CN104276580B - Synthesis has the method for the GeAPO zeolite of CHA topological structure - Google Patents
Synthesis has the method for the GeAPO zeolite of CHA topological structure Download PDFInfo
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Abstract
The present invention relates to a kind of method that synthesis has the GeAPO zeolite of CHA topological structure, mainly solve synthesis in prior art and there is the problem that the GeAPO zeolite cost of CHA topological structure is high.The present invention by ge source, aluminum source, phosphorus source, template R, ammonia, water are mixed in proportion, wherein GeO2:Al2O3:P2O5:R:NH3:H2The mol ratio of O is (0.001～2.5): 1:(0.2～3.0): (0.3～15): (0.3～15): (20～500), crystallization the most under hydrothermal conditions, crystallized product is through filtering, washing, dry the GeAPO zeolite that i.e. can obtain there is CHA topological structure, method is easy, easy, template low cost, preferably resolve this problem, can be used for having in the commercial production of the GeAPO zeolite of CHA topological structure, capryl alcohol dehydration is prepared octene and is had preferable reactivity worth by GeAPO zeolite simultaneously, can be used in the commercial production that octene is prepared in capryl alcohol dehydration.
Description
Technical field
The present invention relates to a kind of method that synthesis has the GeAPO zeolite of CHA topological structure.
Background technology
The nineties in 20th century, Ge element value in poromerics synthesizes causes the interest of people.If because
In the periodic table of elements, Ge Yu Si is in same main group and adjacent periods.Ge Yu Si has certain qualitative similarity, can be as Si
Substitute element, the silicate molecular sieve of synthesis Ge element doping or with the germanate molecular sieve of silicate isomorphism, as FAU,
CAN, LTA, MFI, AST, DFT etc..Meanwhile, Ge also has the character of uniqueness, is mainly reflected in Ge O bond distance (about 1.76 angstroms) big
In Si O bond distance (about 1.61 angstroms), Ge O Ge bond angle (about 1300) less than Si O Si (about 1450).Ge element has more flexible
Bond distance and bond angle, add the controllability of structure, it is possible to form the secondary structure unit that some element silicons are hardly formed, as
Double four-membered rings (D4R), three-membered ring etc., it is possible to create the novel topological structure different from Conventional Portland, such as ITQ-n series chemical combination
Thing, ASV, SOS, STW, SOF, PUN, JST etc..At present by introducing Ge element, obtain the molecular sieve knot of ten various news
Structure, such as IFR, IHW, IRR, ISV, ITE, ITH, ITR ,-ITV, ITW, IWR, IWS, IWV, IWW.
It addition, Ge element can also construct quasi-molecule sieve-type Vaculating antigen material.Owing to the ionic radius (53pm) of germanium is big
In silicon atom radius (41pm), Ge is easier to form chemical bond with multiple oxygen atoms；Therefore germanium atom is except GeO4Tetrahedral
Beyond coordination mode, it is also possible to form GeO5Trigonal biyramid/tetragonal pyramid and GeO6The multiple coordination modes such as octahedron.Flexible and changeable
Coordination mode and bigger degree of freedom make germanate system can obtain diversified structure type；Simultaneously can also shape
Become the cluster secondary structure unit that Conventional Portland cannot obtain, for constructing the germanate structure of super large duct and low skeletal density
Provide possibility.Document [Chemical Communications, 1991:483-485] reports with organic amine as template
The germanate Ge of synthesis6O13·NMe4OH, document [Chemistry of Materials, 1992,4:808-812] is reported
Germanate [the Ge that synthesizes for template with organic amine18O38(OH)4]8-[(C2N2H10)2+]4·2H2O, document [Angewandte
Chemie International Edition, 1998,37:129-131] report the micropore that first case contains nine-atomic ring
Germanate (NH4)2Ge7O15(ICMM-1), enter flourish 20 years from this germanate.
