CN102351210A - Preparation method for synthesizing MCM-22 molecular sieves by using cyclohexane as template agent - Google Patents
Preparation method for synthesizing MCM-22 molecular sieves by using cyclohexane as template agent Download PDFInfo
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- CN102351210A CN102351210A CN2011102001931A CN201110200193A CN102351210A CN 102351210 A CN102351210 A CN 102351210A CN 2011102001931 A CN2011102001931 A CN 2011102001931A CN 201110200193 A CN201110200193 A CN 201110200193A CN 102351210 A CN102351210 A CN 102351210A
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- molecular sieve
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- hexahydroaniline
- sodium metaaluminate
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Abstract
The invention relates to a preparation process of MCM-22 molecular sieves, which uses silica gel and sodium metaaluminate as raw materials and uses cyclohexane as a template agent, the alkalinity is regulated through the sodium metaaluminate, sodium hydroxide or hydrochloric acid, the mixed materials are stirred and aged for 12 to 48h at 50 to 100 DEG C and are stirred and crystallized for 3 to 10 days at 100 to 200 DEG C, and series of MCM-22 molecular sieves with different silica alumina ratios are synthesized. The preparation method has the advantages that the conception is novel, raw materials are easy to obtain, the process operation is safe, and the propylene conversion rate and the isopropyl benzene selectivity of the obtained product are high in propylene and benzene alkylation reaction.
Description
Technical field
The present invention relates to the processing method of MCM-22 molecular sieve, more specifically saying so a kind of is the preparation method of the synthetic MCM-22 molecular sieve of template with the hexahydroaniline.
Background technology
The MCM-22 molecular sieve is the new catalytic material of one type of MWW structure that the nineties Mobile company develops in last century; Have unique ten-ring duct and twelve-ring opening structure; Good hydrothermal stability and special acid site distribute; In multiple catalyzed reaction, show good activity, cause that people pay close attention to greatly.Usually, the raw material of synthetic MCM-22 molecular sieve is a silica gel, sodium metaaluminate; Organic formwork agent is a hexamethylene imine.But the synthesis condition of MCM-22 molecular sieve is relatively harsher, very easily changes brilliant, and hexamethylene imine toxicity is very big, costs an arm and a leg, and has limited the promotion and application of MCM-22 molecular sieve.
Summary of the invention
The purpose of this invention is to provide a kind of is template with the hexahydroaniline, through the consumption control basicity and the silica alumina ratio of adjustment sodium metaaluminate, the processing method of synthetic MCM-22 molecular sieve.It is characterized in that it is is template with the hexahydroaniline, with silica gel, sodium metaaluminate is a raw material, through sodium metaaluminate, and sodium hydroxide or hydrochloric acid allotment basicity, the MCM-22 molecular sieve of synthesizing series Different Silicon aluminum ratio comprises the following steps:
(1) in autoclave, add the water that measures successively, sodium metaaluminate, sheet alkali or hydrochloric acid after stirring under the hexahydroaniline, normal temperature, add silica gel, are stirred to and are uniformly mixed into glue; Wherein available mole proportioning is:
(2) be warming up to 50～100 ℃, stir ageing 12～48 hours;
(3) be warming up to 100～200 ℃, stirred crystallization 3～10 days;
(4) molecular sieve of separating is washed to pH=6～7, and dry under 120 ℃, 500～650 ℃ of roastings obtain the MCM-22 molecular sieve.
The processing method of synthetic MCM-22 molecular sieve of the present invention is characterized in that described template is reagent or industrial goods hexahydroaniline.
The processing method of synthetic MCM-22 molecular sieve of the present invention is characterized in that the consumption may command basicity and the silica alumina ratio of described sodium metaaluminate.
The processing method of synthetic MCM-22 molecular sieve of the present invention is characterized in that the described sodium metaaluminate that passes through, and sodium hydroxide (or hydrochloric acid) is allocated aluminium amount and basicity simultaneously, the silica alumina ratio of control product and synthetic required suitable basicity condition.
The material silica gel that is used for synthetic MCM-22 molecular sieve according to the invention is (with SiO
2Meter), sodium metaaluminate is (with Al
2O
3Meter), hexahydroaniline is template (in RN), and basicity is (with OH
-Meter), the mole proportioning of various materials is:
The present invention is with silica gel, and sodium metaaluminate is a raw material, is template with the hexahydroaniline, and through sodium metaaluminate, sodium hydroxide and hydrochloric acid allotment basicity have the MCM-22 molecular sieve of certain silica alumina ratio with synthetic, and concrete processing step is:
1 water that in autoclave, adds metering successively, sodium metaaluminate, sheet alkali (or hydrochloric acid), hexahydroaniline (being SILVER REAGENT) after stirring under the normal temperature, adds silica gel, continues to be stirred to be uniformly mixed into glue.
