CN1268485A - Zirconium-phosphorus-aluminium molecular sieve composition and its preparation method - Google Patents
Zirconium-phosphorus-aluminium molecular sieve composition and its preparation method Download PDFInfo
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Abstract
A zirconium-phosphorus-aluminium molecular sieve composition possessing AlPO4-5 structure is disclosed, its anhydrous chemical formula is mR:(MsZrxAlyPz)O2 where R represents organic template agent, m represents number of mole of R each mole of (MsZrxAlgP2)O2, M is at least one element selected from Si, B, Ge, Ga, Mn, Ti, Fe, Co and Ni, s. x. y. z represent respectively the mole fraction of substituted element M, Zr, Al and P in tetrahedral oxide. After the precursors of P source, Al source, Zr source and M, the organic template agent and water are mixed according to a certain proportion, it is crystallized to form product. The invented molecular sieve composition can be used as absorbent and catalyst of different reactions.
Description
The invention relates to a kind of composition and preparation thereof of Zirconium-phosphorus-aluminium molecular sieve, further say so about a kind of AlPO of having
4The Zirconium-phosphorus-aluminium molecular sieve composition of-5 crystalline structure and preparation thereof.
USP4310440 at first discloses aluminium phosphate molecular sieve (AlPO
4) structure and preparation, the sial tetrahedron does not appear in this novel molecular sieve first in the framework of molecular sieve structure, but by AlO
2And PO
2Tetrahedron is formed, and framework of molecular sieve is electric neutrality, does not have exchangeable cation.Aluminium phosphate molecular sieve adopts hydrothermal crystallization method synthetic, is earlier equimolar active hydrated aluminum oxide and phosphoric acid to be mixed the generation phosphaljel in water, and then adds organic formwork agent, and the back crystallization under 125～200 ℃ of autogenous pressures that stirs obtains.AlPO wherein
4The d-spacing that the X-light powdery diffractometry spectrogram of-5 phosphate aluminium molecular sieves contains at least is as shown in the table: 2 θ, ° d, dust 100 * I/I
07.4-7.6 11.9-11.6 10014.85-15.2 5.97-5.83 13-4319.7-20.1 4.51-4.42 39-9220.8-21.2 4.27-4.19 37-8722.3-22.7 3.99-3.92 62-11825.9-26.25 3.44-3.39 22-35
EP83109860 and USP4440871 have disclosed a kind of aluminium silicophosphate molecular sieve (SAPO), are to substitute part aluminium and phosphorus with silicon, form by PO
2, AlO
2, SiO
2The framework of molecular sieve that constitutes, its anhydrous composition empirical formula is mR: (Si
xAl
yP
z) O
2, R represents a kind of template in the molecular sieve crystal pore structure at least in the formula, m represents that R is with respect to every mole of (Si
xAl
yP
z) O
2Mole number, its value is 0～0.3; X, y, z represent the molar fraction of silicon, aluminium and phosphorous oxides respectively, and the Schwellenwert of x, y, z is 0.01, are preferably 0.02, and its maximum respectively is 0.98,0.60 and 0.52.
The disclosed titanium phosphate aluminium molecular sieve of EP0121232A2 (TAPO) is to form with part phosphorus and aluminium that titanium replaces in the aluminum phosphate, and its anhydrous chemical constitution empirical formula is mR: (Ti
xAl
yP
z) O
2, R represents a kind of template in the molecular sieve crystal pore structure at least in the formula, m represents that R is with respect to every mole of (Ti
xAl
yP
z) O
2Mole number, its value is 0～5, x, y, z represent the molar fraction of titanium, aluminium and phosphorous oxides respectively.
Disclosed titanium-the aluminium of CN85103240A-phosphorus-titanium-aluminum-phosphorus-silicon-oxide molecular sieve compositions is to form with part phosphorus and aluminium that titanium and silicon replace in the aluminium phosphate molecular sieve skeleton.
