CN100368086C - Synthetic method for metal ion containing silicon-phosphor-aluminium molecular shieve - Google Patents
Synthetic method for metal ion containing silicon-phosphor-aluminium molecular shieve Download PDFInfo
- Publication number
- CN100368086C CN100368086C CNB200410017714XA CN200410017714A CN100368086C CN 100368086 C CN100368086 C CN 100368086C CN B200410017714X A CNB200410017714X A CN B200410017714XA CN 200410017714 A CN200410017714 A CN 200410017714A CN 100368086 C CN100368086 C CN 100368086C
- Authority
- CN
- China
- Prior art keywords
- molecular sieve
- metal ion
- phosphorus
- silicon
- source
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 229910021645 metal ion Inorganic materials 0.000 title claims abstract description 20
- 238000010189 synthetic method Methods 0.000 title claims abstract description 14
- -1 silicon-phosphor-aluminium Chemical compound 0.000 title claims abstract description 8
- 239000002808 molecular sieve Substances 0.000 claims abstract description 43
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 43
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 20
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 14
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000011574 phosphorus Substances 0.000 claims abstract description 13
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 13
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000010703 silicon Substances 0.000 claims abstract description 12
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims abstract description 11
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 10
- 238000002425 crystallisation Methods 0.000 claims description 21
- 230000008025 crystallization Effects 0.000 claims description 21
- 238000006243 chemical reaction Methods 0.000 claims description 17
- 239000004411 aluminium Substances 0.000 claims description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 11
- 239000002994 raw material Substances 0.000 claims description 10
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 229910001868 water Inorganic materials 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 3
- 229910052797 bismuth Inorganic materials 0.000 claims description 3
- 229910001593 boehmite Inorganic materials 0.000 claims description 3
- 239000002131 composite material Substances 0.000 claims description 3
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- HIVGXUNKSAJJDN-UHFFFAOYSA-N [Si].[P] Chemical compound [Si].[P] HIVGXUNKSAJJDN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 235000011007 phosphoric acid Nutrition 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 abstract description 30
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 abstract description 18
- 238000000034 method Methods 0.000 abstract description 13
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 abstract description 12
- QQONPFPTGQHPMA-UHFFFAOYSA-N Propene Chemical compound CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 abstract description 12
- 229910052799 carbon Inorganic materials 0.000 abstract description 7
- 230000003197 catalytic effect Effects 0.000 abstract description 7
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 abstract description 5
- 150000001875 compounds Chemical class 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- 239000003054 catalyst Substances 0.000 description 17
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 10
- 239000000047 product Substances 0.000 description 7
- 238000003756 stirring Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- 239000000499 gel Substances 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229910006367 Si—P Inorganic materials 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000005119 centrifugation Methods 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000011017 operating method Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 235000015110 jellies Nutrition 0.000 description 2
- 239000008274 jelly Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000012265 solid product Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- 229910017090 AlO 2 Inorganic materials 0.000 description 1
- 241000269350 Anura Species 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- GHTGICGKYCGOSY-UHFFFAOYSA-K aluminum silicon(4+) phosphate Chemical compound [Al+3].P(=O)([O-])([O-])[O-].[Si+4] GHTGICGKYCGOSY-UHFFFAOYSA-K 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 150000001722 carbon compounds Chemical class 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 229910052675 erionite Inorganic materials 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Landscapes
- Catalysts (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to a synthetic method for a metal ion containing a silicon-phosphorus-aluminium molecular sieve. The problems of low catalytic activity and the low selectivity of ethene, propene and butylene in the process that the silicon-phosphorus-aluminium molecular sieve prepared in the prior art is used for preparing low carbon alkene by methanol or dimethyl ether are mainly solved. In the present invention, the problems are well solved by the technical scheme that triethylamine and fluoride are used as compound template agents to crystallize metal ions, a silicon source, a phosphorus source and an aluminum source for not less than 0.5 hour under the condition that temperature is 100 to 250 DEG C. The present invention can be used for the industrial production of the silicon-phosphorus-aluminium molecular sieve.
Description
Technical field
The present invention relates to the synthetic method of metal ion containing Si-P, particularly about a kind of be the synthetic method that raw material is produced the effective catalyst of low-carbon alkene (ethene or propylene) by dimethyl ether or methyl alcohol, the synthetic method of promptly metallic SAPO-34 molecular sieve.
