CN1274596C - Process for preparing metallic-ion-containing Si-P-Al molecular sieve - Google Patents
Process for preparing metallic-ion-containing Si-P-Al molecular sieve Download PDFInfo
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- CN1274596C CN1274596C CN 200410024735 CN200410024735A CN1274596C CN 1274596 C CN1274596 C CN 1274596C CN 200410024735 CN200410024735 CN 200410024735 CN 200410024735 A CN200410024735 A CN 200410024735A CN 1274596 C CN1274596 C CN 1274596C
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Abstract
The present invention relates to a process for synthesizing a metallic ion containing Si-P-Al molecular sieve. The problems of low catalytic activity and the low selectivity of ethene, propene and butylene in the process that a Si-P-Al 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 tetraethyl ammonium hydroxide and morpholine are used as compound template agents for crystallizing metallic 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 process can be used for the industrial production of the Si-P-Al molecular sieve.
Description
Technical field
The present invention relates to the preparation method of metal ion containing Si-P, particularly about a kind of be the preparation method that raw material is produced the effective catalyst of low-carbon alkene (ethene or propylene) by dme or methyl alcohol, the preparation 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 refining of petroleum.But for oil, price increase and supply problem of unstable were arranged in short duration, then have the resource storage capacity limited for a long time, thereby produce the problem of " oil crisis ".By methyl alcohol or dme 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, dme is quite ripe, and raw material sources are abundant, such as coal, Sweet natural gas and solid waste being passed through synthetic gas (CO+H
2) directly synthetic obtaining.For this novel process, appropriate catalyst is a key point.Mobil company had once adopted the catalyzer of ZSM-5 molecular sieve as MTO, but bigger duct and the stronger surface acidity of this molecular sieve makes it as the MTO catalyzer time, and the selectivity of ethene, propylene is lower, can generate by products such as aromatic hydrocarbons, paraffin.In addition, investigators have also adopted the molecular sieve of aperture such as erionite, T zeolite, chabazite or the ZK-5 molecular sieve catalyzer as this novel process, 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 silicon aluminium phosphate 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 chabazite, and have moderate acid and good thermostability and hydrothermal stability.Anhydrous chemical constitution can be expressed as: mR (Si
xAl
yP
z) O
2, wherein R is the template that exists in the molecular sieve crystal micropore, and m is the mole number 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 metal-salt in the gelation 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 metal-salt 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 dme to produce the low carbon olefin hydrocarbon catalytic activity low, ethene, propylene and the low problem of butylene selectivity provide a kind of preparation method of new metal ion containing Si-P.This preparation method has the synthetic aluminium silicophosphate molecular sieve that obtains when being used for methyl alcohol or dme 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 preparation method of metal ion silicon phosphorus aluminium SAPO-34 molecular sieve, raw material comprises silicon source, phosphorus source, aluminium source, metal-salt and water, by tetraethyl ammonium hydroxide and morpholine is composite mould plate agent, and the feed molar of reaction system consists of: mRnM (Si
aAl
bP
c): dH
2O, wherein M is a metal ion, R=x tetraethyl ammonium hydroxide+y morpholine, m=0.03～0.6, n=0.03～0.6, x+y=1, x＞0, y＞0, x: y=0.01～1: 1, a=0.01～0.98, b=0.01～0.6, c=0.01～0.6, and satisfy a+b+c=1, the condition of d=2～500, reaction raw materials is to make the gel crystallization under 100～250 ℃ of conditions at crystallization temperature, the crystallization time is for being no less than 0.5 hour, and gained solid after filtration after the crystallization is again through washing be drying to obtain molecular sieve.
In the technique scheme, the metal ions M preferred version is for being selected from Cu, Co, Fe, Ca, Bi or Zn; The crystallization temperature preferable range is 150～225 ℃, and crystallization time preferable range is 40～90 hours.Phosphorus source preferred version is an ortho-phosphoric acid, and silicon source preferred version is silicon sol, active silica or tetraethoxy, and aluminium source preferred version is activated alumina, pseudo-boehmite or aluminum alkoxide.The order of addition(of ingredients) preferred version of tetraethyl ammonium hydroxide and morpholine is for being added in the reaction system x simultaneously: the preferable range of y is 0.1～0.5: 1, and more preferably scope is 0.2～0.3: 1.
