CN1120977A - Method of preparing modified molecular sieve with metal surfactant - Google Patents
Method of preparing modified molecular sieve with metal surfactant Download PDFInfo
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- CN1120977A CN1120977A CN 94117471 CN94117471A CN1120977A CN 1120977 A CN1120977 A CN 1120977A CN 94117471 CN94117471 CN 94117471 CN 94117471 A CN94117471 A CN 94117471A CN 1120977 A CN1120977 A CN 1120977A
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Abstract
Metal surfactant is adsorbed onto outer surface of molecular sieve and then calcined to obtain modified molecular sieve. The method of the present invention can regulate the acidity of outer surface of molecular sieve, make its outer surface have metal activity while its inner surface has acidity, or produce other modified molecular sieve with special structure. The modified molecular sieve has raised selectivity while maintaining the activity.
Description
The invention belongs to the method for molecular sieve being carried out modification.
Molecular sieve has the pore structure and the very big specific area of rule, mainly as adsorbent, catalyst and catalyst carrier, thereby is widely used in chemical industry, medical and health, environmental protection and national defence field.Even to this day, the synthetic technology of molecular sieve is quite complete, and not only its pore structure can be controlled but also each hetero-atom molecular-sieve also constantly is synthesized out.The method of modifying of molecular sieve has multiple as ion-exchange, the isomorphous replacement method, hydrothermal treatment consists method etc., but these method of modifying all are to molecular sieve surfaces externally and internally modification together.The main feature of molecular sieve is its shape selectivity, shape selectivity is from its regular pore structure, because its outer surface does not have shape selectivity, people work out some molecular sieve outer surface modification technologies for this reason, such as covering outer surfaces with various bonding agents or poison molecular sieve outer surface with some organic macromolecules such as trimethoxy phosphine, but these method of modifying often are accompanied by the reduction of molecular sieve activity.
The object of the present invention is to provide a kind of molecular sieve activity that improves, the method that adopts metal surfactant molecular sieve outer surface to be carried out modification.
Method of modifying of the present invention comprises the steps:
(1) preliminary treatment of molecular sieve: in 300-600 ℃ of calcination 1-6 hour, taking-up placed drier to be cooled to room temperature with molecular sieve;
(2) absorption of metal surfactant: be dissolved in metal surfactant in the organic solvent and remove moisture content, then with the above-mentioned pretreated molecular sieve 0.5-24 of this solution impregnation hour;
(3) absorption post processing:, and then dried by the fire 0.5-8 hour under the temperature of 0.8-2.0 TO (TO is the boiling point of organic solvent) with the molecular sieve filtration after the above-mentioned absorption;
(4) calcination: the molecular sieve after the oven dry rises to 200-400 ℃ of calcination 0.5-3.0 hour with 0.3-10 ℃/minute programming rate, and then is warming up to 400-600 ℃ of calcination 1.0-6.0 hour.
The present invention adopts metal surfactant that molecular sieve is carried out modification, makes metal surfactant be adsorbed in the outer surface of molecular sieve, makes the organic moiety decomposition of metal surfactant stay metal oxide after calcination.These metal oxides can also produce new activated centre at molecular sieve outer surface except that can covering the original activated centre of molecular sieve outer surface.
The absorption of metal surfactant can be made into the solution that concentration is 0.001-1.0M with metal surfactant according to needed load capacity, and with this solution impregnation molecular sieve, its dip time is 0.5-24 hour, organic solvent is fallen in the suction of can reducing pressure then, and its pressure can be lower than the saturated vapor pressure of organic solvent.
The main starting point of said method is that the outer surface to molecular sieve carries out acidity and regulates, adopt metal surfactant to handle molecular sieve and stay corresponding metal oxide at its outer surface, and these metal oxides have Acidity of Aikalinity of different nature, the modified molecular screen outer surface of this type also can have the metal active center, and inner surface has acid centre.
In addition, for carrying out modification, handles by the molecular sieve to some special constructions, can also in one step of metal surfactant absorption of said method, use the hybrid metal surfactant more than 2 kinds to make it be dissolved in organic solvent, use this solution impregnation molecular sieve then, thereby make the outer surface of molecular sieve have the hybrid metal activated centre and its inner surface has acid centre.