Background technology
Ethene, the effect of propylene in modern chemistry industry hold the balance.Up to this point, most ethene, propylene all come from PETROLEUM PROCESSING.But for oil, rise in price and supply problem of unstable were arranged in short-term, then have the resource storage capacity limited for a long time, thereby produce the problem of " oil crisis ".By methyl alcohol or dimethyl ether is that to produce low-carbon alkene (MTO or DTO) be the novel process that is hopeful to replace petroleum path most to catalytic material.The synthesis technique of methyl alcohol, dimethyl ether is quite ripe, and raw material sources are abundant, such as coal, natural gas and solid waste being passed through synthesis gas (CO+H
2) directly synthetic obtaining.For this new technology, appropriate catalyst is a key point.Mobil company had once adopted the catalyst of ZSM-5 molecular sieve as MTO, but bigger duct and the stronger surface acidity of this molecular sieve makes it as the MTO catalyst time, and the selectivity of ethene, propylene is lower, can generate accessory substances such as aromatic hydrocarbons, paraffin.In addition, researchers have also adopted the molecular sieve of aperture such as erionite, T zeolite, chabasie or the ZK-5 molecular sieve catalyst as this new technology, though these small pore molecular sieves have improved the selectivity of low-carbon alkene to a certain extent, their coking rates are big, and inactivation is very fast.
In U.S. Pat 4440871, U.S. carbon compound company (UCC) has developed novel SAPO series molecular sieve (SAPO-n).Wherein SAPO-34 has represented the catalytic performance preferable to MTO.Synthesized silicon-aluminum phosphate SAPO-34 molecular sieve is by SiO
2, AlO
2 -, PO
2 +Three kinds of tetrahedrons interconnect and form, and have structure, window diameter range 0.43～0.50 nanometer of class chabasie, and have moderate acid and good heat endurance and hydrothermal stability.Anhydrous chemical composition can be expressed as: mR (Si
xAl
yP
z) O
2, wherein R is the template agent that exists in the molecular sieve crystal micropore, and m is the molal quantity of R, and x, y, z are respectively the mole fraction of Si, Al, P, and satisfy x+y+z=1.
In order further to improve the selectivity of ethene, propylene, be necessary the acidity of SAPO-34 molecular sieve is regulated, one of method is exactly to add a spot of slaine in the gel process of synthetic SAPO-34 molecular sieve.Perhaps metal ion is introduced the SAPO-34 molecular sieve by the method for liquid ion-exchange.
Exxon had once delivered one piece of patent (US 6040264), introduced alkaline-earth metal Sr in the SAPO-34 molecular sieve, and catalyst performance is improved.After introducing Sr, C in the methanol conversion system olefine reaction
2 =And C
3 =Total recovery can be up to 89.5%, and ethene compares up to 2.3 with propylene.But the Sr slaine is expensive and be difficult to obtain.
Among the Chinese patent CN 1167654A, in molecular sieve, introduced alkaline-earth metal Ca by the method for ion-exchange
2+, also make catalytic performance obtain certain improvement, but the amount that generates byproduct methane is many.
Summary of the invention
Technical problem to be solved by this invention is that the aluminium silicophosphate molecular sieve that makes in the conventional art is used for methyl alcohol or dimethyl ether to produce the low carbon olefin hydrocarbon catalytic activity low, ethene, propylene and the low problem of butylene selectivity provide a kind of synthetic method of new metal ion containing Si-P.This synthetic method has the synthetic aluminium silicophosphate molecular sieve that obtains when being used for methyl alcohol or dimethyl ether system ethene, propylene and butylene process, catalytic activity height, product ethene, propylene and the high characteristics of butylene selectivity.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of synthetic method of metal ion silicon phosphorus aluminium SAPO-34 molecular sieve, raw material comprises silicon source, phosphorus source, aluminium source, slaine and water, by triethylamine and fluoride is composite mould plate agent, and the feed molar of reaction system consists of: mRnFdM (Si
aAl
bP
c) O
2Wherein R is a triethylamine, and m is the molal quantity of triethylamine, and F is a fluorine ion, n is the molal quantity of fluorine ion, M is a metal ion, and d is the molal quantity of metal ion, m=0.03～0.6, n=0.03～0.6, d=0.03～0.6, a=0.01～0.98, b=0.01～0.6, c=0.01～0.6, and satisfy the condition of a+b+c=1, and reaction raw materials is to make the gel crystallization under 100～250 ℃ of conditions at crystallization temperature, the crystallization time is no less than 0.5 hour, get solid after the crystallization after filtration, through washing and being drying to obtain molecular sieve, wherein metal ions M is selected from Cu again, Co, Fe, Ca, Bi or Zn, phosphorus source and fluoride are to join in the reaction system simultaneously.
