CN103787358B - A kind of beta-molecular sieve of phosphorous and metal - Google Patents
A kind of beta-molecular sieve of phosphorous and metal Download PDFInfo
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Abstract
The invention provides a kind of beta-molecular sieve of phosphorous and metal, it is characterized in that, with P
2o
5meter phosphorus content accounts for the heavy % of 1-10, accounts for the heavy % of 0.5-10 with metal oxide metal content, 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.
Description
Technical field
The invention relates to a kind of active component for cracking hydrocarbon, is the beta-molecular sieve and preparation method thereof about a kind of phosphorous and transition metal 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 β zeolite, β zeolite 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 β zeolite for probe reaction; 1988, the Stacking Fault Structure that Newsam and Higgins etc. adopt tectonic model, simulation powdery diffractometry determines β zeolite first.β zeolite 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.
In many catalyzed chemical reaction processes, need the active ingredient of zeolite 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 zeolite acidity center to reach the specific purposes required by specific reaction.
CN1098028A discloses a kind of beta-zeolite catalyst for toluene disproportionation and transalkylation reaction, this catalyzer is made up of β zeolite, 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 zeolite-loaded to X, Y, M, ZSM-12 or β transition-metal Fe, Ni, Co, Pt, Ir, these metals be by dipping method load in the hole of zeolite, 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 β zeolite subject matter is in use embodied in, be on the other hand in reaction process easy dealuminzation thus activity stability is poor.
USP 4,605, a kind of method is proposed in 637, such as contain the ZSM-5 of B, the β zeolite, high silica ZSM-5 zeolite etc. containing B with the zeolite of the low acidity of aluminum phosphate material process such as crystallite state AlPO4-5 in liquid phase water system, Al nuclear power is made to move in the skeleton of zeolite, thus improve the acidity of zeolite, increase lytic activity.
A kind of method of modifying of β zeolite is proposed in CN1043450A, the method is that Na β zeolite is pumped part framework aluminum with acid after roasting, then carrying out potassium exchange makes zeolite 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 zeolite be 0.01 ~ 0.5 heavy %, then dry, roasting; The hydrocarbon processing catalyzer as relating to hydroisomerization reaction is applicable to through the β zeolite that the method is modified.
Propose a kind of method of modifying of β zeolite in CN 1179994A, the method by Na β zeolite ammonium ion exchange to the Na on zeolite
2o content is less than 0.1 heavy %; Then the β zeolite acid treatment exchanged by above-mentioned ammonium pumps part framework aluminum, makes its silica alumina ratio be greater than 50; β zeolite after above-mentioned dealuminzation is mixed post-drying with phosphoric acid or phosphoric acid salt, makes P on gained zeolite
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 β zeolite of the method.
Propose a kind of method of modifying of β zeolite in CN1205249A, the method comprises the β zeolite powder synthesized and contains Al
2o
3source, P
2o
5source, SiO
2source, H
2o
2and the mixture of water is according to β zeolite: 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 β zeolite be significantly improved, and its crystallization reservation degree also can be made to be improved simultaneously.
CN1872685A discloses a kind of modified beta zeolite, it is characterized in that the anhydrous chemical expression of this β zeolite, (0 ~ 0.3) Na2O(0.5 ~ 10 are counted with the quality of oxide compound) Al2O3(1.3 ~ 10) P2O5(0.7 ~ 15) MxOy(70 ~ 97) SiO2, wherein, M is selected from the one in Fe, Co, Ni, Cu, Mn, Zn and Sn.This zeolite is applied in catalytic cracking, can as the active ingredient of catalyzer or auxiliary agent.
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 Al MAS NMR, the feature of aluminium species is different from prior art completely.
Therefore.An object of the present invention is to provide and is a kind ofly different from a kind of phosphorus of prior art feature and metal-modified beta-molecular sieve, and two of object is to provide the preparation method of this molecular sieve.
The beta-molecular sieve of phosphorous and transition metal provided by the invention, is characterized in that, with P
2o
5meter phosphorus content accounts for the heavy % of 1-10, accounts for the heavy % of 0.5-10 with metal oxide metal content, this molecular sieve
27in Al MAS 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.
The present invention still further provides the preparation method of above-mentioned phosphorus and metal-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 with after removed template method, dealuminzation, then carry out phosphorus and metal-modified step.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) introducing P contained compound and metallic compound carry out modification to molecular sieve;
(4) calcination process at least 0.5 hour at 400 ~ 800 DEG C.