2 with after the autoclave sealing, is warming up to 50～100 ℃, stirs ageing 12～48 hours.
3 are warming up to 100～200 ℃, stir crystallization 3～10 days.
4 reduce to discharging behind the normal temperature and pressure with autoclave, and the product molecular sieve is separated from mother liquor.Wash ℃ following drying to pH=6～7,120,500～650 ℃ of following roastings obtain molecular screen primary powder, turning out to be the MCM-22 molecular sieve through X-diffraction (XRD) test.Product MCM-22 molecular sieve XRD spectra as shown in Figure 1.
Adopt the essential characteristics of the synthetic MCM-22 molecular sieve of processing method of the present invention to be:
1 to substitute hexamethylene imine with inexpensive safe hexahydroaniline be template.
2 through sodium metaaluminate, and sodium hydroxide (or hydrochloric acid) is allocated basicity and aluminium amount simultaneously, controls the silica alumina ratio and synthetic required suitable basicity condition of product in the lump.
Description of drawings
Fig. 1 is a MCM-22 molecular sieve XRD spectra.
Embodiment
For simple and purpose clearly, hereinafter appropriate omission the description of known technology, in order to avoid those unnecessary details influences are to the description of present technique scheme.Below in conjunction with preferred embodiment, the present invention is done further description, what illustrate especially is that sodium metaaluminate, hexahydroaniline can have been bought from market.
In 2 liter autoclaves, add 1.5 liters of pure water successively, 54 milliliters of sodium metaaluminates, sodium hydroxide 8 grams, 126 milliliters of hexahydroaniline, normal temperature stirs after 2 hours down, adds silica gel 181 grams, continues to stir 4 hours to being uniformly mixed into glue.With after the autoclave sealing, be warming up to 80 ℃, stir ageing 24 hours, be warming up to 150 ℃ then, stir crystallization and after 7 days autoclave reduced to discharging behind the normal temperature and pressure, the product molecular sieve is separated from mother liquor.Wash to pH=6～7,120 ℃ dry 4 hours down, template are driven away in 500 ℃ of following roastings, activates 6 hours, obtain white molecular screen primary powder, test turning out to be the MCM-22 molecular sieve through X-ray diffraction (XRD).Through chemical analysis, silica alumina ratio is 55, is adsorbate with the normal hexane, and measuring adsorptive capacity with conventional physical adsorption method (BET) is 104g/g.
Embodiment 2
Alkylated reaction with propylene and benzene is the catalytic activity of probe test MCM-22 molecular sieve; Concrete method is: 20 grams of the MCM-22 molecular sieve after the activation among the filling embodiment 1 in fixed-bed reactor; Under 140 ℃; Air speed 1.2h-1; Successive reaction was taken a sample after 100 hours; Use the gas chromatographic analysis reaction product, reaction result is for being: propylene conversion is: 99%, and the selectivity of isopropyl benzene is: 92%.
Embodiment 3
In 2 liter autoclaves, add 1.5 liters of pure water successively, 42 milliliters of sodium metaaluminates, sodium hydroxide 15 grams, stirring added silica gel 181 grams after 2 hours under 126 milliliters of the hexahydroaniline, normal temperature, pressed the synthetic and sign MCM-22 molecular sieve of method of embodiment 1.Turn out to be the MCM-22 molecular sieve through X-ray diffraction (XRD) test.Through analyzing, silica alumina ratio is 75, and adsorptive capacity is 102g/g.Carry out the alkylated reaction of propylene and benzene by the method for embodiment 2, reaction result is for being: propylene conversion is: 99.8%, and the selectivity of isopropyl benzene is: 93%.
Embodiment 4
In 2 liter autoclaves, add 1.5 liters of pure water successively, 68 milliliters of sodium metaaluminates, sodium hydroxide 5 grams, stirring added silica gel 181 grams after 2 hours under 126 milliliters of the hexahydroaniline, normal temperature, pressed the synthetic and sign MCM-22 molecular sieve of method of embodiment 1.Turn out to be the MCM-22 molecular sieve through X-ray diffraction (XRD) test.Through analyzing, silica alumina ratio is 45, and adsorptive capacity is 98g/g.Carry out the alkylated reaction of propylene and benzene by the method for embodiment 2, reaction result is for being: propylene conversion is: 99%, and the selectivity of isopropyl benzene is: 92.5%.