In the technique scheme, the fluoride preferred version is a hydrofluoric acid.The crystallization temperature preferable range is 150～225 ℃.Crystallization time preferable range is 40～90 hours.Phosphorus source preferred version is an orthophosphoric acid, and silicon source preferred version is Ludox, active silica or ethyl orthosilicate, and aluminium source preferred version is activated alumina, boehmite or aluminum alkoxide.
When above-mentioned molecular sieve was specifically synthetic, its silicon source can be Ludox, active silica or ethyl orthosilicate, and the aluminium source can be boehmite, alcoxyl aluminium or activated alumina.The raw material of template agent, silicon source, aluminium source, phosphorus source and water meets following formula: 0.03～0.6R:(Si
0.01～0.98: Al
0.01～0.6: P
0.01～0.6): 2～500H
2O:0.03～0.6M
M represents slaine
Concrete molecular sieve preparation method carries out according to the following steps:
1,, takes by weighing a certain amount of silicon source, phosphorus source, aluminium source, water, template agent, slaine according to the proportioning in the said structure formula;
2,, and stir the formation gel fully with the mixing of materials that weighs up;
3, with 2 resulting gels, 100～250 ℃ of following crystallization again, the reaction time is greater than 0.5 hour, the solid that the product behind the crystallization filters and centrifugation obtains, through wash, drying can obtain metallic SAPO-34 molecular screen primary powder.Its drying can air dry or 80 ℃ again～150 ℃ under carry out.The characteristics of above-mentioned building-up process are that added template agent used HF-triethylamine composite mould plate agent, and have added a spot of slaine in synthetic crystallization liquid process.
The metallic SAPO-34 molecular sieve that the present invention synthesizes can carry out following processing, makes catalyst:
1, the metallic SAPO-34 molecular screen primary powder that will utilize the inventive method to prepare carries out roasting and removes the template agent in air under 300～700 ℃, becomes active catalyst;
2, the metallic SAPO-34 molecular sieve of calcination process being crossed adds binding agent, for example SiO
2, Al
2O
3, MgO, TiO etc. mix, moulding, drying is carried out roasting again and is made catalyst in 300～700 ℃ of temperature ranges.
Through above-mentioned 1, or 1 and 2 containing metal SAPO-34 molecular sieve catalyst after handling when being used for methyl alcohol or dimethyl ether conversion producing light olefins, reaction temperature is 300～500 ℃, reaction pressure is a normal pressure, preferable reaction temperature is 400～500 ℃, and the weight space velocity of methyl alcohol or dimethyl ether was at 1.0～5.0 o'clock, and conversion of raw material can reach 100%, ethene～butylene selectivity of light olefin can reach 96.4%, obtain better technical effect.
The present invention is further elaborated below by embodiment.
The specific embodiment
[embodiment 1]
Synthesizing of SAPO-34 molecular sieve
According to formula 0.03HF:3.0Et
3N:0.6SiO
2: Al
2O
3: P
2O
5: 60H
2O takes by weighing raw material.
Earlier with a certain amount of rAl
2O
3H2O, positive acid solution, hydrofluoric acid fully mix and form the homogeneous jelly.Keep stirring, add Ludox successively, triethylamine mends a certain amount of deionized water at last.Fully stir the back and form the crystallization mixed liquor.200 ℃ of following crystallization 48 hours, product obtained solid product after centrifugation with the crystallization mixed liquor that obtains above, it 110 ℃ of oven dry in baking oven is spent the night, and the XRD test shows, products obtained therefrom is the SAPO-34 molecular sieve, and does not have other impurity peaks.
[embodiment 2]
Synthesizing of metallic SAPO-34 molecular sieve
According to formula 0.03HF:3.0Et
3N:0.6SiO
2: Al
2O
3: P
2O
5: 60H
2O:0.03Zn (NO
3)
2Take by weighing raw material.