When above-mentioned molecular sieve specifically prepared, its silicon source can be silicon sol, active silica or tetraethoxy, and the aluminium source can be pseudo-boehmite, alcoxyl aluminium or activated alumina.The raw material of template, 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 metal-salt, and R is the double template that tetraethyl ammonium hydroxide and morpholine are formed, and the molar fraction of every kind of template in double template is all non-vanishing.
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, metal-salt 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 times 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 seasoning or 80 ℃ again～150 ℃ under carry out.The characteristics of above-mentioned building-up process are the composite mould plate agent that added template has used tetraethyl ammonium hydroxide and morpholine to form, and have added a spot of metal-salt in synthetic crystallization liquid process.
The metallic SAPO-34 molecular sieve of synthetic of the present invention can carry out following processing, makes catalyzer:
1, the metallic SAPO-34 molecular screen primary powder that will utilize the inventive method to prepare carries out roasting and removes template 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 catalyzer 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, temperature of reaction is 300～500 ℃, reaction pressure is a normal pressure, preferable temperature of reaction is 400～500 ℃, and the weight space velocity of methyl alcohol or dme was at 1.0～5.0 o'clock, and conversion of raw material can reach 100%, ethene～butylene selectivity of light olefin can reach 96.86%, obtain better technical effect.
The present invention is further elaborated below by embodiment, but do not limit the present invention.
Embodiment
[embodiment 1]
According to formula (0.5TEAOH+2.0Morpholine): 0.6SiO
2: Al
2O
3: P
2O
5: 60H
2O takes by weighing raw material.
Earlier with a certain amount of rAl
2O
3H
2O, positive acid solution fully mix and form the homogeneous jelly.Keep whipped state, add silicon sol successively, mixed templates is the mixture of tetraethyl ammonium hydroxide and morpholine, mends a certain amount of deionized water at last.Fully stir the back and form the crystallization mixed solution.200 ℃ of following crystallization 48 hours, product obtained solid phase prod after centrifugation with the crystallization mixed solution 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 the SAPO-34 molecular sieve of containing metal Zn
According to formula (0.5TEAOH+2.0Morpholine): 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 rAl
2O
3H
2O, positive acid solution fully mix and form the homogeneous jelly.Keep whipped state, add the composite mould plate agent that zinc nitrate aqueous solution, silicon sol, tetraethyl ammonium hydroxide and morpholine are formed successively, mend a certain amount of deionized water at last.Fully stir the back and form the crystallization mixed solution.With the crystallization mixed solution that obtains above 200 ℃ of following crystallization 48 hours, product obtains solid phase prod 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]
Synthesizing of the SAPO-34 molecular sieve of containing metal Bi
According to formula (0.5TEAOH+2.0Morpholine): 0.6SiO
2: Al
2O
3: P
2O
5: 60H
2O: 0.03Bi (NO
3)
2Take by weighing raw material.
Earlier with a certain amount of rAl
2O
3H
2O, positive acid solution fully mix and form the homogeneous jelly.Keep whipped state, add the composite mould plate agent that the Bismuth trinitrate aqueous solution, silicon sol, tetraethyl ammonium hydroxide and morpholine are formed successively, mend a certain amount of deionized water at last.Fully stir the back and form the crystallization mixed solution.With the crystallization mixed solution that obtains above 200 ℃ of following crystallization 48 hours, product obtains solid phase prod 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 4]
The preparation of SAPO-34 molecular sieve catalyst
With embodiment 1, embodiment 2, and the former powder that makes among the embodiment 3 was removed template in 3.0 hours 600 ℃ of following roastings, carry out compressing tablet respectively, broken back sieve is got 20～40 purpose granularity parts, and numbering is respectively CS-01, CS-02, and the CS-03 catalyzer is waited to check and rate.