Through development for many years, germanate has had considerable in many-sides such as synthetic method, structural chemistry, constitutional chemistries
Progressive.From synthetic method, develop into solvent-thermal process from initial Hydrothermal Synthesis and concentrate colloidal sol synthesis etc.；From template
Selection on see, develop into complicated organic amine, metal complex and the rigidity of many amidos and highly branched chain from simple organic amine
Quaternary amine alkali/season phosphonium salt；From construction features, develop into macropore, super large duct and low bone from initial nine-atomic ring central hole structure
The structure of frame density；From skeleton component, from single pure germanium system to by B, Al, Ga, In, Si, Zn, Zr etc. more than ten
Plant element and be incorporated into the complex system of inorganic skeleton；From the dimension of structure, there is tufted structure, one-dimensional chain and the pipe of zero dimension
Shape structure, two-dimensional layer and double layer structure and three dimensional skeletal structure etc..In a word, germanate is inhaled with " glamour " of its uniqueness
Draw the concern of people.
Ge with Al ionic radius is close, it is possible to increase the multiformity of germanate structure.So far, a series of have known point
The aluminum germanate of son sieve topological classification has been synthesized, such as [Al-Ge-O]-NAT [Journal of Materials
Chemistry, 2000, 10: 451-455]、LOS [Soviet Physics Doklady. 1978, 23: 789-
791]、LTA [Journal of the Chemical Society (Resumed) 1959: 195-208]、JBW
[Microporous and Mesoporous Materials, 2002, 52: 65-78]、CAN [Soviet Physics
Crystalography. 1986, 31: 516-519]、ABW [Microporous and Mesoporous Materials,
2000, 34: 273-279]、RHO[Microporous and Mesoporous Materials, 1999, 28: 139-
154] and GIS [Chemistry of Materials, 2000,12:3760-3769] etc..Document [Nature, 1998,
395:154-157] the charge matching principle of phosphate system is applied in germanate synthetic system, it is successfully obtained new
The compound UCSB-7 (BSV) of grain husk topology molecular sieve type.Document [Journal of the American Chemical
Society, 2009,131:6080-6081] utilize trimethylethyl ammonium hydroxide for template, synthesize an example and have entirely
The aluminum germanate molecular sieve PKU-9 of new topological structure, molecular formula is | (C5H14N)+ 8|[Ge28Al8O72]。
From the eighties in last century, after aluminium phosphate molecular sieve is synthesized, aluminum phosphate and Transition metal substituted aluminum phosphate
The synthesis of molecular sieve is attracted attention by increasing people, owing to it has latent in fields such as absorption, catalysis, ion exchange and separation
Application prospect.Open-framework aluminium phosphate molecular sieve is by AlO4And PO4Tetrahedron is the most alternately arranged to be formed.Recently, people
Attempt to be incorporated in aluminium phosphate molecular sieve skeleton transition metal ions, synthesize and there is special catalytic property and optical property
Aluminium phosphate molecular sieve.Document [Inorganic Chemistry, 2012,51 (1): 225-229] reports (C5H14N2)
[Co2Al4P6O24] and (C5H14N2)[Zn2Al4P6O24] zeolite of two kinds of structures, document [Dalton Transactions,
2011,40 (36): 9289-9294] (C is reported3H4N2)2FeAl3P4O16(C3H4N2)2CrAl3P4O16Two kinds of structures
Zeolite, document [Inorganic Chemistry, 2008,48 (1): 198-203] reports has LAU topologies
(C3N2H5)8|[M8Al16P24O96](M=Co, Mn, Zn).With triethylenediamine cobalt as structure directing agent, document [Solid State
Sciences, 2009,11 (3): 622-627] [d, the l-Co (en) of zero dimension are synthesized3]2[Al(HPO4)2(H1.5PO4)2
(H2PO4)2](H3PO4)4, document [Journal of Solid State Chemistry, 2005,178 (6): 1929-
1934] one-dimensional aluminum phosphate chain d-Co (en) of chirality is synthesized3[AlP2O8]·6.5H2O, document [Chemistry of
Materials, 1997,9 (4): 976-980] synthesize Layered aluminophosphate [d-Co (en)3][Al3P4O16]·3H2O。
Document [Zeolites 19:449-451,1997] reports the GeAPO-11 synthesis side with AEL topological structure
Method.