Earlier with a certain amount of rAl2O
3H2O, positive acid solution, hydrofluoric acid fully mix and form the homogeneous jelly.Keep stirring, add zinc nitrate aqueous solution, Ludox, triethylamine successively, mend a certain amount of deionized water at last.Fully stir the back and form the crystallization mixed liquor.With the crystallization mixed liquor that obtains above 200 ℃ of following crystallization 48 hours, product obtains solid product after centrifugation, it 110 ℃ of oven dry in baking oven is spent the night, the XRD test shows, products obtained therefrom is the SAPO-34 molecular sieve, and do not have other impurity peaks, illustrate that metal ion has entered the skeleton of molecular sieve equably.
[embodiment 3]
The preparation of SAPO-34 molecular sieve catalyst
Successively the former powder that makes among embodiment 1 and the embodiment 2 was removed the template agent in 3.0 hours 600 ℃ of following roastings, carry out compressing tablet respectively, broken back sieve is got 20～40 purpose granularity parts, numbering respectively is CS-01, CS-02 catalyst, waits to check and rate.
[embodiment 4]
The examination of SAPO-34 molecular sieve catalyst performance
Adopt fixed-bed catalytic reactor, embodiment 1 and embodiment 2 resulting CS-01, CS-02 catalyst are carried out catalyst examination experiment respectively.Experiment condition is, the catalyst useful load is 1.46 grams, and reaction temperature is 450 ℃, and reaction pressure is a normal pressure, and the weight space velocity of first alcohol and water was respectively 1.25 hours
-1With 3.75 hours
-1, the flow of nitrogen is 50 ml/min.The results are shown in Table 1.
The result of table 1 methanol-to-olefins reaction
| Sample | Methanol conversion (weight %) | Reaction time *(hour) | Hydrocarbon product distribution (weight %) | ||||||||
| CH 4 | C 2H 6 | C 2H 4 | C 3H 8 | C 3H 6 | C 4H 10 | C 4H 8 | C 5 + | C 2 ＝～C 4 ＝ | |||
| CS-01 | 100％ | 60 | 2.57 | 0.63 | 51.06 | 1.31 | 34.83 | 0.0 | 8.48 | 1.12 | 94.37 |
| CS-02 | 100％ | 60 | 1.10 | 0.34 | 56.23 | 0.39 | 33.17 | 0.066 | 7.04 | 1.66 | 96.44 |
* the reaction time is defined as before the dimethyl ether appearance, and the oxygenate rate is 100% time
From table 1, can see, the SAPO-34 sieve sample of containing metal zinc is compared with the SAPO-34 molecular sieve that does not add metal, not only can so that low-carbon alkene particularly the selectivity of (ethene+propylene) to improve, and to the not influence of stability of catalyst.
[embodiment 5]
Press each condition and the operating procedure of embodiment 2, just with Zn (NO
3)
2Change Cu (NO into
3)
2, at last the Cu-SAPO-34 molecular sieve of cupric.
[embodiment 6]
Press each condition and the operating procedure of embodiment 2, just with 0.03Zn (NO in the formula
3)
2Change into 0.2Fe (NO
3)
3, at last the Fe-SAPO-34 molecular sieve of iron content.
[embodiment 7]
Press each condition and the operating procedure of embodiment 2, just with 0.03Zn (NO in the formula
3)
2Change 0.6Bi (NO into
3)
3, at last the Bi-SAPO-34 molecular sieve of bismuth-containing.
Claims (5)
1. the synthetic method of a metal ion silicon phosphorus aluminium SAPO-34 molecular sieve, raw material comprises silicon source, phosphorus source, aluminium source, slaine and water, is composite mould plate agent by triethylamine and fluoride, the feed molar of reaction system consists of: mRnFdM (Si
aAl
bP
c) O
2Wherein R is a triethylamine, and m is the molal quantity of triethylamine, and F is a fluorine ion, n is the molal quantity of fluorine ion, M is a metal ion, and d is the molal quantity of metal ion, m=0.03～0.6, n=0.03～0.6, d=0.03～0.6, a=0.01～0.98, b=0.01～0.6, c=0.01～0.6, and satisfy the condition of a+b+c=1, and reaction raw materials is to make the gel crystallization under 100～250 ℃ of conditions at crystallization temperature, the crystallization time is no less than 0.5 hour, get solid after the crystallization after filtration, through washing and being drying to obtain molecular sieve, wherein metal ions M is selected from Cu again, Co, Fe, Ca, Bi or Zn, phosphorus source and fluoride are to join in the reaction system simultaneously.