Silica removal and/or titanium are as outside the backbone element, and other heteroatoms also can replace phosphorus and the aluminium backbone element as the molecular sieve tetrahedral oxide.Magnesium-aluminium-phosphorus-titanium-aluminum-phosphorus-silicon-oxide molecular sieve compositions is disclosed as CN8510228A; CN85103238A discloses cobalt-aluminium-phosphorus-titanium-aluminum-phosphorus-silicon-oxide molecular sieve compositions; CN85103257 discloses zinc-aluminium-phosphorus-titanium-aluminum-phosphorus-silicon-oxide molecular sieve compositions; CN85103260A discloses manganese-aluminium-phosphorus-titanium-aluminum-phosphorus-silicon-oxide molecular sieve compositions; CN85103247A discloses iron-aluminium-phosphorus-titanium-aluminum-phosphorus-silicon-oxide molecular sieve compositions; CN85104262A discloses boron-aluminium-phosphorus-titanium-aluminum-phosphorus-silicon-oxide molecular sieve compositions; CN85103199A discloses by oxide compound that is selected from arsenic, beryllium, boron, gallium, germanium, lithium or vanadium and AlO
2 -, PO
2 +The tetrahedral oxide molecular sieve that forms; The disclosed a kind of aluminium phosphate molecular sieve composition of CN85103259A, be by the element that is selected from one of arsenic, beryllium, boron, chromium, gallium, germanium, lithium and vanadium be selected from the tetrahedral oxide units skeleton structure that the element of one of cobalt, iron, magnesium, manganese, titanium and zinc and phosphorus and aluminium constitute; The disclosed combination of molecular sieve of CN85101026A is with iron and/or titanium and is selected from that a kind of in magnesium, manganese, cobalt, the zinc replaces part phosphorus, aluminium forms as the backbone element of tetrahedral oxide.
CN1036376A is disclosed a kind ofly to form the aluminium phosphate molecular sieve (code name is VPI-5) of tetrahedron lattice by aluminium and phosphorus and the oxide compound that is selected from substituted metals such as silicon, magnesium, titanium, cobalt, tin or zirconium, and it has the crystalline structure of VFI.Its reaction mixture colloidal oxide molar consists of: Al
2O
3: (0.8～1.2) P
2O
5: (10～100) H
2O also comprises 0.02～4 mole organic formwork agent and 0.001～0.5 mole substituted metal oxide compound, and the organic formwork agent that it uses comprises TBAH, dipropyl amine and diamylamine etc.
In molecular sieve was synthetic, the difference of raw material type comprised the difference of phosphorus source, aluminium source, organic formwork agent and various substituted element compounds, material proportion and synthesis step different, and the molecular sieve that has different structure generates.Up to the present, the difference that has been synthesized out is formed phosphate aluminium molecular sieve and is had an appointment 200 kinds, and the skeleton structure type of determining has 24 kinds at least; Replace part phosphorus, aluminium and have Li, Be, B, Mg, Si, Ti, Mn, Fe, Co, Zn, Ga, Ge, As, Zr etc., form the skeleton positively charged ion of monovalence to pentavalent with unit that phosphorus and aluminium form oxide compound tetrahedron skeleton structure; The duct size has covered the pore diameter range from aperture (0.3nm) to macropore (1.4nm); Pore volume is at 0.18～0.48cm
3Between/the g.
But do not see so far and have AlPO
4-5 crystalline structure, zirconium replace the report of part phosphorus aluminium as the molecular sieve of tetrahedral oxide backbone element.
The purpose of this invention is to provide a kind of AlPO of having
4The Zirconium-phosphorus-aluminium molecular sieve composition of-5 crystalline structure.
Another object of the present invention provides the preparation method of this novel Zirconium-phosphorus-aluminium molecular sieve composition.
Zirconium-phosphorus-aluminium molecular sieve composition provided by the invention, the d-distance values that its X-light powdery diffractometry spectrogram contains at least is shown in Table A:
Table A
2 θ, ° d, dust 100 * I/I
0
7.4-7.6?????????????????11.9-11.6???????????100
14.85-15.2??????????????5.97-5.83???????????16-22
19.7-20.1???????????????4.51-4.42???????????50-66
20.8-21.2???????????????4.27-4.19???????????80-107
22.3-22.7???????????????3.99-3.92???????????144-163
25.9-26.25??????????????3.44-3.39???????????52-67
Its anhydrous chemical expression is: mR: (M
sZr
xAl
yP
z) O
2
The organic formwork agent of R representative in the internal crystallization pore system in the formula; The m representative is every mole (M relatively
sZr
xAl
yP
z) O
2The mole number of R, its value is 0～5; M represents at least a substituted element that can constitute the tetrahedral oxide skeleton structure, is selected from least a element in silicon, boron, germanium, gallium, manganese, titanium, iron, cobalt and the nickel; S, x, y, z represent substituted element M, zirconium, aluminium and the phosphorus molar fraction in tetrahedral oxide respectively, and their span is between 0.005～0.97.