Document [Jilin University's natural science journal, 4:85-88,1990] report the phosphoric acid germanium with AFI topological structure
The synthesis of aluminum molecular screen GeAPO-5.
Document [petroleum journal (PETROLEUM PROCESSING), 2011,27(2): 313-315] reports has MFI topological structure Ge-
The synthesis of ZSM-5 zeolite film.
Document [Jilin University's natural science journal, 2:112-114,1990] reports has MFI topological structure Ge-
The synthesis of ZSM-5 zeolite.
Document [science journal, 48:761-765,1990] report the conjunction with MRE topological structure Ge-ZSM-48 zeolite
Become.
Patent CN200980128392.7 discloses the method for the most phosphorous Cu zeolite with CHA structure of synthesis.
Patent CN200580040907.X discloses the method for the most phosphorous zeolite with CHA structure of synthesis.
Patent CN10238739A discloses the method for the most phosphorous zeolite with CHA structure of synthesis.
Patent CN101808740A discloses the method for synthesis MeAPO zeolite, but there is no synthesis in embodiment and have CHA and open up
The method flutterring the GeAPO zeolite of structure.
Patent CN101720252A discloses the method for synthesis germanium zeolite, but there is no synthesis in embodiment and have CHA topology
The method of the GeAPO zeolite of structure.
Patent US6540970B1 discloses the method for synthesis MeAPO zeolite, but there is no synthesis in embodiment and have CHA and open up
The method flutterring the GeAPO zeolite of structure.
Patent US4888167 discloses the method for synthesis GeAPO zeolite, only embodiment 7 and gives synthesis and have CHA and open up
The method flutterring the GeAPO-34 zeolite of structure.But the template that this patent synthesis GeAPO-34 zeolite uses is tetraethyl hydroxide
, there is the shortcoming that cost is high in ammonium.
Capryl alcohol is dehydrated octene processed and typically uses the aluminium oxide catalyst of modification.Paper (the sec-n-octyl alcohol gas phase that Huang Qing etc. deliver
Dehydration synthesis 2-octene, Industrial Catalysis, in March, 2007, volume 15, the 3rd phase, P50-53) report, at 330 DEG C, 0.35h-1Air speed
Under, 2-octene yield is up to 93%.Height is taken the lead etc. and paper (the modified aluminas catalysis Dehydration of primary alcohols synthesis 1-alkene such as to be delivered
Research, Journal of Dalian University of Technology Total, July calendar year 2001, volume 41, the 4th phase, P412-415) report, by aluminium oxide catalyst
Modification, 340 DEG C, under normal pressure, capryl alcohol conversion ratio reaches 96.8%, and Octenes selectivity is about 70%, and prior art all exists reaction
The shortcoming that temperature is high, Octenes selectivity is low.
In sum, there is high the lacking of cost in the method for the GeAPO zeolite that conventional art synthesis has CHA topological structure
Point, existing capryl alcohol in the art is dehydrated the shortcoming that octene reaction temperature processed is high, Octenes selectivity is low.
Summary of the invention
The technical problem to be solved is the GeAPO zeolite that in conventional art, synthesis has CHA topological structure
There is the shortcoming that cost is high in method, it is provided that a kind of new synthesis has the method for the GeAPO zeolite of CHA topological structure, the method
Easy, easy, template low cost, preferably resolves this problem, can be used for having the GeAPO zeolite of CHA topological structure
In commercial production.
