CN103771437B - A kind of phosphorous modified beta molecular sieve - Google Patents
A kind of phosphorous modified beta molecular sieve Download PDFInfo
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- CN103771437B CN103771437B CN201210417720.9A CN201210417720A CN103771437B CN 103771437 B CN103771437 B CN 103771437B CN 201210417720 A CN201210417720 A CN 201210417720A CN 103771437 B CN103771437 B CN 103771437B
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Abstract
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
27al? MAS? in NMR, the ratio of chemical shift to be 40 ± 3ppm resonance signal peak area and chemical shift be 54ppm ± 3ppm resonance signal peak area is more than or equal to 1.In this molecular sieve, fully, framework aluminum is adequately protected for phosphorus and framework aluminum coordination, has excellent hydrothermal stability and better product selectivity.
Description
Technical field
The invention relates to a kind of molecular sieve and preparation method thereof, is about a kind of phosphorous modified beta molecular sieve and preparation method thereof furtherly.
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 in the scope of tens to hundreds of modulation.Martens etc. utilize decane to disclose the skeleton structure of 12 yuan of annular distances of beta-molecular sieve for probe reaction; 1988, the Stacking Fault Structure that Newsam and Higgins etc. adopt tectonic model, simulation powdery diffractometry determines beta-molecular sieve first.Beta-molecular sieve has twelve-ring intersection pore passage structure, and the 12 yuan of annular apertures being parallel to the one-dimensional channels of (001) crystal face are 0.75 ~ 0.57nm, and another is 0.65 ~ 0.56nm with 12 yuan of annular apertures of the two-dimensional channel of (100) crystal plane be parallel.Beta-molecular sieve is the high-silica zeolite of unique a kind of macropore three-dimensional structure found 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 DEG C), hydrothermal stability and wear resisting property.Due to the constitutional features of uniqueness, in a series of catalyzed reaction, beta-molecular sieve has good heat and hydrothermal stability, acid resistance, anti-coking and catalytic activity, excellent performance is shown in catalysis, absorption etc., therefore be with a wide range of applications, developed rapidly in recent years and become a kind of novel catalytic material.Can be used in the refining of petroleum such as hydrocracking, hydro-isomerization, olefin hydration and petrochemical process after modification or some metal constituent element of load.
In many catalyzed chemical reaction processes, need the active ingredient of molecular sieve as catalyzer having metal or metal ion (as Ni, Co, Cu, Ag, Zn, Fe, Mn, Cr, Zr, Mo, W, alkaline-earth metal, rare earth metal etc.) with load or exchange, or utilize the hydrogenation of this metal, dehydrogenation functionality, or utilize the synergy at this metal and acidic zeolite center to reach the specific purposes required by specific reaction.
CN1098028A discloses a kind of beta-molecular sieve catalyzer for toluene disproportionation and transalkylation reaction, this catalyzer is made up of beta-molecular sieve, the binding agent of 5 ~ 90 % by weight, the metal being selected from Ni, Co, Cu, Ag, Sn, Ga etc. of 0.05 ~ 5 % by weight of 10 ~ 90 % by weight, and metal wherein adopts pickling process load.
USP5,453,553 disclose a kind of benzene and laurylene reacts the processing method preparing dodecylbenzene, the catalyzer wherein used is obtained one or more in X, Y, M, ZSM-12 or beta-molecular sieve carrying transition metal Fe, Ni, Co, Pt, Ir, these metals be by dipping method load in the hole of molecular sieve, this catalyzer obviously can improve the stability of dodecylbenzene synthesis used catalyst, but must face the object of reacting under nitrogen atmosphere and just can reach and improving activity stability.
It is on the one hand in the process removing its template, easily make its structure suffer damage that beta-molecular sieve subject matter is in use embodied in, be on the other hand in reaction process easy dealuminzation thus activity stability is poor.