Method of modifying of the present invention can also in other some molecular sieve modified methods such as ion-exchange in conjunction with the preparation special construction molecular sieve.The molecular sieve of this type is broadly divided into several, a kind ofly is that outer surface has acid centre and inner surface has the molecular sieve at metal active center.The modification purpose of this molecular sieve is will eliminate the surfaces externally and internally that obtains with ion-exchange all to have the defective of metal ion, and the metal active center of outer surface is eliminated.Its method of modifying carries out as follows:
1. with ion-exchange internal and external surface of molecular sieve all is exchanged into the activated centre with metal ion,
2. molecular sieve gives processing: be dissolved in metal surfactant in the organic solvent and remove moisture content, and then with the above-mentioned pretreated molecular sieve 0.5-24 of this solution impregnation hour,
3. the elimination in outer surface activated centre: α-hydrocarbyl replaces carboxylic acid can be dissolved in organic solvent, making its concentration is 0.1-1.0M, with the above molecular sieve of this solution impregnation, and backflow 0.5-6.0 hour, filter, with identical organic solvent washing molecule, the organic solvent with above α-hydrocarbyl replaces carboxylic acid repeats above operation again, 2-10 time so repeatedly
4. absorption post processing: with the molecular sieve filtration after the above-mentioned absorption, under 0.8-2.0TO (TO is the boiling point of organic solvent) temperature, dried by the fire 0.5-8 hour then,
5. calcination: the molecular sieve after the oven dry rises to 200-400 ℃ of calcination 0.5-3.0 hour with 0.3-10 ℃/minute programming rate, and then is warming up to 400-600 ℃ of calcination 1.0-6.0 hour.
Step 3 in the said method is changed into the absorption of metal surfactant, adopt the metal surface different with the ion-exchange agent of living, the result of Chu Liing makes the outer surface of the molecular sieve that modification obtains have a kind of metal active center and inner surface has another kind of metal active center like this.
The molecular sieve of another kind of special construction is to make the activated centre of its surfaces externally and internally have suitable proportion, the method of modifying of this molecular sieve is with metal surfactant molecular sieve to be done modification earlier to handle, thereby makes an amount of same metal ion species of its surface exchange make the metal active center of surfaces externally and internally have suitable ratio with ion-exchange then.
The ion-exchange that this method is mentioned can adopt the ion-exchange of conventional, well-known to carry out.
Metal surfactant in the method for the invention can be the metal carboxylate of non-monovalence, and also the method by organic synthesis connects an organic chain and makes with complexing of metal ion then on metal chelating agent, and its organic chain length is at four more than the carbon.
The described organic solvent of said method can be benzene, dimethylbenzene, industrial crude benzol, benzinum, also industrial solvent.
Method of modifying of the present invention is compared with existing molecular sieve modified method to have easy and simple to handlely, and cost is low, is easy to industrialization, has the advantage of general applicability.The shape selectivity of molecular sieve improves after the modification, show as reaction selectivity and improve in catalytic reaction, but activity does not reduce.This method of modifying combines with other method of modifying can prepare the molecular sieve of various special constructions.
Embodiment one
The modification 1 of methyl alcohol amination ZSM-5 molecular sieve
The product of methyl alcohol amination is monomethyl amine (MMA), dimethylamine (DMA), negative products such as trimethylamine (TMA) and dimethyl ether, the selectivity of its total amine of Hydrogen ZSM-5 molecular sieve is generally all more than 90%, this reacts needed product is MMA and DNA, the pore structure of molecular sieve helps the generation of MMA and DMA, but is that reaction power distributes at the product that molecular sieve outer surface produced, and needs molecular sieve outer surface acidity is carried out modulation for this reason.
1. the preliminary treatment of molecular sieve:
In 540 ℃ of calcinations 5 hours, taking-up placed drier to be chilled to room temperature with molecular sieve.
2. the absorption of metal surfactant:
A. dewatering of metal surfactant: Magnesium dilaurate can be dissolved in the benzinum (60-90 ℃) and place designed " a kind of remove the device that anhydrates " (this device is applied for utility model patent simultaneously) of inventor to heat extracting and dewatered 2 hours from oil-water emulsion.
B. the absorption of metal surfactant: the laurate magnesia mixture is made into the petroleum ether solution of concentration 0.078M, and with this solution impregnation HZSM-5 molecular sieve, its dip time is 24 hours, organic solvent is fallen in the suction of can reducing pressure then.
3. absorption post processing:
Absorption back molecular sieve rises to 80 ℃ of bakings 1.5 hours with 1 ℃/minute intensification degree.
4. calcination:
Molecular sieve is risen to 225 ℃ of calcinations 3.0 hours with 0.5 ℃/minute programming rate, be warming up to 540 ℃ of calcinations 5.0 hours then.
The footpath of molecular sieve element distributes modification result: Fig. 1 mutually after the modification in order to record with XPS band argon ion etching, as can be seen from the figure etching only the content of 1 minute element magnesium just to decay to weighing apparatus fixed, this explanation element magnesium only loads on the thickness of about 1 nanometer of molecular sieve outer surface, and reactive activity and selectivity see Table 1.
Embodiment two
Methyl alcohol amination ZSM-5 molecular sieve modified 2
1. the preliminary treatment of molecular sieve:
In 500 ℃ of calcinations 5 hours, taking-up placed drier to be chilled to room temperature with molecular sieve.