According to combination of molecular sieve provided by the invention, it has the X-light powdery diffractometry spectrogram shown in the Table A, d-distance values and AlPO that it contains at least
4-5 X-light powdery diffractometry spectrogram is basic identical, illustrates that they have identical crystalline structure, promptly they all have be parallel to the C axle alternately 4-and 6-unit annulated column around the cylinder-like structure that forms, the aperture is 12 yuan of rings, spacer is P6cc.
I
0Diffraction peak intensity when being 11.9 dusts-11.6 dust for spacing d value, I are the intensity of other diffraction peak, I/I
0Be used for representing relative intensity.
According to combination of molecular sieve provided by the invention, it is to constitute as the backbone element of molecular sieve tetrahedral oxide with aluminium, phosphorus, zirconium and at least a substituted element M.S, x, y, z represent substituted element M, zirconium, aluminium and the phosphorus molar fraction in tetrahedral oxide respectively, and the preferred span of s, x, y, z is respectively 0.01～0.15,0.01～0.1,0.4～0.6,0.2～0.5.
At least a substituted element that can constitute the tetrahedral oxide skeleton structure of described M representative, substituted element is selected from least a in silicon, boron, germanium, gallium, manganese, titanium, iron, cobalt and the nickel, at least a in preferred boron, silicon, iron, the gallium, more preferably boron or silicon; S represents the molar fraction of M, and when M was multiple substituted element, the molar fraction sum of multiple substituted element should be not more than 0.97, and wherein the molar fraction of every kind of substituted element can be identical or different, and its value minimum is 0.005.
The value size of m depends on synthetic decomposition or the desorption degree that reaches organic formwork agent in the last handling process of molecular sieve in the chemical constitution expression formula.
The hydrothermal crystallization synthetic method of above-mentioned Zirconium-phosphorus-aluminium molecular sieve composition provided by the invention, be that the reaction mixture that the precursor of phosphorus source, aluminium source, zirconium source, substituted element M, organic formwork agent and water are formed can reacted under the condition of crystallization, the X-light powdery diffractometry d-spacing of Zirconium-phosphorus-aluminium molecular sieve composition that makes formation is substantially shown in Table A.
More particularly, the method for synthetic Zirconium-phosphorus-aluminium molecular sieve composition provided by the invention comprises, with precursor, organic formwork agent and the water of phosphorus source, aluminium source, zirconium source, substituted element M, presses Al
2O
3: (0.05～30) P
2O
5: (0.01～5) ZrO
2: (0.01～1) MO
N/2: (0.1～40) R: (10～800) H
2The mole proportioning of O is mixed into glue, place airtight pressurized vessel, crystallization is 2 hours～30 days under 100～200 ℃, autogenous pressure, and solid product is separated, reclaimed to the X-light powdery diffractometry d-spacing of Zirconium-phosphorus-aluminium molecular sieve composition that makes formation with ordinary method substantially shown in Table A then.
The mole proportion optimization Al of the precursor of said phosphorus source, aluminium source, zirconium source and substituted element M, organic formwork agent and the formed mixed glue solution of water
2O
3: (0.2～1.5) P
2O
5: (0.01～0.5) ZrO
2: (0.1～1) MO
N/2: (1～4) R: (30～80) H
2O.
The raw material of synthetic Zirconium-phosphorus-aluminium molecular sieve composition of the present invention can have multiple choices:
That the phosphorus source can be selected from is elemental phosphorous, ortho-phosphoric acid, phosphorus oxide, phosphoric acid ester or both or both above mixture among them, and preferred phosphorus source is an ortho-phosphoric acid.