In order to solve above-mentioned technical problem, the technical solution used in the present invention is as follows: a kind of synthesis has CHA topological structure
The method of GeAPO zeolite, ge source, aluminum source, phosphorus source, template R, ammonia, water are mixed in proportion, then crystallization temperature be 80～
250 DEG C, crystallization time is crystallization under conditions of 24～1200 hours, and crystallized product obtains having CHA through filtering, wash, drying
The GeAPO zeolite of topological structure；Under above-mentioned reaction condition, the mol ratio of reactant includes:
GeO2/ Al2O30.001～2.5
P2O5/ Al2O30.2～3.0
R/ Al2O30.3～15
NH3/ Al2O30.3～15
H2O/ Al2O320～500
Described template R be in 4 bromide, tetraethylammonium bromide, 4-propyl bromide, tetrabutyl ammonium bromide extremely
Few one.
Ge source is at least one in germanium oxide, germanic acid, hydroxide germanium, germanium tetrahydride；Template R be 4 bromide,
One in tetraethylammonium bromide, 4-propyl bromide or tetrabutyl ammonium bromide；Aluminum source be aluminum nitrate, aluminum sulfate, three aluminum ethylate .s,
In aluminum isopropylate., isobutanol aluminum, boehmite, boehmite at least one；Phosphorus source is at least one in phosphoric acid, pyrophosphoric acid；
Crystallization temperature is 100～210 DEG C, and crystallization time is 96～1100 hours.
The mol ratio of the reaction system of optimization of the present invention includes:
GeO2/ Al2O30.01～2.0
P2O5/ Al2O30.5～2.0
R/ Al2O30.5～10
NH3/ Al2O30.5～10
H2O/ Al2O340～300
The mol ratio of the reaction system that the present invention more optimizes includes:
GeO2/ Al2O30.9～1.8
P2O5/ Al2O30.5～1.9
R/ Al2O30.5～0.8
NH3/ Al2O30.5～8
H2O/ Al2O340～250
Preferably ge source is at least one in germanium oxide, hydroxide germanium.
Preferably R is tetraethylammonium bromide.
Preferably aluminum source is at least one in boehmite, boehmite.
Preferably phosphorus source is phosphoric acid.
Preferably crystallization temperature scope is 120～200 DEG C, and crystallization time is 100～1000 hours.
By patent CN200910070655.5, CN00126629.2, CN200910070654.0 and
CN200910070657.4, it is known that Tetramethylammonium hydroxide, tetraethyl ammonium hydroxide, TPAOH, four fourth hydrogen-oxygen bromines
Changing ammonium is that raw material is through complicated by 4 bromide, tetraethylammonium bromide, 4-propyl bromide, tetrabutyl ammonium bromide respectively
Chemical process is prepared from.Ammonium bromide is more many than ammonium hydroxide low price.The present invention is by the allotment to material molar ratio, excellent
Changing crystallization temperature and crystallization time, achieve unforeseeable technique effect, present invention synthesis has CHA topological structure
The method of GeAPO zeolite, uses ammonia and ammonium bromide to do template and greatly reduce the synthesis cost of zeolite.Work as GeO2:Al2O3:
P2O5:R:NH3:H2The mol ratio of O is (0.001～2.5): 1:(0.2～3.0): (0.3～15): (0.3～15): (20～
500), time, the GeAPO zeolite with CHA topological structure, beneficially industrialized production can be prepared.
Use the inventive method, ge source, aluminum source, phosphorus source, template, ammonia, water are mixed in proportion, wherein GeO2:Al2O3:
P2O5:R:NH3:H2The mol ratio of O is (0.001～2.5): 1:(0.2～3.0): (0.3～15): (0.3～15): (20～
500), then crystallization under hydrothermal conditions, crystallized product i.e. can obtain having CHA topological structure through filtering, wash, drying
GeAPO zeolite, the present invention can synthesize GeAPO zeolite under mild conditions, has synthesis condition gentle, synthesizes low cost, work
The simple advantage of skill.
A kind of method of synthesizing octene, with capryl alcohol aqueous solution that weight percent concentration is 5 ~ 100% as raw material, in reaction
Temperature is 150 ~ 400 DEG C, and the volume space velocity of capryl alcohol is 0.1 ~ 25 hour-1Under the conditions of, it is pungent that reaction raw materials contacts generation with catalyst
Alkene；Wherein used catalyst is the described GeAPO zeolite with CHA topological structure.