2. according to the synthetic method of the described metal ion silicon of claim 1 phosphorus aluminium SAPO-34 molecular sieve, it is characterized in that fluoride is a hydrofluoric acid.
3. according to the synthetic method of the described metal ion silicon of claim 1 phosphorus aluminium SAPO-34 molecular sieve, it is characterized in that crystallization temperature is 150～225 ℃.
4. according to the synthetic method of the described metal ion silicon of claim 1 phosphorus aluminium SAPO-34 molecular sieve, it is characterized in that the crystallization time is 40～90 hours.
5. according to the synthetic method of the described metal ion silicon of claim 1 phosphorus aluminium SAPO-34 molecular sieve, it is characterized in that the phosphorus source is an orthophosphoric acid, the silicon source is Ludox, active silica or ethyl orthosilicate, and the aluminium source is activated alumina, boehmite or aluminum alkoxide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB200410017714XA CN100368086C (en) | 2004-04-16 | 2004-04-16 | Synthetic method for metal ion containing silicon-phosphor-aluminium molecular shieve |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB200410017714XA CN100368086C (en) | 2004-04-16 | 2004-04-16 | Synthetic method for metal ion containing silicon-phosphor-aluminium molecular shieve |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1683078A CN1683078A (en) | 2005-10-19 |
| CN100368086C true CN100368086C (en) | 2008-02-13 |
Family
ID=35262682
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB200410017714XA Expired - Lifetime CN100368086C (en) | 2004-04-16 | 2004-04-16 | Synthetic method for metal ion containing silicon-phosphor-aluminium molecular shieve |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100368086C (en) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100448537C (en) * | 2005-11-17 | 2009-01-07 | 中国科学院大连化学物理研究所 | Catalyst for chloromethane conversion to produce low carbon olefin and its uses |
| CN101121148B (en) * | 2006-08-08 | 2010-05-12 | 中国科学院大连化学物理研究所 | Direct forming method of fluidized reaction catalyst containing molecular sieve |
| CN101165018B (en) * | 2006-10-20 | 2010-05-12 | 中国石油化工股份有限公司 | Method for producing ethylene and propylene |
| CN101711992B (en) * | 2008-09-29 | 2012-05-30 | 宁夏大学 | Catalyst for selectively producing propene by methanol or dimethyl ether and preparation method thereof |
| CN102372288B (en) * | 2010-08-23 | 2013-05-08 | 中国石油化工股份有限公司 | Method for preparing SAPO-34 molecular sieve |
| CN101947467B (en) * | 2010-09-14 | 2012-09-05 | 辽宁石油化工大学 | Preparation process for synthesizing catalyst for low-carbon olefin by carbon dioxide hydrogenation one-step method |
| CN103030158B (en) * | 2011-09-29 | 2015-01-07 | 中国石油化工股份有限公司 | Synthetic method of SAPO-44 molecular sieve modified by rare earth metals |
| CN104096591B (en) * | 2013-04-07 | 2016-08-10 | 刘希尧 | Mto catalyst and preparation method thereof |
| US20150231617A1 (en) * | 2014-02-19 | 2015-08-20 | Ford Global Technologies, Llc | Fe-SAPO-34 CATALYST FOR USE IN NOX REDUCTION AND METHOD OF MAKING |
| CN115770613B (en) * | 2022-12-02 | 2024-03-12 | 江西省科学院应用化学研究所 | Molecular sieve catalyst and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4935216A (en) * | 1984-04-13 | 1990-06-19 | Uop | Zinc-aluminum-phosphorus-silicon-oxide molecular sieve compositions |
| CN1167654A (en) * | 1996-06-07 | 1997-12-17 | 中国科学院大连化学物理研究所 | Metal modified small-porosity P-Si-Al molecular sieve catalyst, its preparing process and use thereof |
| CN1308019A (en) * | 1999-12-30 | 2001-08-15 | 中国科学院大连化学物理研究所 | Porous metal-silicon aluminium phosphate molecular sieve and its synthesis process |
| CN1467155A (en) * | 2002-07-10 | 2004-01-14 | 中国石油化工股份有限公司 | Method for preparing aluminium silicophosphate molecular sieve |
| US6710009B2 (en) * | 1998-10-15 | 2004-03-23 | Mitsubishi Gas Chemical Company, Inc. | Catalysts for producing methylamines and method for manufacturing the same |
-
2004
- 2004-04-16 CN CNB200410017714XA patent/CN100368086C/en not_active Expired - Lifetime