The aluminium source comprises the hydrate of aluminium such as aluminium colloidal sol, alumina gel, boehmite, plan boehmite, monohydrate alumina, bayerite and two or more mixture arbitrarily among them, the oxide compound of alcohol radical aluminium, aluminium and their mixture also can be used as the aluminium source, wherein preferred aluminium source is monohydrate alumina or alcohol radical aluminium, more preferably monohydrate alumina.
The zirconium source is selected from one of zirconium white, ethanol zirconium, propyl alcohol zirconium, zirconyl chloride, Zircosol ZN, zirconium sulfate, formic acid zirconium, zirconium acetate, wherein preferred Zircosol ZN or zirconyl chloride.
In proportioning raw materials formula provided by the invention, n is the oxidation valence state of substituted element M, MO
N/2It is at least a oxide compound.Substituted element M is at least a in silicon, boron, germanium, gallium, manganese, titanium, iron, cobalt and the nickel, at least a in preferred silicon, boron, gallium, the iron, and preferred substituted element is a kind of in silicon, boron, gallium, the iron.
When said substituted element was silicon, the silicon source can be selected from one of the alkoxide of fuming silica, silicon sol, silicon or alkalimetal silicate, wherein preferred silicon sol.
When said substituted element was boron, the boron source was boric acid or boron trioxide.
When said substituted element is above-mentioned other element beyond silica removal and the boron, the precursor of this substituted element can be oxide compound, oxyhydroxide, the organic or inorganic salt of this substituted element, can be selected from a kind of in the nitrate, vitriol, muriate, bromide, iodide, formate, acetate, ethylate, propylate of this substituted element, wherein preferably nitrate or acetate.
R is an organic formwork agent, and said organic formwork agent is a kind of material that plays structure-directing effect in the crystal generative process, it is generally acknowledged that it has two kinds of effects of electric charge and space.Organic formwork agent generally contains the element of periodic table of elements VA family, particularly nitrogen, phosphorus, arsenic and antimony, better is nitrogen or phosphorus, preferably nitrogen.The organic formwork agent that is used for synthesizing P-Al molecular sieve is numerous, as quaternary ammonium cation, aliphatic amide, hydramine etc., in the present invention, the organic formwork agent of Shi Yonging is selected from one of triethylamine, tripropyl amine, trolamine and TPAOH or any two or more mixture among them.
The reaction mixture colloid carries out crystallization in an airtight pressurized vessel, said reaction conditions so that the X-light powdery diffractometry d-spacing of the Zirconium-phosphorus-aluminium molecular sieve that forms shown in Table A, be as the criterion.Preferred condition is 120～180 ℃ of following crystallization 10 hours～5 days.After crystallization was finished, said separation, the ordinary method that reclaims product are meant filtered or processes such as centrifugal, washing, drying and roasting.
Combination of molecular sieve provided by the invention, the PO in its skeleton tetrahedron
2 +Or AlO
2 -Produced residual electric charge by the oxide compound isomorphous substitution of zirconium and other substituted element, make it have performances such as catalysis, absorption, ion-exchange.It can be used as Hydrocarban coversion catalysts, uses in reaction process such as cracking, hydrocracking, isomerization, reformation, alkylation.For example, under certain condition, with combination of molecular sieve provided by the invention with mineral acid treatment after, its strength of acid H
0＜-8.2, can be used as catalyzer, under 200～300 ℃, the reaction conditions of 3～5Mpa, be used for alkylation reaction of arene.
The following example will the present invention is further illustrated, but the present invention is not so limited.
Example 1～13
These example explanation substituted elements are that boron, organic formwork agent are the preparation of the boron Zirconium-phosphorus-aluminium molecular sieve of triethylamine (brief note is TETN).
The boric acid aqueous solution of getting 198 gram one hydrated aluminum stones and 4.5% is mixed into slurries I.Remove phosphoric acid and the Zircosol ZN or the zirconyl chloride of ionized water adding 85%, stirring and dissolving forms slurries II.Slurries I, II and TETN three are mixed, place three liters of crystallizing kettles, 165 ℃ of crystallization are after 40 hours, filtration, washing, drying, 600 ℃ of following roastings 3 hours.Making boron respectively is the boron Zirconium-phosphorus-aluminium molecular sieve of substituted element, and their X-light powdery diffractometry chromatogram characteristic conforms to Table A.