Simultaneously as the GeAPO zeolite with CHA topological structure has suitable acidity, octene is prepared in capryl alcohol dehydration
There is preferable reactivity worth, can be used in the commercial production that octene is prepared in capryl alcohol dehydration.Octene reaction is prepared in capryl alcohol dehydration, with
Weight percent concentration be the capryl alcohol aqueous solution of 5 ~ 100% be raw material, be 150 ~ 400 DEG C in reaction temperature, relative to the body of capryl alcohol
Long-pending air speed is 0.1 ~ 25 hour-1Under the conditions of, reaction raw materials contacts generation octene with catalyst；Wherein used catalyst is for having
The GeAPO zeolite of CHA topological structure, has suitable acidity and duct knot owing to having the GeAPO zeolite of CHA topological structure
Structure, when using it for the reaction that octene is prepared in capryl alcohol dehydration, has that reaction temperature is low, capryl alcohol conversion ratio high, Octenes selectivity is high
Advantage, evaluation result shows, capryl alcohol conversion ratio is up to 100%, and Octenes selectivity, up to 99%, achieves good technology effect
Really.
Below by embodiment, the present invention is further elaborated.
Accompanying drawing explanation
The XRD figure of the GeAPO zeolite with CHA topological structure that Fig. 1 synthesizes for [embodiment 1].
The SEM photograph of the GeAPO zeolite with CHA topological structure that Fig. 2 synthesizes for [embodiment 1].
The NH of the GeAPO zeolite with CHA topological structure that Fig. 3 synthesizes for [embodiment 1]3-TPD schemes.
Detailed description of the invention
[embodiment 1]
By GeO2:Al2O3:P2O5:R:NH3:H2O=1.15:1.00:1.00:0.80:3.20:135.50 weighs each material,
Germanium oxide, boehmite, phosphoric acid, tetraethylammonium bromide, ammonia and water are mixed, stirs 20 minutes, load in reactor, 150 DEG C
Crystallization 240 hours.Crystallization product filters, is washed to pH value is 8, dries 12 hours in 120 DEG C, prepares and has CHA topological structure
GeAPO zeolite, XRD spectra is shown in that Fig. 1, SEM photograph are shown in Fig. 2.
The performance evaluation of catalyst is carried out on fixed-bed tube reactor (25 × 500 millimeters of rustless steels of Ф), catalyst
Useful load is 10 milliliters.Product uses Agilent4890 gas chromatograph to analyze respectively after gas-liquid separation.Reaction condition
And reaction result is shown in Table 2.
[embodiment 2]
By GeO2:Al2O3:P2O5:R:NH3:H2O=0.15:1.00:1.35:0.58:1.20:145.60 weighs each material,
Germanium oxide, boehmite, phosphoric acid, tetraethylammonium bromide, ammonia and water are mixed, stirs 20 minutes, load in reactor, 100
DEG C crystallization 1100 hours.Crystallization product filters, is washed to pH value is 8, dries 12 hours in 120 DEG C, prepares and has CHA topology knot
The GeAPO zeolite of structure.
The performance evaluation of catalyst is carried out on fixed-bed tube reactor (25 × 500 millimeters of rustless steels of Ф), catalyst
Useful load is 10 milliliters.Product uses Agilent4890 gas chromatograph to analyze respectively after gas-liquid separation.Reaction condition
And reaction result is shown in Table 2.
[embodiment 3]
By GeO2:Al2O3:P2O5:R:NH3:H2O=2.18:1.00:1.74:2.13:3.60:44.70 weighs each material, will
Germanic acid, boehmite, pyrophosphoric acid, 4 bromide, ammonia and water mixing, stir 20 minutes, loads in reactor, 130 DEG C of crystalline substances
Change 680 hours.Crystallization product filters, is washed to pH value is 8, dries 12 hours in 120 DEG C, prepares and has CHA topological structure
GeAPO zeolite.