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4935216A (en) * | 1984-04-13 | 1990-06-19 | Uop | Zinc-aluminum-phosphorus-silicon-oxide molecular sieve compositions |
| CN1167654A (en) * | 1996-06-07 | 1997-12-17 | 中国科学院大连化学物理研究所 | Metal modified small-porosity P-Si-Al molecular sieve catalyst, its preparing process and use thereof |
| US6710009B2 (en) * | 1998-10-15 | 2004-03-23 | Mitsubishi Gas Chemical Company, Inc. | Catalysts for producing methylamines and method for manufacturing the same |
| CN1308019A (en) * | 1999-12-30 | 2001-08-15 | 中国科学院大连化学物理研究所 | Porous metal-silicon aluminium phosphate molecular sieve and its synthesis process |
| CN1467155A (en) * | 2002-07-10 | 2004-01-14 | 中国石油化工股份有限公司 | Method for preparing aluminium silicophosphate molecular sieve |
Non-Patent Citations (2)
| Title |
|---|
| SAPO-34分子筛研究新近展. 刘红星等.工业催化，第10卷第(4)期. 2002 * |
| Zn改性的SAPO-34分子筛的制备及其催化性能. 谢在库等.石油化工，第32增刊卷. 2003 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1683078A (en) | 2005-10-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101767800B (en) | Method for preparing SAPO-34 molecular sieve | |
| CN102822124A (en) | Method for making a catalyst comprising a phosphorus modified zeolite to be used in a MTO process | |
| CN103157502B (en) | Catalyst of preparing ethylene and propylene by carbinol and / or dimethyl ether, preparing method and application thereof | |
| CN104556143A (en) | SAPO-34/ZSM-5 composite molecular sieve and synthesis method of composite molecular sieve | |
| CN108745410A (en) | A kind of preparation method of phosphorous multi-stage porous ZSM-5/Y composite molecular screens | |
| CN104888842B (en) | A kind of catalytic cracking catalyst and preparation method and application | |
| CN100368086C (en) | Synthetic method for metal ion containing silicon-phosphor-aluminium molecular shieve | |
| CN101857244B (en) | Silicoaluminophosphate molecular sieve and preparation method and application thereof | |
| CN102372291A (en) | Preparation method of SAPO-18 / SAPO-34 intergrowth molecular sieve | |
| CN104828842A (en) | Preparation method of SAPO-5 and SAPO-34 symbiotic composite molecular sieve | |
| CN104056652A (en) | Core-shell ZSM-5 molecular sieve microsphere catalyst | |
| CN101259431A (en) | Cobalt modification silicoaluminophosphate molecular sieve and its preparation and catalytic application in MTO | |
| CN104108726A (en) | Silicoaluminophosphate molecular sieve with high silica-alumina ratio and CHA structure, and synthetic method thereof | |
| CN104117384A (en) | Toluene methylation catalyst and method for producing p-xylene in presence of same | |
| CN1683079A (en) | Catalyst for reaction to produce olefine with methanol | |
| CN104107721B (en) | ZSM-11/SAPO-11 binary structure zeolites catalyst, preparation method and applications | |
| CN103030158B (en) | Synthetic method of SAPO-44 molecular sieve modified by rare earth metals | |
| CN101318667A (en) | Metal modified silicon aluminum phosphoric molecular sieve, preparation method and catalysis application in MTO thereof | |
| CN1268591C (en) | Method for preparing olefin by conversion of methanol | |
| CN103663483A (en) | Synthesis method of SAPO-34 molecular sieve and catalyst prepared from SAPO-34 molecular sieve | |
| CN1274596C (en) | Process for preparing metallic-ion-containing Si-P-Al molecular sieve | |
| CN103043677A (en) | Modified ferrierite as well as preparation method and application thereof | |
| CN101580248B (en) | Aluminosilicophosphate molecular sieve SAPO-34 and preparation method thereof | |
| CN101195093A (en) | Chromium modified silicon aluminum phosphoric acid molecular sieve, preparation method and application thereof | |
| CN103663485A (en) | P-Si-IM-5 molecular sieve as well as preparation and application of catalyst containing P-Si-IM-5 molecular sieve |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CX01 | Expiry of patent term | ||
| CX01 | Expiry of patent term |
Granted publication date: 20080213 |