USP4,605, proposing a kind of method in 637, is with crystallite state AlPO in liquid phase water system
4the molecular sieves of low acidity such as-5 process such as aluminum phosphate material such as grade, as containing the ZSM-5 of B, the beta-molecular sieve, high silica ZSM-5 molecular sieve etc. containing B, makes Al nuclear power move in the skeleton of molecular sieve, thus improves the acidity of molecular sieve, increases lytic activity.
A kind of method of modifying of beta-molecular sieve is proposed in CN1043450A, the method is that Na beta-molecular sieve is pumped part framework aluminum with acid after roasting, then carrying out potassium exchange makes molecular sieve potassium content be 0.5 ~ 2.5 heavy %, after drying, roasting with comprise potassium hydrogen phosphate-potassium primary phosphate, Hypophosporous Acid, 50-potassium hypophosphite, phosphorous acid-potassium phosphite, the microcosmic salt buffered soln of weakly acidic pH at room temperature soaks 4 ~ 10 hours, take the circumstances into consideration washing or do not wash to make phosphorus content on molecular sieve be 0.01 ~ 0.5 heavy %, then dry, roasting; The hydrocarbon processing catalyzer as relating to hydroisomerization reaction is applicable to through the beta-molecular sieve that the method is modified.
Propose a kind of method of modifying of beta-molecular sieve in CN1179994A, the method by Na beta-molecular sieve ammonium ion exchange to the Na on molecular sieve
2o content is less than 0.1 heavy %; Then the beta-molecular sieve acid treatment that above-mentioned ammonium exchanges is pumped part framework aluminum, make its silica alumina ratio be greater than 50; Beta-molecular sieve after above-mentioned dealuminzation is mixed post-drying with phosphoric acid or phosphoric acid salt, makes P on gained molecular sieve
2o
5amount be 2 ~ 5 heavy %; Last under water vapour atmosphere with 450 ~ 650 DEG C of hydrothermal calcines 0.5 ~ 4 hour.Higher alkene can be obtained when the cracking reaction for hydro carbons, especially the productive rate of isomeric olefine and lower coke yield by the modified beta-molecular sieve of the method.
Propose a kind of method of modifying of beta-molecular sieve in CN1205249A, the method comprises the former powder of beta-molecular sieve synthesized 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 400 ~ 650 DEG C of roastings 1 ~ 5 hour again, 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 its crystallization reservation degree also can be made to be improved simultaneously.
Summary of the invention
Contriver by being surprised to find that after 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 AlMASNMR, chemical shift is that the feature of 40 ± 3ppm and 54ppm ± 3ppm aluminium species resonance signal is but different from prior art.
Therefore.An object of the present invention is to provide a kind of a kind of phosphorous modified beta molecular sieve being 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 AlMASNMR, the ratio of chemical shift to be 40 ± 3ppm resonance signal peak area and chemical shift be 54ppm ± 3ppm resonance signal peak area is more than or equal to 1.
Present invention also offers the preparation method of above-mentioned phosphorous modified beta molecular sieve, it is characterized in that comprising the former powder of beta-molecular sieve in the temperature range of 200 DEG C to 800 DEG C, through the non-overlapping temperature range process of at least two from low to high to carry out the step of P Modification after removed template method again.More specifically, comprise the steps:
(1) sodium form beta-molecular sieve is exchanged the Na made on molecular sieve through ammonium
2o content is less than 0.2 heavy %;
(2) molecular sieve step (1) obtained after drying, calcination process at least 0.5 hour at 200-400 DEG C, then calcination process at least 0.5 hour removed template method at being warmed up to 500-800 DEG C in 2 hours at the most;
(3) introduce P contained compound and modification is carried out to molecular sieve;
(4) calcination process at least 0.5 hour at 400 ~ 800 DEG C.