The performance evaluation of catalyst is carried out on fixed-bed tube reactor (25 × 500 millimeters of rustless steels of Ф), catalyst
Useful load is 10 milliliters.Product uses Agilent4890 gas chromatograph to analyze respectively after gas-liquid separation.Reaction condition
And reaction result is shown in Table 2.
[embodiment 4]
By GeO2:Al2O3:P2O5:R:NH3:H2O=0.65:1.00:2.33:3.00:4.20:351.30 weighs each material,
Germanium oxide, aluminum nitrate, phosphoric acid, tetraethylammonium bromide, ammonia and water are mixed, stirs 20 minutes, load in reactor, 180 DEG C of crystalline substances
Change 432 hours.Crystallization product filters, is washed to pH value is 8, dries 12 hours in 120 DEG C, prepares and has CHA topological structure
GeAPO zeolite.
The performance evaluation of catalyst is carried out on fixed-bed tube reactor (25 × 500 millimeters of rustless steels of Ф), catalyst
Useful load is 10 milliliters.Product uses Agilent4890 gas chromatograph to analyze respectively after gas-liquid separation.Reaction condition
And reaction result is shown in Table 2.
[embodiment 5]
By GeO2:Al2O3:P2O5:R:NH3:H2O=1.66:1.00:0.79:1.17:2.20:439.20 weighs each material,
Germanium oxide, aluminum nitrate, phosphoric acid, 4-propyl bromide, ammonia and water are mixed, stirs 20 minutes, load in reactor, 190 DEG C of crystalline substances
Change 144 hours.Crystallization product filters, is washed to pH value is 8, dries 12 hours in 120 DEG C, prepares and has CHA topological structure
GeAPO zeolite.
The performance evaluation of catalyst is carried out on fixed-bed tube reactor (25 × 500 millimeters of rustless steels of Ф), catalyst
Useful load is 10 milliliters.Product uses Agilent4890 gas chromatograph to analyze respectively after gas-liquid separation.Reaction condition
And reaction result is shown in Table 2.
[embodiment 6]
By GeO2:Al2O3:P2O5:R:NH3:H2O=1.75:1.00:0.92:13.59:9.39:117.60 weighs each material,
Germanium oxide, boehmite, phosphoric acid, tetraethylammonium bromide, ammonia and water are mixed, stirs 20 minutes, load in reactor, 200 DEG C
Crystallization 96 hours.Crystallization product filters, is washed to pH value is 8, dries 12 hours in 120 DEG C, prepares and has CHA topological structure
GeAPO zeolite.
The performance evaluation of catalyst is carried out on fixed-bed tube reactor (25 × 500 millimeters of rustless steels of Ф), catalyst
Useful load is 10 milliliters.Product uses Agilent4890 gas chromatograph to analyze respectively after gas-liquid separation.Reaction condition
And reaction result is shown in Table 2.
[embodiment 7]
By GeO2:Al2O3:P2O5:R:NH3:H2O=0.83:1.00:0.38:10.03:13.41:51.80 weighs each material,
Germanium oxide, aluminum isopropylate., phosphoric acid, tetraethylammonium bromide, ammonia and water are mixed, stirs 20 minutes, load in reactor, 210 DEG C
Crystallization 1000 hours.Crystallization product filters, is washed to pH value is 8, dries 12 hours in 120 DEG C, prepares and has CHA topological structure
GeAPO zeolite.
The performance evaluation of catalyst is carried out on fixed-bed tube reactor (25 × 500 millimeters of rustless steels of Ф), catalyst
Useful load is 10 milliliters.Product uses Agilent4890 gas chromatograph to analyze respectively after gas-liquid separation.Reaction condition
And reaction result is shown in Table 2.
[embodiment 8]
By GeO2:Al2O3:P2O5:R:NH3:H2O=0.01:1.00:1.94:8.11:4.26:83.20 weighs each material, will
Hydroxide germanium, boehmite, phosphoric acid, tetraethylammonium bromide, ammonia and water mixing, stir 20 minutes, loads in reactor, 150 DEG C
Crystallization 960 hours.Crystallization product filters, is washed to pH value is 8, dries 12 hours in 120 DEG C, prepares and has CHA topological structure
GeAPO zeolite.
