-10, preferably accounts for the heavy % of 5-9.
Phosphorous modified beta molecular sieve provided by the invention, its
27in Al MAS NMR, chemical shift is the four-coordination framework aluminum species that 54 ± 3ppm resonance signal characterizes, chemical shift be 40 ± 3ppm resonance signal characterize be and the framework aluminum species of phosphorus coordination.Modified beta molecular sieve provided by the invention, this molecular sieve
27in Al MASNMR, chemical shift is that 40 ± 3ppm resonance signal peak area and chemical shift are that the ratio of 54ppm ± 3ppm resonance signal peak area is more than or equal to 1, is preferably greater than or equal to 2, for example 1.5 to 5 value.
Above-mentioned phosphorous modified beta molecular sieve provided by the invention comprises that by former beta-molecular sieve powder (containing the sodium type beta-molecular sieve of organic formwork agent) step of carrying out again phosphorus modification after at least two non-overlapping temperature ranges are from low to high processed with removed template method obtains in the temperature range of 200 ℃ to 800 ℃.More particularly comprise the steps:
(1) sodium type beta-molecular sieve is made to the Na on molecular sieve through ammonium exchange
2o content is less than 0.2 heavy %;
(2) molecular sieve step (1) being obtained after drying, is processed at least 0.5 hour under 200-400 ℃ of temperature range, then under 500-800 ℃ of temperature range, processes at least 0.5 hour removed template method being warmed up in 2 hours at the most;
(3) introduce P contained compound molecular sieve is carried out to modification;
(4) calcination process at least 0.5 hour at 400～800 ℃.
In preparation method provided by the invention, in said step (1), the sodium type beta-molecular sieve (as USP3,308,069, CNZL00107486.5) that said sodium type beta-molecular sieve is conventional crystallization gained.In usually said sodium type beta-molecular sieve, sodium content is counted the heavy % of 4-6 with sodium oxide.Said ammonium exchanges to reduce the process of sodium content, preferably according to molecular sieve: ammonium salt: H
2o=1:(0.1～1): the weight ratio of (5～10) exchange at least 0.5 hour at room temperature to 100 ℃, the preferred process of filtering after 0.5～2 hour, such ammonium exchange process can repeat 1～4 time, so that the Na on molecular sieve
2o content is less than 0.2 heavy %.Said ammonium salt can be conventional inorganic ammonium salt, can be selected from one of ammonium chloride, ammonium sulfate or ammonium nitrate or their mixture.
In preparation method provided by the invention, said step (2) is the molecular sieve that adopts low temperature to obtain to the interval treatment step of differing temps (1) of high temperature, the process of removed template method.Said processing is in the interval of 200 ℃ to 800 ℃, in at least two non-overlapping temperature ranges from low to high, carry out, said low temperature range is 200-400 ℃, preferred 300-350 ℃, and said high temperature range is 500-800 ℃, preferred 500-600 ℃.For example, said processing is by Na after the exchange of step (1) ammonium
2the molecular sieve that O content is less than 0.2 heavy % after dry first 200-400 ℃, preferred calcination process at least 0.5 hour at 300-350 ℃, preferably 1～12 hour, then 2 hours at the most, be preferably warmed up under 500-800 ℃ of temperature range calcination process in 1 hour at least 0.5 hour, preferably 1～8 hour.In step (2), also can, before above-mentioned said two temperature ranges are processed, first at least process 1 hour at 120-180 ℃.
In preparation method provided by the invention, introduce P contained compound in step (3) product of step (2) is carried out to modification.Said P contained compound is selected from one of phosphoric acid, ammonium hydrogen phosphate, primary ammonium phosphate or ammonium phosphate or its mixture.Preferably adopt impregnation method to carry out, said dipping is by the P contained compound aqueous solution of the molecular sieve after removed template method and calculated amount in room temperature to 95 ℃ making beating evenly, dries.
The invention provides in preparation method, step (4) is that the beta-molecular sieve product of phosphorus modification that step (3) is obtained is at 400～800 ℃, preferably calcination process at least 0.5 hour at 500-600 ℃, preferred 0.5-8 hour.Wherein said calcination process process can adopt dry roasting also can adopt wet roasting, and said wet roasting is preferably at 1-100%, more preferably carry out under 100% steam atmosphere.
The present invention is further illustrated for the following examples, but not thereby limiting the invention.
In each embodiment and comparative example, Na in each sample beta-molecular sieve
2o, P
2o
5, Al
2o
3, SiO
2content for x-ray fluorescence method measure (referring to " Petrochemical Engineering Analysis method (RIPP experimental technique) ", the volumes such as Yang Cuiding, Science Press, nineteen ninety publish).