Table 1 is listed the composition of example 1～13 used zirconium source, feed molar proportioning and gained boron Zirconium-phosphorus-aluminium molecular sieve.
Table 1
| Example | The zirconium source | The feed molar proportioning | Form |
| ????1 | ??ZrO(NO 3) 2 | ??Al 2O 3∶0.5P 2O 5∶0.05ZrO 2∶0.8B 2O 3∶TETN∶80H 2O | ??(B 0.247Zr 0.013??Al 0.510P 0.230)O 2 |
| ????2 | ??ZrO(NO 3) 2 | ??Al 2O 3∶0.8P 2O 5∶0.05ZrO 2∶0.6B 2O 3∶TETN∶80H 2O | ??(B 0.163Zr 0.012??Al 0.470P 0.355)O 2 |
| ????3 | ??ZrO(NO 3) 2 | ??Al 2O 3∶P 2O 5∶0.05ZrO 2∶0.6B 2O 3∶TETN∶80H 2O | ??(B 0.138Zr 0.012??Al 0.467P 0.383)O 2 |
| ????4 | ??ZrO(NO 3) 2 | ??Al 2O 3∶1.2P 2O 5∶0.05ZrO 2∶0.5B 2O 3∶TETN∶80H 2O | ??(B 0.092Zr 0.011??Al 0.470P 0.427)O 2 |
| ????5 | ??ZrO(NO 3) 2 | ??Al 2O 3∶1.5P 2O 5∶0.05ZrO 2∶0.5B 2O 3∶TETN∶80H 2O | ??(B 0.078Zr 0.010??Al 0.463P 0.449)O 2 |
| ????6 | ??ZrOCl 2 | ??Al 2O 3∶0.6P 2O 5∶0.2ZrO 2∶0.8B 2O 3∶TETN∶80H 2O | ??(B 0.238Zr 0.020??Al 0.502P 0.240)O 2 |
| ????7 | ??ZrOCl 2 | ??Al 2O 3∶0.6P 2O 5∶0.5ZrO 2∶0.7B 2O 3∶TETN∶80H 2O | ??(B 0.219Zr 0.031??Al 0.507P 0.243)O 2 |
| ????8 | ??ZrOCl 2 | ??Al 2O 3∶P 2O 5∶0.5ZrO 2∶0.12B 2O 3∶TETN∶80H 2O | ??(B 0.050Zr 0.029??Al 0.488P 0.433)O 2 |
| ????9 | ??ZrOCl 2 | ??Al 2O 3∶P 2O 5∶0.8ZrO 2∶0.2B 2O 3∶1.7TETN∶80H 2O | ??(B 0.065Zr 0.039??Al 0.479P 0.417)O 2 |
| ????10 | ??ZrOCl 2 | ??Al 2O 3∶P 2O 5∶0.8ZrO 2∶0.12B 2O 3∶4TETN∶80H 2O | ??(B 0.039Zr 0.040??Al 0.491P 0.430)O 2 |
| ????11 | ??ZrOCl 2 | ??Al 2O 3∶P 2O 5∶0.5ZrO 2∶0.12B 2O 3∶TETN∶60H 2O | ??(B 0.042Zr 0.030??Al 0.488P 0.440)O 2 |
| ????12 | ??ZrOCl 2 | ??Al 2O 3∶P 2O 5∶0.3ZrO 2∶0.12B 2O 3∶TETN∶40H 2O | ??(B 0.046Zr 0.025??Al 0.489P 0.440)O 2 |
| ????13 | ??ZrOCl 2 | ??Al 2O 3∶P 2O 5∶0.2ZrO 2∶0.2B 2O 3∶2TETN∶80H 2O | ??(B 0.047Zr 0.016??Al 0.490P 0.447)O 2 |
Example 14～16
Change the organic formwork agent in the example 3,7,11 into tripropyl amine respectively, other condition is constant, and making boron is the boron Zirconium-phosphorus-aluminium molecular sieve of substituted element, and their X-light powdery diffractometry chromatogram characteristic conforms to Table A.