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 and transition metal provided by the invention, is characterized in that, accounts for the heavy % of 1-10 in P2O5 phosphorus content, accounts for the heavy % of 0.5-10 with metal oxide metal content, this molecular sieve
27in Al MAS 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.
Modified beta molecular sieve provided by the invention, with P
2o
5meter phosphorus content accounts for the heavy % of 0.5-10, preferably accounts for the heavy % of 3-9, accounts for the heavy % of 0.5-10 with metal oxide metal content, preferably accounts for the heavy % of 0.5-5.One or more preferably in Fe, Co, Ni, Cu, Mn, Zn and Sn of said metal.
Phosphorus provided by the invention and transition metal modified beta-molecular sieve, its
27in Al MAS NMR, 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 Al MAS 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, is preferably greater than or equal to 2, a value of such as 1 to 5.
The present invention still further provides the preparation method of above-mentioned phosphorus and metal-modified beta-molecular sieve, be characterised in that and comprise 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 with after removed template method, then carry out phosphorus and metal-modified step.。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) introducing P contained compound and metallic compound carry out modification to molecular sieve;
(4) calcination process at least 0.5 hour at 400 ~ 800 DEG C.
Preparation method provided by the invention, compared with the modifying process of existing beta-molecular sieve, the key distinction is that method of modifying of the present invention is by former for beta-molecular sieve powder after the staging treating roasting removed template method from low temperature to high temperature, then carries out the modification of phosphorus and transition metal.
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, carry out modification in step (3) introducing P contained compound and the product of metallic compound to step (2).Said P contained compound is selected from phosphoric acid, ammonium hydrogen phosphate, one of primary ammonium phosphate or ammonium phosphate or its mixture.Said metallic compound is selected from the water-soluble salt of metal, and the water-soluble salt of said metal is selected from vitriol, nitrate, chlorate.Said metal be selected from Fe, Co, Ni, Cu, Mn, Zn, Sn one or more.The water-soluble salt of said metal exemplifies but is not limited to ferric sulfate, rose vitriol, single nickel salt, copper sulfate, manganous sulfate, zinc sulfate, tin sulphate, iron nitrate, Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES, nickelous nitrate, cupric nitrate, manganous nitrate, zinc nitrate, nitric acid tin, iron(ic) chloride, cobalt chloride, nickelous chloride, cupric chloride, Manganous chloride tetrahydrate, zinc chloride, tin chloride etc.
Step (3) said modifying process can adopt the mode of dipping or ion-exchange to carry out.Wherein said dipping can adopt again following three kinds of modes:
A. the P contained compound aqueous solution of the molecular sieve after removed template method and calculated amount is pulled an oar in room temperature to 95 DEG C and evenly dry, under 400 ~ 800 DEG C of conditions after roasting, then mix with the compound water solution containing one of Fe, Co, Ni, Cu, Mn, Zn, Sn of calculated amount in room temperature to 95 DEG C, dry.
B. the P contained compound aqueous solution of the molecular sieve after removed template method and calculated amount is pulled an oar in room temperature to 95 DEG C and evenly dry, oven dry is mixed in room temperature to 95 DEG C again with the compound water solution containing one of Fe, Co, Ni, Cu, Mn, Zn, Sn of calculated amount, wherein also can by the reversed order of the above-mentioned two kinds of solution of dipping.
C. the molecular sieve after removed template method is mixed post-drying with the mixed aqueous solution of the compound of one of Fe, Co, Ni, Cu, Mn, Zn, Sn in room temperature to 95 DEG C with the P contained compound of calculated amount.
In step (3) said modifying process, said ion-exchange is: pulled an oar in room temperature to 95 DEG C by the P contained compound aqueous solution of the molecular sieve after removed template method and calculated amount and evenly dry, under 400 ~ 800 DEG C of conditions after roasting, again with calculated amount containing the compound water solution of one of Fe, Co, Ni, Cu, Mn, Zn, Sn by 1:(5 ~ 20) solid-to-liquid ratio mix after, filter after stirring 2 ~ 3 hours at 80 ~ 95 DEG C, can repeated exchanged repeatedly, after exchanging, the washing of gained samples with water repeatedly, is dried.