2. the absorption of metal surfactant:
A. dewatering of metal surfactant: valeric acid magnesium can be dissolved in benzinum (60-90 ℃) and heat extracting and dewatered 1 hour.
B. the absorption of metal surfactant:
Valeric acid magnesium is made into the petroleum ether solution that concentration is 0.475M, and with this solution impregnation HZSM-5 molecular sieve, its dip time is 24 hours, makes it vapor away solvent naturally.
3. absorption post processing:
After the absorption molecular sieve is risen to 80 ℃ of bakings 1.5 hours with 1 ℃/minute programming rate.
4. calcination:
Molecular sieve is risen to 225 ℃ of calcinations 3.0 hours with 0.5 ℃/minute programming rate, be warming up to 540 ℃ of calcinations 5.0 hours then.
Embodiment three
The modification 3 of methyl alcohol amination ZSM-5 molecular sieve
1. the preliminary treatment of molecular sieve:
In 500 ℃ of calcinations 5 hours, taking-up placed drier to be chilled to room temperature with molecular sieve.
2. the absorption of metal surfactant:
A. dewatering of metal surfactant: laurate copper can be dissolved in benzinum (60-90 ℃) and heat extracting and dewatered 2 hours.
B. the absorption of metal surfactant:
The agent of laurate copper is made into the petroleum ether solution that concentration is 0.11OM, and with this solution impregnation HZSM-5 molecular sieve, its dip time is 24 hours, makes it vapor away solvent naturally.
3. absorption post processing:
After the absorption molecular sieve is raised to 80 ℃ of bakings 1.5 hours with 1 ℃/minute programming rate.
4. calcination:
Molecular sieve is risen to 225 ℃ of calcinations 5.0 hours with 0.5 ℃/minute programming rate, be warming up to 540 ℃ of calcinations 5.0 hours then.
Embodiment four
The modification 1 of normal heptane aromatisation molecular sieve
The aromatization activity center is the acid site but also needs the metal active center that used reactive metal is Zn, 1. the preliminary treatment of molecular sieve:
In 540 ℃ of calcinations 5 hours, taking-up placed drier to be chilled to room temperature with molecular sieve.
2. the absorption of metal surfactant:
A. dewatering of metal surfactant: zinc laurate can be dissolved in the heating extracting of benzinum (60-90 ℃) back and dewater 2 hours.
B. the absorption of metal surfactant:
The zinc laurate agent is made into the petroleum ether solution that concentration is 0.8M, and with this solution impregnation HZSM-5 molecular sieve, its dip time is 24 hours, makes it vapor away solvent naturally.
3. absorption post processing:
After the absorption molecular sieve is raised to 80 ℃ of bakings 2.5 hours with 1 ℃/minute programming rate.
4. calcination:
Molecular sieve is risen to 250 ℃ of calcinations 3 hours with 0.5 ℃/minute programming rate, be warming up to 540 ℃ of calcinations 5.0 hours then.
Embodiment five
The adjusting of metal active center ratio before the normal heptane aromatisation molecular sieve surfaces externally and internally
1. zinc surface activating agent modified HZSM-5 molecular sieve:
2. ion-exchanged
With concentration is that the zinc nitrate of 1.0M floods the molecular sieve after the above modification and is heated to 85 ℃ of insulations 65 hours, filters, and with distilled water washing 2 times, so repeats once.
3. experiment shows, the active activity with exchange molecular sieve once of the molecular sieve that so makes is constant substantially, but aromatic selective significantly improves, if ion-exchange secondary then active significantly decline selectivity also descend.
The comparison of sieve reactivity worth is analyzed in table 1 modified molecular screen and non-modification
The non-modification of the non-modification modification of catalyst modification
Example one example two example three examples, four examples five (1 time) examples five (2 times)
Conversion ratio (%) 96.62 96.28-96.72 100 99.68 96.71 100
Monomethyl amine ten dimethylamine aromatic hydrocarbons
Selectivity (%) 66.32 58.00 67.66 53.12 61.9 64.24 62.90 45.52
Claims (9)
1. one kind is adopted metal surfactant to the method that molecular sieve carries out modification, it is characterized in that carrying out as follows:
(1) preliminary treatment of molecular sieve: in 300-600 ℃ of calcination 1-6 hour, taking-up placed drier to be cooled to room temperature with molecular sieve;
(2) absorption of metal surfactant: be dissolved in metal surfactant in the organic solvent and remove moisture content, then with the above-mentioned pretreated molecular sieve 0.5-24 of this solution impregnation hour;
(3) absorption post processing:, under 0.8-2.0To (To is the boiling point of organic solvent) temperature, dried by the fire 0.5-8 hour then with the molecular sieve filtration after the above-mentioned absorption;
(4) calcination: the molecular sieve after the oven dry rises to 200-400 ℃ of calcination 0.5-3.0 hour with 0.3-10 ℃/minute programming rate, and then is warming up to 400-600 ℃ of calcination 1.04-6.0 hour.