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, fully, framework aluminum is adequately protected for phosphorus and framework aluminum coordination, 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 AlMASNMR, the ratio of chemical shift to be 40 ± 3ppm resonance signal peak area and chemical shift be 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 AlMASNMR, chemical shift be 54 ± 3ppm resonance signal characterize four-coordination framework aluminum species, chemical shift be 40 ± 3ppm resonance signal characterize be the framework aluminum species with phosphorus coordination.Modified beta molecular sieve provided by the invention, this molecular sieve
27in AlMASNMR, the ratio of chemical shift to be 40 ± 3ppm resonance signal peak area and chemical shift be 54ppm ± 3ppm resonance signal peak area is more than or equal to 1, is preferably greater than or equal to 2, a value of such as 1.5 to 5.
Above-mentioned phosphorous modified beta molecular sieve provided by the invention comprises by former for beta-molecular sieve powder (the sodium form beta-molecular sieve containing organic formwork agent) in the temperature range of 200 DEG C to 800 DEG C, obtains with the step of carrying out P Modification after removed template method again through the non-overlapping temperature range process of at least two from low to high.More particularly comprise the steps:
(1) sodium form beta-molecular sieve is exchanged the Na made on molecular sieve through ammonium
2o content is less than 0.2 heavy %;
(2) molecular sieve step (1) obtained after drying, processes at least 0.5 hour under 200-400 DEG C of temperature range, then under being warmed up to 500-800 DEG C of temperature range in 2 hours at the most, processes at least 0.5 hour removed template method;
(3) introduce P contained compound and modification is carried out to molecular sieve;
(4) calcination process at least 0.5 hour at 400 ~ 800 DEG C.
In preparation method provided by the invention, in said step (1), said sodium form beta-molecular sieve is the sodium form beta-molecular sieve (as USP3,308,069, CNZL00107486.5) of conventional crystallization gained.In usually said sodium form beta-molecular sieve, sodium content counts the heavy % of 4-6 with sodium oxide.Said ammonium exchanges with the process reducing sodium content, preferably according to molecular sieve: ammonium salt: H
2o=1:(0.1 ~ 1): the process that the weight ratio of (5 ~ 10) exchanges at least 0.5 hour, preferably filters after 0.5 ~ 2 hour at room temperature to 100 DEG C, such ammonium exchange process can repeat 1 ~ 4 time, to make the Na on molecular sieve
2o content is less than 0.2 heavy %.Said ammonium salt for conventional inorganic ammonium salt, can be selected from ammonium chloride, one of ammonium sulfate or ammonium nitrate or their mixture.
In preparation method provided by the invention, said step (2) be adopt low temperature to high temperature differing temps interval treatment step (1) obtain molecular sieve, removed template method process.Said process is in the interval of 200 DEG C to 800 DEG C, carry out in the non-overlapping temperature range of at least two from low to high, said low temperature range is 200-400 DEG C, preferred 300-350 DEG C, and said high temperature range is 500-800 DEG C, preferred 500-600 DEG C.Such as, said process is Na after being exchanged by step (1) ammonium
2the molecular sieve that O content is less than 0.2 heavy % first calcination process at least 0.5 hour at 200-400 DEG C, preferably 300-350 DEG C after the drying, preferably 1 ~ 12 hour, then in 2 hours at the most, preferably 1 hour, calcination process is warmed up under 500-800 DEG C of temperature range at least 0.5 hour, preferably 1 ~ 8 hour.In step (2), also before above-mentioned said two temperature range process, first at least can process 1 hour at 120-180 DEG C.
In preparation method provided by the invention, introduce the product of P contained compound to step (2) in step (3) and carry out modification.Said P contained compound is selected from phosphoric acid, ammonium hydrogen phosphate, one of primary ammonium phosphate or ammonium phosphate or its mixture.Preferred employing impregnation method carries out, and said dipping is pull an oar evenly by the P contained compound aqueous solution of the molecular sieve after removed template method and calculated amount in room temperature to 95 DEG C, dries.