The invention provides in preparation method, step (4) is the phosphorus and metal-modified beta-molecular sieve product calcination process at least 0.5 hour, the preferably 0.5-8 hour at 400 ~ 800 DEG C, preferably 500-600 DEG C that step (3) are 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, in each beta-molecular sieve sample, Na
2o, Fe
2o
3, Co
2o
3, NiO, CuO, Mn
2o
3, ZnO, SnO
2, Al
2o
3, SiO
2, P
2o
5content 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),
7al MAS NMR adopts Bruker Avance III 500MHz 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; Get above-mentioned molecular sieve 100g(butt), by 6.8gH
3pO
4(concentration 85%) and 3.2gCu (NO
3)
23H
2o is dissolved in 100g water, dries with molecular sieve hybrid infusion; Gained sample 550 DEG C of calcination process 2 hours, i.e. molecular sieve provided by the invention.
Elementary analytical chemistry consists of 0.1Na
2o6.6Al
2o
33.8P
2o
51.0CuO88.6SiO
2.
27al MASNMR 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 30 minutes, is warming up to 500 DEG C of calcination process, 4 hours removed template methods; Get above-mentioned molecular sieve 100g(butt), by 11.8gH
3pO
4(concentration 85%) and 6.3gCuCl
2be dissolved in 100g water, dry with molecular sieve hybrid infusion; Gained sample 550 DEG C of calcination process 2 hours, i.e. molecular sieve provided by the invention.
Elementary analytical chemistry consists of 0.1Na
2o6.0Al
2o
36.7P
2o
53.4CuO83.7SiO
2.
27al MASNMR 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 600 DEG C of calcination process, 4 hours removed template methods for 50 minutes; Get above-mentioned molecular sieve 100g(butt), by 4.2gNH
4h
2pO
4be dissolved in 100g water, dry with molecular sieve hybrid infusion, through 550 DEG C of calcination process 2 hours; Be the Cu (NO of 5% in the ratio of solid-to-liquid ratio 5:1 and concentration by above-mentioned sample
3)
2solution exchanges 2 hours at 80 ~ 90 DEG C, filters, then exchanges several times, until reach aim parameter, then 550 DEG C of calcination process 2 hours, i.e. and molecular sieve provided by the invention.
Elementary analytical chemistry consists of 0.03Na
2o6.4Al
2o
33.4P
2o
52.0CuO88.2SiO
2.
27alMAS NMR peak area ratio lists in table 1.
Embodiment 4
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, 300 DEG C of calcination process 2 hours, is then warming up to 550 DEG C of calcination process, 4 hours removed template methods for 60 minutes; Get above-mentioned molecular sieve 100g(butt), by 6.9gH
3pO
4(concentration 85%) and 8.1gFe (NO
3)
39H
2o is dissolved in 90g water, dries with molecular sieve hybrid infusion; Gained sample 550 DEG C of calcination process 2 hours, i.e. molecular sieve provided by the invention.
Elementary analytical chemistry consists of 0.1Na
2o6.4Al
2o
33.9P
2o
51.4Fe
2o
388.1SiO
2.
27alMAS NMR peak area ratio lists in table 1.
Embodiment 5
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; Get above-mentioned molecular sieve 100g(butt), by 9.3gH
3pO
4(concentration 85%) and 33.6gCo (NO
3) 6H
2o is dissolved in 90g water, dries with molecular sieve hybrid infusion; Gained sample at 550 DEG C, calcination process 2 hours, i.e. molecular sieve provided by the invention under 100% steam atmosphere.
Elementary analytical chemistry consists of 0.1Na
2o5.8Al
2o
35.2P
2o
59.3Co
2o
379.6SiO
2.
27alMAS NMR peak area ratio lists in table 1.
Embodiment 6
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; Get above-mentioned molecular sieve 100g(butt), by 6.0gH
3pO
4(concentration 85%) and 6.3gNi (NO
3)
26H
2o is dissolved in 90g water, dries with molecular sieve hybrid infusion; Gained sample 550 DEG C of calcination process 2 hours, i.e. molecular sieve provided by the invention.
Elementary analytical chemistry consists of 0.08Na
2o6.4Al
2o
34.1P
2o
51.7NiO87.7SiO
2.
27alMAS NMR peak area ratio lists in table 1.