Example 17～19
Change the organic formwork agent in the example 3,7,11 into trolamine respectively, other condition is constant, and making boron is the boron Zirconium-phosphorus-aluminium molecular sieve of substituted element, and their X-light powdery diffractometry chromatogram characteristic conforms to Table A.
Example 20～22
Change the organic formwork agent in the example 3,7,11 into TPAOH respectively, other condition is constant, and making boron is the boron Zirconium-phosphorus-aluminium molecular sieve of substituted element, and their X-light powdery diffractometry chromatogram characteristic conforms to Table A.
Example 23～28
Change the boric acid aqueous solution in the example 1,2,13,15,19,20 into aqueous solution of silica gel, other condition is constant, and making silicon is the silicon Zirconium-phosphorus-aluminium molecular sieve of substituted element, forms to see Table 2, and their X-light powdery diffractometry chromatogram characteristic conforms to Table A.
Table 2
| Example | Molecular sieve is formed |
| ????23 | ??(Si 0.194Zr 0.011Al 0.552P 0.243)O 2 |
| ????24 | ??(Si 0.140Zr 0.013Al 0.481P 0.366)O 2 |
| ????25 | ??(Si 0.048Zr 0.015Al 0.502P 0.445)O 2 |
| ????26 | ??(Si 0.202Zr 0.029Al 0.509P 0.260)O 2 |
| ????27 | ??(Si 0.041Zr 0.031Al 0.491P 0.437)O 2 |
| ????28 | ??(Si 0.131Zr 0.011Al 0.463P 0.395)O 2 |
It below is the example of other substituted element.
Example 29～35
According to the feed molar proportioning of example 13, the preparation substituted element is respectively the Zirconium-phosphorus-aluminium molecular sieve composition of gallium, iron, cobalt, titanium, nickel, germanium.The precursor of used substituted element M and molecular sieve composition see Table 3, and their X-light powdery diffractometry chromatogram characteristic conforms to Table A.
Table 3
| Example | The precursor of substituted element M | Molecular sieve is formed |
| ??29 | Gallium nitrate | (Ga 0.074Zr 0.018Al 0.498P 0.420)O 2 |
| ??30 | Iron nitrate | (Fe 0.085Zr 0.015Al 0.490P 0.410)O 2 |
| ??31 | Xiao Suangu | (Co 0.074Zr 0.016Al 0.497P 0.413)O 2 |
| ??32 | Titanium tetrachloride | (Ti 0.061Zr 0.013Al 0.501P 0.425)O 2 |
| ??33 | Nickelous nitrate | (Ni 0.075Zr 0.013Al 0.496P 0.416)O 2 |
| ??34 | Germanium chloride | (Ge 0.071Zr 0.014Al 0.495P 0.420)O 2 |
| ??35 | Manganous sulfate | (Mn 0.056Zr 0.012Al 0.502P 0.430)O 2 |
It below is the example of multiple substituted element.
Example 36～39
According to the feed molar proportioning of example 1, the preparation substituted element is respectively the Zirconium-phosphorus-aluminium molecular sieve composition of boron and gallium, boron and iron, silicon and cobalt, titanium and nickel, silicon and germanium.The title of the precursor of used substituted element M and see Table 4 in the mole number of relative 1 mole of aluminum oxide of oxide compound and the composition of product molecular sieve.Their X-light powdery diffractometry chromatogram characteristic all conforms to Table A.
Table 4
| Example | The precursor of M and consumption thereof | Molecular sieve is formed |
| ??36 | Boric acid 0.5mol+ gallium nitrate 0.5mol | (B 0.140Ga 0.092Zr 0.011Al 0.499P 0.248)O 2 |
| ??37 | Boric acid 0.2mol+ iron nitrate 0.8mol | (B 0.140Fe 0.102Zr 0.010Al 0.503P 0.245)O 2 |
| ??38 | Silicon sol 0.4mol+ Xiao Suangu 0.6mol | (Co 0.130Si 0.104Zr 0.010Al 0.506P 0.250)O 2 |
| ??39 | Silicon sol 0.3mol+ germanium chloride 0.7mol | (Ge 0.110Si 0.132Zr 0.011Al 0.499P 0.248)O 2 |
Example 40
This example illustrates the application of Zirconium-phosphorus-aluminium molecular sieve composition provided by the invention in alkylation reaction of arene.
