CN102341349A - Process for the preparation of layered silicates - Google Patents
Process for the preparation of layered silicates Download PDFInfo
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- CN102341349A CN102341349A CN2010800103703A CN201080010370A CN102341349A CN 102341349 A CN102341349 A CN 102341349A CN 2010800103703 A CN2010800103703 A CN 2010800103703A CN 201080010370 A CN201080010370 A CN 201080010370A CN 102341349 A CN102341349 A CN 102341349A
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Abstract
A process for the preparation of a layered silicate containing at least silicon and oxygen is provided. The process comprises (1) providing a mixture containing silica and/or at least one silica precursor, water, at least one tetraalkylammonium compound selected from the group consisting of a diethyldimethylammonium compound, a triethylmethylammonium compound, and a mixture of a diethyldimethylammonium compound and a triethylmethylammonium compound, and at least one base, and optionally at least one suitable seeding material; and (2) heating of the mixture obtained according to (1) under autogenous pressure (hydrothermal conditions) to a temperature in the range of from 120 to 160 DEG C for a period in the range of from 5 to 10 days to give a suspension containing the layered silicate.
Description
The present invention relates to contain the preparation method of the layered silicate of silicon and oxygen at least, it comprises
(1) provides and contain silicon-dioxide and/or at least a silica precursor; Water, at least a tetraalkyl ammonium compound and at least a alkali, and the mixture of optional at least a suitable seed crystal material; Said tetraalkyl ammonium compound is selected from the group of following composition; The diethyl-dimethyl ammonium compound, the mixture of triethyl ammonium methyl compound and diethyl-dimethyl ammonium and triethyl ammonium methyl compound;
(2) will under autogenous pressure (hydrothermal condition), be heated to 120 ℃ to 160 ℃ according to the mixture that (1) obtains, reach 5 to 10 days, obtain containing the suspension-s of this layered silicate.
Further, the present invention relates to obtain or obtainable layered silicate, and relate to specific silicate with novel texture through method of the present invention.Simultaneously, the present invention relates to can be from the tectosilicate (tectosilicate) of this layered silicate preparation.In addition, the present invention relates to the specific end use of this layered silicate and/or this tectosilicate.
In the art, know layered silicate.For example, such as at J.Song, H.Gies; Studies in Surface Science and Catalysis, the 15th volume, those disclosed material can be mentioned in 2004, the 295-300 pages or leaves.
In various technical fields, such as, for example, catalysis or absorption all have continuous needs, the especially silicate of pair type material respectively and allow to make the needs of the novel process of the custom materials that is used to solve specific catalysis or absorption problem.
Therefore, an object of the present invention is to provide the new process of preparation layered silicate, it can be used for, and for example, above-mentioned field perhaps is used as precursor in the tectosilicate preparation.Another purpose of the present invention provides new stratified material.Further, can expect, can be used as the starting raw material that columnar silicon hydrochlorate (pillard silicate) prepares from material or this new stratified material that this novel process obtains.
Therefore, the present invention relates to contain the preparation method of the layered silicate of silicon and oxygen at least, it comprises
(1) provides and contain silicon-dioxide and/or at least a silica precursor; Water, at least a tetra-allkylammonium based compound and at least a alkali, and the mixture of optional at least a suitable seed crystal material; Said tetra-allkylammonium based compound is selected from the group of following composition; The diethyl-dimethyl ammonium compound, the mixture of triethyl ammonium methyl based compound and diethyl-dimethyl ammonium and triethyl ammonium methyl based compound;
(2) will under autogenous pressure (hydrothermal condition), be heated to 120 ℃ to 160 ℃ according to the mixture that (1) obtains, reach 5 to 10 days, obtain containing the suspension-s of this layered silicate.
According to the present invention, except that at least a tetraalkyl ammonium compound, also can use a kind of alkali that is different from this compound.The instance of these alkali is volatile caustic NH
4OH, alkali metal hydroxide or alkaline earth metal hydroxides, such as sodium hydroxide or Pottasium Hydroxide, perhaps two of these compounds kinds or more kinds of mixtures.In this case, at least a tetraalkyl ammonium compound contains one or more suitable negatively charged ion, and halide anion for example is such as fluorion or cl ions or bromide anion or iodide ion.
Preferably, this at least a tetraalkyl ammonium compound contains with good grounds (1) as anionic alkali.Basic anion instance in this article comprises, especially, and hydroxide ion or aluminate ion.Preferred especially basic anion is a hydroxide ion.
Therefore, the mixture that in (1), provides preferably contains diethyl-dimethyl-volatile caustic, triethyl ammonium hydroxide, the perhaps mixture of diethyl-dimethyl ammonium hydroxide and triethyl ammonium hydroxide.
Especially preferably, the mixture that in (1), provides only contains a kind of tetraalkyl ammonium compound, more preferably is a kind of tetra-alkyl ammonium hydroxide, especially diethyl-dimethyl ammonium hydroxide.
Because this preferred embodiment, simultaneously preferably, to go up basically not contain according to the mixture of (1) and be different from common negatively charged ion hydroxy, said common negatively charged ion is usually as the gegenion of tetraalkyl ammonium ion.Preferably, go up basically according to the mixture of (1) and not contain halide-ions, such as bromide anion or fluorion.In this article, term " is substantially devoid of " and generally refers to, and the said anionic content separately in said mixture is no more than 500ppm.