Embodiment 7
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; Get above-mentioned molecular sieve 100g(butt), by 6.0gH
3pO
4(concentration 85%) and 35.4gMn (NO
3)
2be dissolved in 90g water, dry with molecular sieve hybrid infusion; Gained sample 550 DEG C of calcination process 2 hours, i.e. molecular sieve provided by the invention.
Elementary analytical chemistry consists of 0.09Na
2o6.1Al
2o
33.6P
2o
56.1Mn
2o
384.1SiO
2.
27alMAS NMR peak area ratio lists in table 1.
Embodiment 8
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; Get above-mentioned molecular sieve 100g(butt), by 4.8gH
3pO
4(concentration 85%) and 5.9gZn (NO
3)
26H
2o is dissolved in 90g water, dries with molecular sieve hybrid infusion; Gained sample 550 DEG C of calcination process 2 hours, i.e. molecular sieve provided by the invention.
Elementary analytical chemistry consists of 0.14Na
2o6.5Al
2o
33.1P
2o
51.5ZnO88.8SiO
2.
27alMAS NMR peak area ratio lists in table 1.
Embodiment 9
By beta-molecular sieve NH
4c l 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; Get above-mentioned molecular sieve 100g(butt), add 15gH
3pO
4(concentration 85%) and 3.7gSnCl
45H
2o is dissolved in 90g water, dries with molecular sieve hybrid infusion; Gained sample 550 DEG C of calcination process 2 hours, i.e. molecular sieve provided by the invention.
Elementary analytical chemistry consists of 0.10Na
2o6.0Al
2o
39.1P
2o
51.6SnO
283.2SiO
2.
27alMAS NMR peak area ratio lists in table 1.
Embodiment 10
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; Get above-mentioned molecular sieve 100g(butt), add 15gH
3pO
4(concentration 85%) and 3.2gCu (NO
3)
23H
2o, 2.6gZn (NO
3)
26H
2o is dissolved in 90g water, dries with molecular sieve hybrid infusion; Gained sample 550 DEG C of calcination process 2 hours, i.e. molecular sieve provided by the invention.
Elementary analytical chemistry consists of 0.10Na
2o6.0Al
2o
39.1P
2o
51.0CuO0.6ZnO83.2SiO
2.
27al MAS NMR peak area ratio lists in table 1.
Comparative example 1
This comparative example illustrates without the phosphorus of dealumination treatment and transition metal modified beta-molecular sieve (preparing according to the method for CN1872685A).
By 100g(butt) beta-molecular sieve NH
4cl solution exchanges washing to Na
2o content, lower than 0.2 % by weight, filters to obtain filter cake; Add 6.9gH
3pO
4(concentration 85%) and 8.1gFe (NO
3)
39H
2o is dissolved in 90g water, dries with filter cake hybrid infusion; Gained sample 550 DEG C of calcination process 2 hours, i.e. molecular sieve provided by the invention.Elementary analytical chemistry consists of 0.1Na
2o6.0Al
2o
34.1P
2o
51.5Fe
2o
388.3SiO
2.
27al MAS NMR peak area ratio lists in table 1.
Comparative example 2
By beta-molecular sieve, (Shandong catalyst plant is produced, SiO
2/ Al
2o
3=25, sodium oxide content 4.5%) use 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; Get above-mentioned molecular sieve 100g(butt), by 6.8gH
3pO
4(concentration 85%) and 3.2gCu (NO
3)
23H
2o is dissolved in 100g water, dries with molecular sieve hybrid infusion; Gained sample 550 DEG C of calcination process 2 hours, i.e. molecular sieve provided by the invention.
Elementary analytical chemistry consists of 0.1Na
2o6.6Al
2o
33.7P
2o
51.1CuO88.6SiO
2.
27al MASNMR 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; Get above-mentioned molecular sieve 100g(butt), add 15gH
3pO
4(concentration 85%) and 3.2gCu (NO
3)
23H
2o, 2.6gZn (NO
3)
26H
2o is dissolved in 90g water, dries with molecular sieve hybrid infusion; Gained sample 550 DEG C of calcination process 2 hours, i.e. molecular sieve provided by the invention.
Elementary analytical chemistry consists of 0.10Na
2o6.0Al
2o
39.0P
2o
51.0CuO0.7ZnO83.2SiO
2.
27al MAS NMR peak area ratio lists in table 1.
Table 1
Embodiment 11
The present embodiment illustrates and adopts modified beta molecular sieve provided by the invention to be used in solar oil catalytic cracking, for the impact of olefine selective.