27al MAS NMR adopts Bruker Avance III 500MHz nuclear magnetic resonance analyser to test, and resonance peak spectrogram carries out adopting integration to calculate each peak area after swarming matching.
Embodiment 1
By beta-molecular sieve, (Shandong catalyst plant is produced, SiO
2/ Al
2o
3=25, the heavy % of sodium oxide content 4.5, lower with) use NH
4the exchange of Cl solution is washed to Na
2o content, lower than 0.2 % by weight, filters to obtain filter cake; Dry, gained sample, 350 ℃ of calcination process 2 hours, is then warming up to 4 hours removed template methods of 550 ℃ of calcination process for 40 minutes; Add 14gH
3pO
4(concentration 85%) is dissolved in 90g water, dries with the molecular sieve hybrid infusion after the above-mentioned roasting of 100g; Gained sample is at 550 ℃ of calcination process 2 hours, i.e. molecular sieve provided by the invention.
The physical data of sample and
27al MAS NMR peak area ratio is listed in table 1.
Embodiment 2
By beta-molecular sieve NH
4the exchange of Cl solution is washed to Na
2o content, lower than 0.2 % by weight, filters to obtain filter cake; Dry, gained sample, 150 ℃ of calcination process 2 hours, is then warming up to 350 ℃ of calcination process 2 hours for 30 minutes, then within 40 minutes, is warming up to 4 hours removed template methods of 550 ℃ of calcination process; Add 10g (NH
3)
2hPO
4(concentration 85%) is dissolved in 90g water, dries with the molecular sieve hybrid infusion after the above-mentioned roasting of 100g; Gained sample is at 550 ℃ of calcination process 2 hours, i.e. molecular sieve provided by the invention.
The physical data of sample and
27al MAS NMR peak area ratio is listed in table 1.
Embodiment 3
By beta-molecular sieve NH
4the exchange of Cl solution is washed to Na
2o content, lower than 0.2 % by weight, filters to obtain filter cake; Dry, gained sample, 350 ℃ of calcination process 2 hours, is then warming up to 4 hours removed template methods of 550 ℃ of calcination process for 40 minutes; Add 17gH
3pO
4(concentration 85%) is dissolved in 90g water, dries with the molecular sieve hybrid infusion after the above-mentioned roasting of 100g; Gained sample is at 550 ℃, calcination process 2 hours, i.e. molecular sieve provided by the invention under 100% steam atmosphere.
The physical data of sample and
27al MAS NMR peak area ratio is listed in table 1.
Comparative example 1
This comparative example is prepared the process of phosphorous beta-molecular sieve according to the method for CN1179994A.
By 100g(butt) beta-molecular sieve joins in the ammoniumsulphate soln of the heavy % of 2000ml4 in 90 ℃ and stirs exchange 1h, after filtration, exchanges once with same method again, filters the silicofluoric acid H of filter cake and 3 weight %
2siF
6solution 500ml reacts 2h at 60 ℃, refilters, and be phosphoric acid and the 3g pseudo-boehmite (Al of 85% heavy % by filter cake and 14g concentration
2o
3the heavy % of content 67) mixture of composition mixes, in baking oven after 110 ℃ of oven dry, put into tubular type muffle furnace with 550 ℃ at logical steam roasting 2h, the weight space velocity of water flowing steam is 2h
-1, obtain comparative example 1 molecular sieve.
The physical data of sample and
27al MAS NMR peak area ratio is listed in table 1.
Comparative example 2
Beta-molecular sieve, according to the method processing of embodiment 1, but was not carried out to calcination process before phosphorus modification, obtain comparative example 2 molecular sieves.
The physical data of sample and
27al MAS NMR peak area ratio is listed in table 1.
Comparative example 3
By beta-molecular sieve NH
4the exchange of Cl solution is washed to Na
2o content, lower than 0.2 % by weight, filters to obtain filter cake; Dry, gained sample is at 4 hours removed template methods of 550 ℃ of calcination process; Add 14gH
3pO
4(concentration 85%) is dissolved in 90g water, dries with the molecular sieve hybrid infusion after the above-mentioned roasting of 100g; Gained sample is at 550 ℃ of calcination process 2 hours, i.e. molecular sieve provided by the invention.
The physical data of sample and
27al MAS NMR peak area ratio is listed in table 1.
Table 1
Embodiment 4
The present embodiment explanation adopts phosphorous modified beta molecular sieve provided by the invention for ethylcyclohexane catalytic cracking, for the impact of hydrothermal stability and selectivity of light olefin.