The invention provides in preparation method, step (4) is beta-molecular sieve product calcination process at least 0.5 hour, preferably 0.5-8 hour at 400 ~ 800 DEG C, preferably 500-600 DEG C of P Modification step (3) obtained.Wherein said calcination process process can adopt dry roasting also can adopt wet roasting, and said wet roasting is preferably carried out under 1-100%, more preferably 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 with x-ray fluorescence method measure (see " Petrochemical Engineering Analysis method (RIPP experimental technique) ", the volumes such as Yang Cuiding, Science Press, nineteen ninety publish).
27alMASNMR adopts BrukerAvanceIII500MHz nuclear magnetic resonance analyser to test, and resonance peak spectrogram adopts integration to calculate each peak area after carrying out 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 same) use NH
4cl solution exchanges washing to Na
2o content, lower than 0.2 % by weight, filters to obtain filter cake; Drying, gained sample, 350 DEG C of calcination process 2 hours, is then warming up to 550 DEG C of calcination process, 4 hours removed template methods 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 550 DEG C of calcination process 2 hours, i.e. molecular sieve provided by the invention.
The physical data of sample and
27alMASNMR peak area ratio lists in table 1.
Embodiment 2
By beta-molecular sieve NH
4cl solution exchanges washing to Na
2o content, lower than 0.2 % by weight, filters to obtain filter cake; Drying, gained sample, 150 DEG C of calcination process 2 hours, is then warming up to 350 DEG C of calcination process 2 hours for 30 minutes, then within 40 minutes, is warming up to 550 DEG C of calcination process, 4 hours removed template methods; 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 550 DEG C of calcination process 2 hours, i.e. molecular sieve provided by the invention.
The physical data of sample and
27alMASNMR peak area ratio lists in table 1.
Embodiment 3
By beta-molecular sieve NH
4cl solution exchanges washing to Na
2o content, lower than 0.2 % by weight, filters to obtain filter cake; Drying, gained sample, 350 DEG C of calcination process 2 hours, is then warming up to 550 DEG C of calcination process, 4 hours removed template methods 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 at 550 DEG C, calcination process 2 hours, i.e. molecular sieve provided by the invention under 100% steam atmosphere.
The physical data of sample and
27alMASNMR peak area ratio lists in table 1.
Comparative example 1
This comparative example prepares the process of phosphorous beta-molecular sieve according to the method for CN1179994A.
By 100g(butt) beta-molecular sieve join in the ammoniumsulphate soln of the heavy % of 2000ml4 in 90 DEG C stir exchange 1h, exchange again once with same method after filtration, filter, filter cake with 3 weight % silicofluoric acid H
2siF
6solution 500ml reacts 2h at 60 DEG C, refilters, and is phosphoric acid and the 3g pseudo-boehmite (Al of 85% heavy % by filter cake and 14g concentration
2o
3the heavy % of content 67) mixture that forms mixes, after drying in 110 DEG C in an oven, put into tubular type muffle furnace with 550 DEG C 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
27alMASNMR peak area ratio lists in table 1.
Comparative example 2
By the method process of beta-molecular sieve according to embodiment 1, but do not carry out calcination process before P Modification, obtain comparative example 2 molecular sieve.
The physical data of sample and
27alMASNMR peak area ratio lists in table 1.
Comparative example 3
By beta-molecular sieve NH
4cl solution exchanges washing to Na
2o content, lower than 0.2 % by weight, filters to obtain filter cake; Drying, gained sample is at 550 DEG C of calcination process, 4 hours removed template methods; 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 550 DEG C of calcination process 2 hours, i.e. molecular sieve provided by the invention.
The physical data of sample and
27alMASNMR peak area ratio lists in table 1.
Table 1
Embodiment 4
The present embodiment illustrates and adopts phosphorous modified beta molecular sieve provided by the invention to be used in ethylcyclohexane catalytic cracking, for the impact of hydrothermal stability and selectivity of light olefin.
The sample that above-described embodiment and comparative example obtain is carried out respectively on fixed bed aging equipment 820 DEG C, the process in aging 17 hours of 100% steam, and compressing tablet sieves out 20-40 object particle, catalytic cracking fixed bed micro-anti-on evaluate, stock oil is ethylcyclohexane, appreciation condition is temperature of reaction 650 DEG C, regeneration temperature 650 DEG C, oil inlet quantity 1.56g, 70 seconds oil-feed time, catalyst inventory 2g.