2. the method for claim 1, the absorption that it is characterized in that described metal surfactant can be made into the solution that concentration is 0.001-1.0M with metal surfactant according to needed load capacity, and with this solution impregnation molecular sieve, its dip time 0.5-24 hour, organic solvent is fallen in the suction of can reducing pressure then, and its pressure can be lower than the saturated vapor pressure of organic solvent.
3. method according to claim 1, it is characterized in that the described metal surfactant that is dissolved in organic solvent can be a kind of can also be the multiple metal surfactant that mixes.
4. method according to claim 1, it is characterized in that and to carry out ion-exchange with metal of the same race again through the modified molecular screen after the calcination, make an amount of same metal ion species of its inner surface exchange, thereby make the metal active center of its surfaces externally and internally have suitable ratio.
5. one kind is adopted metal surfactant to the method that molecular sieve carries out modification, it is characterized in that comprising the steps:
(1) internal and external surface of molecular sieve all is exchanged into activated centre with ion-exchange with metal ion;
(2) molecular sieve gives processing: in 300-600 ℃ of calcination 1-6 hour, taking-up placed drier to be cooled to room temperature with molecular sieve;
(3) elimination in outer surface activated centre: α-hydrocarbyl replaces carboxylic acid can be dissolved in organic solvent, making its concentration is 0.1-1.0M, with the above molecular sieve of this solution impregnation, and backflow 0.5-6.0 hour, filter, with identical organic solvent washing molecule, the organic solution with above α-hydrocarbon carboxylic acids repeats above operation, 2-10 time so repeatedly again.
(4) absorption post processing:, under 0.8-2.0T0 (TO is the boiling point of organic solvent) temperature, dried by the fire 0.5-8 hour then with the molecular sieve filtration after the above-mentioned absorption;
(5) calcination: the molecular sieve after the oven dry rises to 200-400 ℃ of calcination 0.5-3.0 hour with 0.3-10 ℃/minute programming rate, and then is warming up to 4000-600 ℃ of calcination 1.0-6.0 hour.
6. method according to claim 5, it is characterized in that the acidic molecular sieve after the calcination is done further modification more in accordance with the method for claim 1 with another kind of metal surface absorbent to be handled, the preparation outer surface has the modified molecular screen that a kind of metal active center inner surface has another kind of activated centre.
7. method according to claim 5, it is characterized in that the step 3 in the said method is changed into the absorption of metal surfactant, adopt the metal surfactant different with ion-exchange, the preparation outer surface has a kind of metal active center, and inner surface has the modified molecular screen at another kind of metal active center.
8. according to the described method of claim 1-7, it is characterized in that described metal surfactant can be the metal carboxylate of non-monovalence, also the method by organic synthesis connects the metal surfactant that an organic chain makes with complexing of metal ion then on metal chelating agent, and its organic chain length should be at four more than the carbon.
9. according to the described method of claim 1-7, it is characterized in that described organic solvent can be benzene, dimethylbenzene, industrial crude benzol, benzinum, also can be industrial solvent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN94117471A CN1048922C (en) | 1994-10-20 | 1994-10-20 | Method of preparing modified molecular sieve with metal surfactant |
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|---|---|---|---|
| CN94117471A CN1048922C (en) | 1994-10-20 | 1994-10-20 | Method of preparing modified molecular sieve with metal surfactant |
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| CN1120977A true CN1120977A (en) | 1996-04-24 |
| CN1048922C CN1048922C (en) | 2000-02-02 |
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| CN94117471A Expired - Fee Related CN1048922C (en) | 1994-10-20 | 1994-10-20 | Method of preparing modified molecular sieve with metal surfactant |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102513144A (en) * | 2011-12-14 | 2012-06-27 | 常州大学 | Preparation method of shape-selective catalyst used for p-dialkyl benzene synthesis process |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| RU1772150C (en) * | 1990-05-21 | 1992-10-30 | Научно-Производственное Объединение "Камень И Силикаты" Армсср | Agent for solid surface clearing |
| CN1046641C (en) * | 1990-12-05 | 1999-11-24 | 中国科学院大连化学物理研究所 | Modified zeolite catalyst for light hydrocardon aromatization reaction |
| CN1023633C (en) * | 1992-10-15 | 1994-02-02 | 大庆石油学院 | Gallium, zinc, platinum modified HZSM-5 catalyst for low-carbon chain hydrocarbon aromatization |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102513144A (en) * | 2011-12-14 | 2012-06-27 | 常州大学 | Preparation method of shape-selective catalyst used for p-dialkyl benzene synthesis process |
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