Raw materials used is chemical pure benzene and industrial hydrocarbon mixture, and wherein the normal olefine of industrial hydrocarbon mixture (comprising C10～C13 alkene) content is 10.7%, and normal paraffin is 82.5%, non-n-alkane 6.8%, and benzene feed alkene mol ratio is 8: 1.
Get the boron Zirconium-phosphorus-aluminium molecular sieve of example 13 preparation, after soaking with the hydrochloric acid solns of 10 heavy %, through fully washing, 600 ℃ of roastings 3 hours.
Fixed bed little anti-in, the 10 milliliters of granularities of packing into are the boron Zirconium-phosphorus-aluminium molecular sieves of 60～80 purposes through above-mentioned processing, at 250 ℃, 4.5Mpa, 1h
-1Carry out benzene alkylation reaction under the air speed condition, stratographic analysis after 100 hours, olefin conversion 99.3%, alkylation rate 98%.
Claims (21)
1, a kind of have an AlPO
4The Zirconium-phosphorus-aluminium molecular sieve composition of-5 crystalline structure, it is characterized in that: the d-spacing that (1) X-light powdery diffractometry spectrogram contains at least is as shown in the table: 2 θ, ° d, dust 100 * I/I
07.4-7.6 11.9-11.6 10014.85-15.2 5.97-5.83 16-2219.7-20.1 4.51-4.42 50-662 0.8-21.2 4.27-4.19 80-10722.3-22.7 3.99-3.92 144-16325.9-26.25 3.44-3.39 52-67, (2) anhydrous chemical expression is: mR:, (M
sZr
xAl
yP
z) O
2
The organic formwork agent of R representative in the internal crystallization pore system in the formula; The m representative is every mole (M relatively
sZr
xAl
yP
z) O
2The mole number of R, its value is 0～5; M representative constitutes the substituted element of tetrahedral oxide skeleton structure, is selected from least a in silicon, boron, germanium, gallium, manganese, titanium, iron, cobalt and the nickel; S, x, y, z represent substituted element M, zirconium, aluminium and the phosphorus molar fraction in tetrahedral oxide respectively, and their span is between 0.005～0.97.
2,, it is characterized in that the span of s, x, y, z is respectively 0.01～0.15,0.01～0.1,0.4～0.6,0.2～0.5 according to the described combination of molecular sieve of claim 1.
3,, it is characterized in that substituted element M is selected from least a in silicon, boron, gallium, the iron according to the described combination of molecular sieve of claim 1.
4,, it is characterized in that substituted element M is boron or silicon according to the described combination of molecular sieve of claim 3.
5, the synthetic method of the described combination of molecular sieve of claim 1 is characterized in that precursor, organic formwork agent and water with phosphorus source, aluminium source, zirconium source, substituted element M, according to Al
2O
3: (0.05～30) P
2O
5: (0.01～5) ZrO
2: (0.01～1) MO
N/2: (0.1～40) R: (10～800) H
2The mole proportioning of O is mixed into glue, place airtight pressurized vessel, crystallization is 2 hours～30 days under 100～200 ℃, autogenous pressure, makes the Zirconium-phosphorus-aluminium molecular sieve composition of formation have X-light powdery diffractometry spectrogram as claimed in claim 1, separates, reclaims solid product then.
6, in accordance with the method for claim 5, the mole proportioning that it is characterized in that into the glue mixture is Al
2O
3: (0.2～1.5) P
2O
5: (0.01～0.5) ZrO
2: (0.1～1) MO
N/2: (1～4) R: (30～80) H
2O.
7, in accordance with the method for claim 5, it is characterized in that the phosphorus source is selected from elemental phosphorous, ortho-phosphoric acid, phosphorus oxide, phosphoric acid ester or both or both above mixture arbitrarily among them.
8, in accordance with the method for claim 7, it is characterized in that the phosphorus source is an ortho-phosphoric acid.
9, in accordance with the method for claim 5, it is characterized in that the aluminium source is selected from aluminium colloidal sol, alumina gel, boehmite, plan boehmite, monohydrate alumina, bayerite and both or both above mixture, the oxide compound of alcohol radical aluminium, aluminium and their mixtures arbitrarily among them.