The sample that above-described embodiment and comparative example obtain is carried out respectively on fixed bed aging equipment 800 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, experimental raw oil is standard solar oil-huge port straight distillation light diesel oil, and its character lists in table 2.Appreciation condition is temperature of reaction 500 DEG C, regeneration temperature 600 DEG C, oil inlet quantity 1.56g, 70 seconds oil-feed time, catalyst inventory 2g.
Evaluation result lists in table 3.
Table 2
| Analysis project | Standard solar oil |
| Density (20 DEG C)/gmL -1 | 0.8149 |
| Sulphur/% | 0.05 |
| Nitrogen/% | 0.007 |
| Boiling range/DEG C | |
| Initial boiling point | 225 |
| Final boiling point | 337 |
From table 3, data can find out that modified molecular screen provided by the invention has excellent activity stability and selectivity of light olefin.Compared with comparative example, product provided by the invention effectively improves the selectivity of light olefin, particularly ethene of crackate and iso-butylene productive rate and has raising by a relatively large margin while improving cracking hydrocarbon ability.Meanwhile, non-alkene dry gas and coke yield do not increase.
Table 3
Claims (12)
1. a beta-molecular sieve for phosphorous and metal, is characterized in that, with P
2o
5meter phosphorus content accounts for the heavy % of 1-10, accounts for the heavy % of 0.5-10 with metal oxide metal content, this molecular sieve
27in Al MAS NMR, the ratio being 54ppm ± 3ppm resonance signal peak area with the framework aluminum species of phosphorus coordination, its chemical shift 40 ± 3ppm resonance signal peak area and four-coordination framework aluminum species, its chemical shift is more than or equal to 1.
2. according to the beta-molecular sieve of claim 1, wherein, said phosphorus content, with P
2o
5meter accounts for the heavy % of 3-9, said metal, accounts for the heavy % of 0.5-5 with metal oxide.
3. according to the beta-molecular sieve of claim 1 or 2, wherein, said metal is selected from one or more in Fe, Co, Ni, Cu, Mn, Zn and Sn.
4. according to the beta-molecular sieve of claim 1, wherein, said molecular sieve
27in Al MAS NMR, be more than or equal to 2 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.
5. the preparation method of the beta-molecular sieve of the phosphorous and metal of one of claim 1-4, 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 with after removed template method, then carry out phosphorus and metal-modified step.
6. the method for claim 5, is characterised in that preparation process comprises 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) introducing P contained compound and metallic compound carry out modification to molecular sieve; (4) calcination process at least 0.5 hour at 400 ~ 800 DEG C.
7. according to the method for claim 6, wherein, said P contained compound is selected from phosphoric acid, ammonium hydrogen phosphate, one of primary ammonium phosphate or ammonium phosphate or its mixture.
8. according to the method for claim 6, it is characterized in that before step (2), the product of step (1) is at least processed 1 hour at 120-180 DEG C.
9. according to the method for claim 6, wherein, said metallic compound is selected from one or more in the compound of Fe, Co, Ni, Cu, Mn, Zn and Sn.
10. according to the method for claim 6 or 9, wherein, said metallic compound is the water-soluble salt of metal.
11. according to the method for claim 10, and wherein, the water-soluble salt of said metal is selected from the one in the vitriol of metal, nitrate or chlorate.
12. according to the method for claim 6, and wherein, the said calcination process process of step (4) is roasting under steam atmosphere.
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| US5951963A (en) * | 1997-03-24 | 1999-09-14 | China Petrochemical Corporation | Phosphorous containing zeolite having MFI type structure |
| CN1386703A (en) * | 2002-04-20 | 2002-12-25 | 吉林大学 | Process for preparing cubic mesoporous Si-Al molecular sieve with strong acidic site |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US5951963A (en) * | 1997-03-24 | 1999-09-14 | China Petrochemical Corporation | Phosphorous containing zeolite having MFI type structure |
| CN1386703A (en) * | 2002-04-20 | 2002-12-25 | 吉林大学 | Process for preparing cubic mesoporous Si-Al molecular sieve with strong acidic site |
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| 磷改性β分子筛的制备及其在苯与乙烯烷基化反应中的应用;晁会霞等;《石油炼制与化工》;20120131;第43卷(第1期);第42-43页 * |
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