Evaluation result lists 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.Compared with comparative example, product provided by the invention effectively improves the selectivity of light olefin of crackate while 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 (9)
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 AlMASNMR, be more than or equal to 1 with the ratio of the framework aluminum species of phosphorus coordination, its chemical shift to be 40 ± 3ppm resonance signal peak area and four-coordination framework aluminum species, its chemical shift be 54ppm ± 3ppm resonance signal peak area.
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, the ratio of said framework aluminum species with phosphorus coordination, its chemical shift to be 40 ± 3ppm resonance signal peak area and four-coordination framework aluminum species, its chemical shift be 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, is characterized in that comprising the steps:
(1) sodium form beta-molecular sieve is exchanged the Na made on molecular sieve through ammonium
2o content is less than 0.2 heavy %;
(2) molecular sieve step (1) obtained after drying, processes at least 0.5 hour under 200-400 DEG C of temperature range, then under being warmed up to 500-800 DEG C of temperature range in 2 hours at the most, processes at least 0.5 hour removed template method;
(3) adopt impregnation method to introduce P contained compound and carry out modification to molecular sieve, said impregnation method is pull an oar evenly by the P contained compound aqueous solution of the molecular sieve after removed template method and calculated amount in room temperature to 95 DEG C, dries;
(4) calcination process at least 0.5 hour at 400 ~ 800 DEG C.
5. according to the method for claim 4, wherein, the said ammonium of step (1) exchanges is according to molecular sieve: ammonium salt: H
2o=1:(0.1-1): the weight ratio of (5-10) exchanges, filters at room temperature to 100 DEG C, and this process is at least carried out once.
6. according to the method for claim 5, wherein, said ammonium salt is selected from the mixture of one or more in ammonium chloride, ammonium sulfate and ammonium nitrate.
7. according to the method for claim 4, it is characterized in that before step (2), the product of step (1) is at least processed 1 hour at 120-180 DEG C.
8. according to the method for claim 4, wherein, said P contained compound is selected from phosphoric acid, ammonium hydrogen phosphate, one of primary ammonium phosphate or ammonium phosphate or its mixture.
9. according to the method for claim 4, wherein, the said calcination process process of step (4) is carried out under 1-100% steam atmosphere.
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| 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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|---|---|---|---|---|
| US4832927A (en) * | 1987-01-14 | 1989-05-23 | Mobil Oil Corporation | Use of poly-nuclear oxo-metalates in synthesis of crystalline oxides |
| EP0619800B1 (en) * | 1991-12-23 | 1997-08-13 | NORSK HYDRO a.s. | Procedure for synthesis of crystalline microporous silico-alumino-phosphates |
| CN101433859A (en) * | 2007-11-15 | 2009-05-20 | 中国石油化工股份有限公司 | Catalyst for alkylation reaction and preparation method thereof |
| CN101450318A (en) * | 2007-11-28 | 2009-06-10 | 中国石油化工股份有限公司 | Modification method of beta-molecular sieve |
-
2012
- 2012-10-26 CN CN201210417720.9A patent/CN103771437B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4832927A (en) * | 1987-01-14 | 1989-05-23 | Mobil Oil Corporation | Use of poly-nuclear oxo-metalates in synthesis of crystalline oxides |
| EP0619800B1 (en) * | 1991-12-23 | 1997-08-13 | NORSK HYDRO a.s. | Procedure for synthesis of crystalline microporous silico-alumino-phosphates |
| CN101433859A (en) * | 2007-11-15 | 2009-05-20 | 中国石油化工股份有限公司 | Catalyst for alkylation reaction and preparation method thereof |
| CN101450318A (en) * | 2007-11-28 | 2009-06-10 | 中国石油化工股份有限公司 | Modification method of beta-molecular sieve |
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