10, in accordance with the method for claim 9, it is characterized in that the aluminium source is selected from monohydrate alumina or alcohol radical aluminium.
11, in accordance with the method for claim 10, it is characterized in that the aluminium source is a monohydrate alumina.
12, in accordance with the method for claim 5, it is characterized in that the zirconium source is selected from one of zirconium white, zirconyl chloride, Zircosol ZN, zirconium sulfate, formic acid zirconium, zirconium acetate, ethanol zirconium, propyl alcohol zirconium.
13, in accordance with the method for claim 12, it is characterized in that the zirconium source is selected from zirconyl chloride or Zircosol ZN.
14, in accordance with the method for claim 5, it is characterized in that substituted element is selected from least a in silicon, boron, gallium, the iron.
15,, it is characterized in that the silicon source is selected from one of the alkoxide of fuming silica, silicon sol, silicon or alkalimetal silicate according to claim 5 and 14 described methods.
16, in accordance with the method for claim 15, it is characterized in that the silicon source is a silicon sol.
17,, it is characterized in that the boron source is boric acid or boron trioxide according to claim 5 and 14 described methods.
18, in accordance with the method for claim 5, when it is characterized in that the element beyond substituted element is silica removal and boron, the precursor of substituted element is selected from a kind of in nitrate, vitriol, muriate, bromide, iodide, formate, acetate, ethylate, the propylate.
19, in accordance with the method for claim 18, the precursor that it is characterized in that substituted element is nitrate or acetate.
20, in accordance with the method for claim 5, it is characterized in that organic formwork agent is selected from quaternary ammonium cation, aliphatic amide or hydramine.
21, in accordance with the method for claim 20, it is characterized in that organic formwork agent is selected from one of triethylamine, tripropyl amine, trolamine and TPAOH or two or more mixture arbitrarily among them.
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| CN 00103380 CN1100002C (en) | 2000-03-03 | 2000-03-03 | Zirconium-phosphorus-aluminium molecular sieve composition and its preparation method |
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| CN 00103380 CN1100002C (en) | 2000-03-03 | 2000-03-03 | Zirconium-phosphorus-aluminium molecular sieve composition and its preparation method |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100376481C (en) * | 2005-04-15 | 2008-03-26 | 浙江工业大学 | Nb-containing aluminium phosphate molecular sieve composition and its prepn and application |
| CN100390058C (en) * | 2006-04-06 | 2008-05-28 | 辽宁石油化工大学 | Synthetic process of ZSM-5 and MAPO-5 two-structure molecular sieve |
| CN101491773B (en) * | 2008-01-25 | 2013-06-12 | 北京石油化工学院 | MCM-41 molecular sieve catalyst containing phosphor aluminum structure unit, preparation method and use thereof |
| CN105646223A (en) * | 2014-12-04 | 2016-06-08 | 中国科学院大连化学物理研究所 | Method used for preparing succinic acid diester via catalytic oxidation esterification of levulinic acid |
-
2000
- 2000-03-03 CN CN 00103380 patent/CN1100002C/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100376481C (en) * | 2005-04-15 | 2008-03-26 | 浙江工业大学 | Nb-containing aluminium phosphate molecular sieve composition and its prepn and application |
| CN100390058C (en) * | 2006-04-06 | 2008-05-28 | 辽宁石油化工大学 | Synthetic process of ZSM-5 and MAPO-5 two-structure molecular sieve |
| CN101491773B (en) * | 2008-01-25 | 2013-06-12 | 北京石油化工学院 | MCM-41 molecular sieve catalyst containing phosphor aluminum structure unit, preparation method and use thereof |
| CN105646223A (en) * | 2014-12-04 | 2016-06-08 | 中国科学院大连化学物理研究所 | Method used for preparing succinic acid diester via catalytic oxidation esterification of levulinic acid |
| CN105646223B (en) * | 2014-12-04 | 2017-12-26 | 中国科学院大连化学物理研究所 | A kind of method that levulic acid catalysis oxidation esterification prepares succinate |
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| Publication number | Publication date |
|---|---|
| CN1100002C (en) | 2003-01-29 |
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