Embodiment 5
In 2 liter autoclaves, add 1.5 liters of pure water successively, 85 milliliters of sodium metaaluminates, 98 milliliters of hydrochloric acid, 126 milliliters of hexahydroaniline, normal temperature stirring down added silica gel 181 grams after 2 hours, pressed the method for embodiment 1 and synthesized the molecular sieve with sign MCM-22.Turn out to be the MCM-22 molecular sieve through X-ray diffraction (XRD) test.Through analyzing, silica alumina ratio is 35, and adsorptive capacity is 116g/g.Carry out the alkylated reaction of propylene and benzene by the method for embodiment 2, reaction result is for being: propylene conversion is: 99.8%, and the selectivity of isopropyl benzene is: 94%.
Embodiment 6
Adopt the industrial goods hexahydroaniline, press the synthetic and sign MCM-22 molecular sieve of method of embodiment 1.Turn out to be the MCM-22 molecular sieve through X-ray diffraction (XRD) test.Through analyzing, silica alumina ratio is 55, and adsorptive capacity is 104g/g.Carry out the alkylated reaction of propylene and benzene by the method for embodiment 2, use the gas chromatographic analysis reaction product, reaction result is for being: propylene conversion is: 99%, and the selectivity of isopropyl benzene is: 92%.
Embodiment 7
In 200 liter autoclaves, add 150 liters of pure water successively, 5.4 liters of sodium metaaluminates, 0.8 kilogram in sodium hydroxide, 12.6 liters of industrial goods hexahydroaniline are pressed the method for embodiment 1 and are synthesized the molecular sieve with sign MCM-22.Turn out to be the MCM-22 molecular sieve through X-ray diffraction (XRD) test.Through analyzing, silica alumina ratio is 55, and adsorptive capacity is 102g/g.Carry out the alkylated reaction of propylene and benzene by the method for embodiment 2, reaction result is for being: propylene conversion is: 98%, and the selectivity of isopropyl benzene is: 91.5%.
Embodiment 8
For outstanding characteristic of the present invention, the present invention and the preparation process and the result thereof of conventional synthetic MCM-22 molecular sieve are compared.
1. conventional synthetic MCM-22 molecular sieve
In 2 liter autoclaves, add 1.5 liters of pure water successively, 35 milliliters of sodium metaaluminates, sodium hydroxide 8 grams; 120 milliliters of hexamethylene imines; Normal temperature stirred down after 0.5 hour, add silica gel 139 grams, and the MCM-22 molecular sieve that adding is equivalent to gel quality affects 0.2% was as crystal seed.With after the autoclave sealing, continue to be stirred to and be uniformly mixed into glue.Be warming up to 150 ℃ then, stir crystallization and after 7 days autoclave reduced to discharging behind the normal temperature and pressure, the product molecular sieve is separated from mother liquor.Wash to pH=6～7,120 ℃ dry 4 hours down, template are driven away in 500 ℃ of following roastings, activates 6 hours, obtain white molecular screen primary powder, test turning out to be the MCM-22 molecular sieve through X-ray diffraction (XRD).Through chemical analysis, silica alumina ratio is 30, is adsorbate with the normal hexane, and measuring adsorptive capacity with conventional physical adsorption method (BET) is 109g/g.Carry out the alkylated reaction of propylene and benzene by the method for embodiment 2, reaction result is for being: propylene conversion is: 99.2%, and the selectivity of isopropyl benzene is: 92%.
2. the present invention synthesizes the MCM-22 molecular sieve of Different Silicon aluminum ratio
(1) in 2 liter autoclaves, add 1.5 liters of pure water successively, 85 milliliters of sodium metaaluminates, 98 milliliters of hydrochloric acid, 126 milliliters of hexahydroaniline, normal temperature stirred down after 2 hours, added silica gel 181 grams, continued to stir 4 hours to being uniformly mixed into glue.With after the autoclave sealing, be warming up to 80 ℃, stir ageing 24 hours, be warming up to 150 ℃ then, stir crystallization and after 7 days autoclave reduced to discharging behind the normal temperature and pressure, the product molecular sieve is separated from mother liquor.Wash to pH=6～7,120 ℃ dry 4 hours down, template are driven away in 500 ℃ of following roastings, activate 6 hours, obtain white molecular screen primary powder.Turn out to be the MCM-22 molecular sieve through X-ray diffraction (XRD) test.Through analyzing, silica alumina ratio is 35, and adsorptive capacity is 116g/g.Carry out the alkylated reaction of propylene and benzene by the method for embodiment 2, reaction result is for being: propylene conversion is: 99.8%, and the selectivity of isopropyl benzene is: 94%.