The performance evaluation of catalyst is carried out on fixed-bed tube reactor (25 × 500 millimeters of rustless steels of Ф), catalyst
Useful load is 10 milliliters.Product uses Agilent4890 gas chromatograph to analyze respectively after gas-liquid separation.Reaction condition
And reaction result is shown in Table 2.
[comparative example 1]
By the condition of [embodiment 1], by GeO2:Al2O3:P2O5:R:NH3:H2O=3.00:1.00:1.00: 0.80:
3.20:135.00 weigh each material, germanium oxide, boehmite, phosphoric acid, tetraethylammonium bromide, ammonia and water are mixed, stirs 20 points
Clock, loads in reactor, 170 DEG C of crystallization 340 hours.Crystallization product filters, is washed to pH value is 8, dries 12 in 120 DEG C little
Time, prepare the GeAPO zeolite with AFI topological structure.
[comparative example 2]
By the condition of [embodiment 1], by GeO2:Al2O3:P2O5:R:NH3:H2O=1.15:1.00:0.15: 0.80:
3.20:135.00 weighs each material, germanium oxide, boehmite, phosphoric acid, tetraethylammonium bromide, ammonia and water is mixed, stirs 20 points
Clock, loads in reactor, 170 DEG C of crystallization 340 hours.Crystallization product filters, is washed to pH value is 8, dries 12 in 120 DEG C little
Time, prepare unformed product.
[comparative example 3]
By the condition of [embodiment 1], by GeO2:Al2O3:P2O5:R:NH3:H2O=1.15:1.00:1.00:0.27:3.20:
135.00 weigh each material, germanium oxide, boehmite, phosphoric acid, tetraethylammonium bromide, ammonia and water are mixed, stirs 20 minutes, dress
Enter in reactor, 170 DEG C of crystallization 340 hours.Crystallization product filters, is washed to pH value is 8, dries 12 hours in 120 DEG C, prepares
Unformed product.
[comparative example 4]
By the condition of [embodiment 1], by GeO2:Al2O3:P2O5:R:NH3:H2O=1.15:1.00:1.00: 0.80:
0.28:135.00 weighs each material, germanium oxide, boehmite, phosphoric acid, tetraethylammonium bromide, ammonia and water is mixed, stirs 20 points
Clock, loads in reactor, 170 DEG C of crystallization 340 hours.Crystallization product filters, is washed to pH value is 8, dries 12 in 120 DEG C little
Time, prepare the GeAPO zeolite with AFI topological structure.
[comparative example 5]
By the condition of [embodiment 1], by GeO2:Al2O3:P2O5:R:NH3:H2O=1.15:1.00:1.00: 0.80:
3.20:600.00 weighs each material, germanium oxide, boehmite, phosphoric acid, tetraethylammonium bromide, ammonia and water is mixed, stirs 20 points
Clock, loads in reactor, 170 DEG C of crystallization 340 hours.Crystallization product filters, is washed to pH value is 8, dries 12 in 120 DEG C little
Time, prepare unformed product.
By embodiment 1 and the comparison of comparative example 1～5, it can be seen that GeO in preparation process2:Al2O3:P2O5:R:
NH3:H2The mol ratio of O is very big on the result impact of preparation, works as GeO2:Al2O3:P2O5:R:NH3:H2The mol ratio of O is (0.001
～2.5): 1:(0.2～3.0): (0.3～15): (0.3～15): time (20～500), can prepare and there is CHA topological structure
GeAPO zeolite, and when the consumption of any raw material exceedes this scope, then will not obtain that there is CHA topological structure
GeAPO zeolite.