The sample that above-described embodiment and comparative example are made carries out 820 ℃, 100% steam respectively on fixed bed aging equipment to be processed for aging 17 hours, and compressing tablet sieves out 20-40 object particle, evaluate on anti-catalytic cracking fixed bed is micro-, stock oil is ethylcyclohexane, appreciation condition is 650 ℃ of temperature of reaction, 650 ℃ of regeneration temperatures, oil inlet quantity 1.56g, 70 seconds oil-feed time, catalyst inventory 2g.
Evaluation result is listed in table 2.
Table 2
From table 2, data can find out that phosphorous modified beta molecular sieve provided by the invention has good activity stability and selectivity of light olefin.Compare with comparative example, product provided by the invention has effectively improved the selectivity of light olefin of crackate in improving cracking hydrocarbon ability, and the productive rate of ethene and productivity of propylene and selectivity all have raising by a relatively large margin.Meanwhile, non-alkene dry gas and coke yield are not significantly increased.
Claims (12)
1. a phosphorous modified beta molecular sieve, is characterized in that, with P
2o
5meter phosphorus content accounts for the heavy % of 3-10, this molecular sieve
27in Al MAS NMR, chemical shift is that 40 ± 3ppm resonance signal peak area and chemical shift are that the ratio of 54ppm ± 3ppm resonance signal peak area is more than or equal to 1.
2. according to the molecular sieve of claim 1, wherein, said with P
2o
5meter phosphorus content accounts for the heavy % of 5-9.
3. according to the molecular sieve of claim 1, wherein, said chemical shift is that 40 ± 3ppm resonance signal peak area and chemical shift are that the ratio of 54ppm ± 3ppm resonance signal peak area is more than or equal to 2.
4. the preparation method of the phosphorous modified beta molecular sieve of one of claim 1-3, it is characterized in that comprising by former beta-molecular sieve powder in the temperature range of 200 ℃ to 800 ℃ the step of carrying out again phosphorus modification after at least two non-overlapping temperature ranges are from low to high processed with removed template method.
5. according to the preparation method of claim 4, it is characterized in that comprising the steps:
(1) sodium type beta-molecular sieve is made to the Na on molecular sieve through ammonium exchange
2o content is less than 0.2 heavy %;
(2) molecular sieve step (1) being obtained after drying, is processed at least 0.5 hour under 200-400 ℃ of temperature range, then under 500-800 ℃ of temperature range, processes at least 0.5 hour removed template method being warmed up in 2 hours at the most;
(3) introduce P contained compound molecular sieve is carried out to modification;
(4) calcination process at least 0.5 hour at 400～800 ℃.
6. according to the method for claim 5, wherein, the said ammonium exchange of step (1) is according to molecular sieve: ammonium salt: H
2o=1:(0.1-1): the exchange at room temperature to 100 ℃ of weight ratio (5-10), filter, this process is at least carried out once.
7. according to the method for claim 6, wherein, said ammonium salt is selected from one or more the mixture in ammonium chloride, ammonium sulfate and ammonium nitrate.
8. according to the method for claim 5, it is characterized in that in step (2) before, the product of step (1) at least being processed 1 hour at 120-180 ℃.
9. according to the method for claim 5, wherein, the process that the said P contained compound of step (3) carries out modification to molecular sieve is to adopt impregnation method to carry out.
10. according to the method for claim 9, wherein, said impregnation method is by the P contained compound aqueous solution of the molecular sieve after removed template method and calculated amount in room temperature to 95 ℃ making beating evenly, dries.
11. according to claim 5,9 or 10 method, and wherein, said P contained compound is selected from one of phosphoric acid, ammonium hydrogen phosphate, primary ammonium phosphate or ammonium phosphate or its mixture.
12. according to the method for claim 5, and wherein, the said calcination process process of step (4) is to carry out under 1-100% steam atmosphere.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2021219064A1 (en) | 2020-04-30 | 2021-11-04 | 中国石油化工股份有限公司 | Modified beta zeolite, catalytic cracking catalyst as well as preparation method therefor and application thereof |
| CN114715910A (en) * | 2021-01-05 | 2022-07-08 | 中国石油化工股份有限公司 | Phosphorus and metal modified ZSM-5 molecular sieve and preparation method thereof |
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| WO2021219064A1 (en) | 2020-04-30 | 2021-11-04 | 中国石油化工股份有限公司 | Modified beta zeolite, catalytic cracking catalyst as well as preparation method therefor and application thereof |
| CN114715910A (en) * | 2021-01-05 | 2022-07-08 | 中国石油化工股份有限公司 | Phosphorus and metal modified ZSM-5 molecular sieve and preparation method thereof |
| CN114715910B (en) * | 2021-01-05 | 2023-05-05 | 中国石油化工股份有限公司 | Phosphorus and metal modified ZSM-5 molecular sieve and preparation method thereof |
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