(2) in 2 liter autoclaves, add 1.5 liters of pure water successively, 68 milliliters of sodium metaaluminates, sodium hydroxide 5 grams, stirring added silica gel 181 grams after 2 hours under 126 milliliters of the hexahydroaniline, normal temperature, pressed the synthetic and sign MCM-22 molecular sieve of method of the foregoing description.Turn out to be the MCM-22 molecular sieve through X-ray diffraction (XRD) test.Through analyzing, silica alumina ratio is 45, and adsorptive capacity is 98g/g.Carry out the alkylated reaction of propylene and benzene by the method for embodiment 2, reaction result is for being: propylene conversion is: 99%, and the selectivity of isopropyl benzene is: 92.5%.
Claims (5)
1. the preparation method of a synthetic MCM-22 molecular sieve is characterized in that it is is template with the hexahydroaniline, with silica gel; Sodium metaaluminate is a raw material, through sodium metaaluminate, and sodium hydroxide or hydrochloric acid allotment basicity; The MCM-22 molecular sieve of synthesizing series Different Silicon aluminum ratio comprises the following steps:
(1) in autoclave, add the water that measures successively, sodium metaaluminate, sodium hydroxide or hydrochloric acid after stirring under the hexahydroaniline, normal temperature, add silica gel, are stirred to and are uniformly mixed into glue;
(2) be warming up to 50～100 ℃, stir ageing 12～48 hours;
(3) be warming up to 100～200 ℃, stirred crystallization 3～10 days;
(4) molecular sieve of separating is washed to pH=6～7, and dry under 120 ℃, 500～650 ℃ of roastings obtain the MCM-22 molecular sieve; Wherein available mole proportioning is:
2. the preparation method of the described synthetic MCM-22 molecular sieve of claim 1 is characterized in that described template is reagent or industrial goods hexahydroaniline.
3. the preparation method of the described synthetic MCM-22 molecular sieve of claim 1 is characterized in that the consumption may command basicity and the silica alumina ratio of described sodium metaaluminate.
4. the preparation method of the described synthetic MCM-22 molecular sieve of claim 1 is characterized in that the described sodium metaaluminate that passes through, and sodium hydroxide or hydrochloric acid are allocated aluminium amount and basicity simultaneously, the silica alumina ratio of control product and synthetic required suitable basicity condition.
5. the preparation method of the described synthetic MCM-22 molecular sieve of claim 1 is characterized in that the mole proportioning of described each material is:
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106536411A (en) * | 2014-06-06 | 2017-03-22 | 巴斯夫欧洲公司 | Synthesis of a boron-containing zeolite with an MWW framework structure |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1789126A (en) * | 2004-12-17 | 2006-06-21 | 中国科学院大连化学物理研究所 | Synthetic method for MCM-22 molecular sieve |
| CN101489677A (en) * | 2006-07-28 | 2009-07-22 | 埃克森美孚化学专利公司 | A mcm-22 family molecular sieve composition, its method of making, and use for hydrocarbon conversions |
| US20100317895A1 (en) * | 2008-02-12 | 2010-12-16 | Buchanan John S | Process For Producing Cyclohexylbenzene |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1789126A (en) * | 2004-12-17 | 2006-06-21 | 中国科学院大连化学物理研究所 | Synthetic method for MCM-22 molecular sieve |
| CN101489677A (en) * | 2006-07-28 | 2009-07-22 | 埃克森美孚化学专利公司 | A mcm-22 family molecular sieve composition, its method of making, and use for hydrocarbon conversions |
| US20100317895A1 (en) * | 2008-02-12 | 2010-12-16 | Buchanan John S | Process For Producing Cyclohexylbenzene |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106536411A (en) * | 2014-06-06 | 2017-03-22 | 巴斯夫欧洲公司 | Synthesis of a boron-containing zeolite with an MWW framework structure |
| JP2017518255A (en) * | 2014-06-06 | 2017-07-06 | ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ | Synthesis of boron-containing zeolite with MWW framework structure |
| US10196276B2 (en) | 2014-06-06 | 2019-02-05 | Basf Se | Synthesis of a boron-containing zeolite with an MWW framework structure |
| CN106536411B (en) * | 2014-06-06 | 2020-05-12 | 巴斯夫欧洲公司 | Synthesis of boron-containing zeolites having MWW framework Structure |
| US10793443B2 (en) | 2014-06-06 | 2020-10-06 | Basf Se | Synthesis of a boron-containing zeolite with an MWW framework structure |
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Application publication date: 20120215 |