Table 1
[comparative example 6]
Weighing boehmite 200 grams, in kneader, adds 2.5 grams of dried starch and mediates 30 minutes, add 200 milliliter 0.5%
Nitric acid is mediated 30 minutes, extruded moulding, dries 12 hours in 120 DEG C, 550 DEG C of roastings 10 hours, obtains the capryl alcohol dehydration of molding
Octene catalyst processed.
The performance evaluation of catalyst is carried out on fixed-bed tube reactor (25 × 500 millimeters of rustless steels of Ф), catalyst
Useful load is 10 milliliters.Product uses Agilent4890 gas chromatograph to analyze respectively after gas-liquid separation.Reaction condition
And reaction result is shown in Table 2.
[comparative example 7]
Use [comparative example 6] catalyst, carry out catalyst performance evaluation, reaction condition and reaction by [comparative example 1] condition
The results are shown in Table 2.
Table 2
Claims (7)
1. synthesis has the method for GeAPO zeolite for CHA topological structure, it is characterized in that ge source, aluminum source, phosphorus source, template
Agent R, ammonia, water are mixed in proportion, then are 100～210 DEG C at crystallization temperature, and crystallization time is brilliant under conditions of 96～1100 hours
Changing, crystallized product is through filtering, wash, dry the GeAPO zeolite obtaining having CHA topological structure；React under above-mentioned reaction condition
The mol ratio of thing includes:
Described template R is in 4 bromide, tetraethylammonium bromide, 4-propyl bromide, tetrabutyl ammonium bromide at least one
Kind.
Synthesis the most according to claim 1 has the method for the GeAPO zeolite of CHA topological structure, it is characterised in that reaction
The mol ratio of thing includes:
。
Synthesis the most according to claim 2 has the method for the GeAPO zeolite of CHA topological structure, it is characterised in that reaction
The mol ratio of thing includes:
。
Synthesis the most according to claim 1 has the method for the GeAPO zeolite of CHA topological structure, it is characterised in that template
Agent R is the one in 4 bromide, tetraethylammonium bromide, 4-propyl bromide or tetrabutyl ammonium bromide.
Synthesis the most according to claim 1 has the method for the GeAPO zeolite of CHA topological structure, it is characterised in that ge source
It is at least one in germanium oxide, germanic acid, hydroxide germanium, germanium tetrahydride.
Synthesis the most according to claim 1 has the method for the GeAPO zeolite of CHA topological structure, it is characterised in that aluminum source
It is at least one in aluminum nitrate, aluminum sulfate, three aluminum ethylate .s, aluminum isopropylate., isobutanol aluminum, boehmite, boehmite.
Synthesis the most according to claim 1 has the method for the GeAPO zeolite of CHA topological structure, it is characterised in that phosphorus source
It is at least one in phosphoric acid, pyrophosphoric acid.
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| US4888167A (en) * | 1984-04-13 | 1989-12-19 | Uop | Germanium-aluminum-phosphorus-oxide molecular sieve compositions |
| CN1832802A (en) * | 2003-08-05 | 2006-09-13 | 埃克森美孚化学专利公司 | Molecular sieve catalyst compositions, their production and use in conversion processes |
| CN101491773A (en) * | 2008-01-25 | 2009-07-29 | 北京石油化工学院 | MCM-41 molecular sieve catalyst containing phosphor aluminum structure unit, preparation method and use thereof |
| CN101993094A (en) * | 2009-08-19 | 2011-03-30 | 汉能科技有限公司 | Cerium-containing silicoaluminophosphate (SAPO) type molecular sieve Ce-APO-34 and preparation method and application thereof |
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| US4888167A (en) * | 1984-04-13 | 1989-12-19 | Uop | Germanium-aluminum-phosphorus-oxide molecular sieve compositions |
| CN1832802A (en) * | 2003-08-05 | 2006-09-13 | 埃克森美孚化学专利公司 | Molecular sieve catalyst compositions, their production and use in conversion processes |
| CN101491773A (en) * | 2008-01-25 | 2009-07-29 | 北京石油化工学院 | MCM-41 molecular sieve catalyst containing phosphor aluminum structure unit, preparation method and use thereof |
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