[embodiment 5]
The examination of SAPO-34 molecular sieve catalyst
Adopt fixed-bed catalytic reactor, with embodiment 1, embodiment 2 and embodiment 3 resulting CS-01, CS-02 and CS-03 catalyzer carry out catalyzer examination experiment respectively.Experiment condition is, the catalyzer loading capacity is 1.46 grams, and temperature of reaction 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 times *(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％ | 6.0 | 1.74 | 0.35 | 54.24 | 0.56 | 33.09 | 0.089 | 8.21 | 2.28 | 95.54 |
| CS-02 | 100％ | 6.0 | 1.38 | 0.39 | 60.12 | 0.40 | 31.22 | 0 | 5.52 | 0.97 | 96.86 |
| CS-03 | 100％ | 6.0 | 1.44 | 0.40 | 56.45 | 0.52 | 33.20 | 0 | 6.55 | 1.44 | 96.20 |
* the reaction times is defined as before the dme appearance, and the oxygenate rate is 100% time
From table 1, can see, the SAPO-34 sieve sample of containing metal zinc or bismuth 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 catalyzer.
Claims (8)
1, a kind of preparation method of metal ion silicon phosphorus aluminium SAPO-34 molecular sieve, raw material comprises silicon source, phosphorus source, aluminium source, metal-salt and water, is composite mould plate agent by tetraethyl ammonium hydroxide and morpholine, the feed molar of reaction system consists of: mRnM (Si
aAl
bP
c): dH
2O, wherein M is a metal ion, R=x tetraethyl ammonium hydroxide+y morpholine, m=0.03～0.6, n=0.03～0.6, x+y=1, x＞0, y＞0, x: y=0.01～1: 1, a=0.01～0.98, b=0.01～0.6, c=0.01～0.6, and satisfy a+b+c=1, the condition of d=2～500, reaction raw materials is to make the gel crystallization under 100～250 ℃ of conditions at crystallization temperature, the crystallization time is for being no less than 0.5 hour, and gained solid after filtration after the crystallization is again through washing be drying to obtain molecular sieve.
2, according to the preparation method of the described metal ion silicon of claim 1 phosphorus aluminium SAPO-34 molecular sieve, it is characterized in that metal ions M is selected from Cu, Co, Fe, Ca, Bi or Zn.
3, according to the preparation 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 preparation method of the described metal ion silicon of claim 1 phosphorus aluminium SAPO-34 molecular sieve, it is characterized in that 40～90 hours crystallization time.
5, according to the preparation 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 ortho-phosphoric acid, the silicon source is silicon sol, active silica or tetraethoxy, and the aluminium source is activated alumina, pseudo-boehmite or aluminum alkoxide.
6, according to the preparation method of the described metal ion silicon of claim 1 phosphorus aluminium SAPO-34 molecular sieve, it is characterized in that tetraethyl ammonium hydroxide and morpholine are to be added in the reaction system simultaneously.
7, according to the preparation method of the described metal ion silicon of claim 1 phosphorus aluminium SAPO-34 molecular sieve, it is characterized in that x: y=0.1～0.5: 1.
8, according to the preparation method of the described metal ion silicon of claim 7 phosphorus aluminium SAPO-34 molecular sieve, it is characterized in that x: y=0.2～0.3: 1.
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| 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 |
| EP1970350A1 (en) * | 2007-03-13 | 2008-09-17 | Total Petrochemicals Research Feluy | Metalloaluminophosphate molecular sieves with lamellar crystal morphology and their preparation |
| 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 |
| CN110240179B (en) * | 2018-03-09 | 2021-05-07 | 国家能源投资集团有限责任公司 | SAPO-34 molecular sieve, and preparation method and application thereof |
| CN109772448A (en) * | 2019-02-14 | 2019-05-21 | 正大能源材料(大连)有限公司 | The preparation method and its application of catalyst containing modified SAPO-34 molecular sieve |
| CN114011457B (en) * | 2021-12-07 | 2023-09-19 | 万华化学集团股份有限公司 | Preparation method of p-ethoxyphenol |
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Application publication date: 20051207 Assignee: Sinopec Nanjing Catalyst Co.,Ltd. Assignor: SHANGHAI Research Institute OF PETROCHEMICAL TECHNOLOGY SINOPEC Contract record no.: X2023310000030 Denomination of invention: Preparation method of silicon phosphorus aluminum molecular sieves containing metal ions Granted publication date: 20060913 License type: Common License Record date: 20230316 |
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