Any suitable compound all can be used as silicon-dioxide or silica precursor in principle.The term " silica precursor " that uses in this article refers to, a kind of compound, and it allows to form the silicate sturcture of layered silicate under selected reaction conditions.Tetraalkoxysilane, such as tetramethoxy-silicane, tetraethoxy-silicane or tetrapropoxysilane can be used as the mode of instance, are mentioned as precursor compound.In process method of the present invention, said silicon-dioxide is preferred especially the use.For example, this type of silicon-dioxide source can be pyrogene (fumed), soft silica, and silicon dioxide gel is such as ludox or the like.Mixture or at least a silicon-dioxide source that can be contemplated that mixture or two kinds or more kinds of silica precursors in two kinds or more kinds of silicon-dioxide source also can be used with the mixture of silica precursor at least.Especially preferred soft silica.Further, preferred soft silica is as unique silica source.
Therefore, the invention still further relates to aforesaid method,, use soft silica wherein according to (1).
In principle, can use any suitable soft silica.What preferably use is to have 10-400m
2The soft silica of the specific surface area of/g (BET, Brunauer-Emmet-Teller are detected at 77K by nitrogen adsorption method according to DIN 66131), preferred 10-100m
2/ g, preferred especially 10-50m
2/ g.Other preferred range is 50-100m
2/ g or 100-300m
2/ g or 300-400m
2/ g.
In the basis mixture of (1), silicon-dioxide and/or silica precursor, the molar ratio of tetraalkyl ammonium compound and water, said silicon-dioxide and/or silica precursor are with SiO
2Calculate, can select according to the layered silicate that will obtain.The specific hydrothermal condition according to (2) is found on amazing ground, and promptly Tc is 120 to 160 ℃, and the crystallization phase has allowed the preparation of novel material when being 5 to 10 days, and this depends on the molar ratio of said material.In addition, except that molar ratio, change the novel material that the crystallization phase can obtain to have these parameter particular combination if find.Therefore believe the flexible theory that the many novel materials that allow the unknown of synthetic this area is provided in 120-160 ℃ Tc and the parameters combination of 5-10 days crystallization phase.
With regard to this Tc, TR is 125 to 155 ℃, more preferably from 130 to 150 ℃, and more preferably from 135 to 145 ℃.Especially, TR is 138 to 142 ℃.
Other conceivable TR is, for example, and 120 to 130 ℃ or 130 to 140 ℃ or 140 to 150 ℃ or 150 to 160 ℃.According to the present invention, during the crystallization of (2), also can use two kinds or more kinds of different temperature.In this article, can attemperation certain value in the above-mentioned scope, keep this temperature certain hour, increase then or reduce the temperature to another value in the above-mentioned scope.Temperature regulation is opposite or be that during hydrothermal crystallization, Tc can little by little reduce or improve as what replenish step by step with this.Generally speaking, the heating rate that applies arrives Tc and/or at (2) heats mixture, all can carry out appropriate selection according to (1) heated mixt no matter be.Preferably, heating rate is 0.1 ℃/minute to 20 ℃/minute, preferably from 0.3 ℃/minute to 15 ℃/minute, especially from 0.5 ℃/minute to 10 ℃/minute.
With regard to above-mentioned silicon-dioxide and/or its precursor, the molar ratio of tetraalkyl ammonium compound and water, its scope is preferably 1: (0.3-0.7): (9-15), more preferably 1: (0.4-0.6): (9-15), and more preferably 1: (0.45-0.55): (9-15).Especially preferred is silicon-dioxide or its precursor: the molar ratio of tetraalkyl ammonium compound is 1: (0.48-0.52), and especially 1: (0.49-0.51).
Therefore, the present invention relates to a kind of aforesaid method, the mixture that wherein obtains according to (1) contains with SiO
2The SiO of meter
2And/or its silica precursor, at least a tetraalkyl ammonium compound and water, its molar ratio is SiO
2: tetraalkyl ammonium compound: water is 1: (0.3-0.7): (9-15), and preferred 1: (0.4-0.6): (9-15), more preferably 1: (0.45-0.55): (9-15).
Therefore, in step (1), the mixture that carries out hydrothermal crystallization in step (2) is provided.Generally speaking, possible is with each order that can imagine, single starting raw material to be mixed.Preferably, silicon-dioxide or its precursor mix with the aqueous mixture that contains tetraalkyl ammonium compound.After these structure directing reagent (structure directing agent) were added, the preferred mixture that obtains that stirs preferably carried out 0.1 to 10 hour, and more preferably from 0.5 to 5 hour, and more preferably 1 to 2 hour.In process according to (1) preparation colloidal solution, preferably 10 to 40 ℃ of temperature, more preferably 15 to 35 ℃, preferred especially 20 to 30 ℃.
Depend on the starting raw material molar ratio of desireing, possiblely be, suitably remove or add suitable quantity of water.For example, use rotatory evaporator or heated mixt carefully, all can realize the removal of water.Water is removed, and preferably under 60 to 85 ℃ of temperature, carries out, more preferably at 65 to 80 ℃, particularly preferably in 65 to 75 ℃.If water is added into or removes, preferably, the mixture that obtains stirred 0.1 to 5 hour, preferred 0.5 to 2 hour.
According to another embodiment of the present invention, contain at least one provenance of at least a element in addition according to the mixture of (1), said element is adapted at carrying out in the layered silicate that the hydrothermal crystallization according to (2) obtains the isomorphous substitution of at least a portion Si atom.Preferred suitable element is selected from the group of following composition, Al, B, Fe, Ti, Sn, Ga, Ge, Zr, V, Nb and their two kinds or multiple mixture.Because the existence of at least one provenance of at least a suitable element, the silicate sturcture that in the hydrothermal crystallization process, forms not only contains the Si atom, also contains at least a suitable element as the isomorphous substitution of Si atom.
For example, if introduced aluminium, possiblely be; Except tetraalkyl ammonium compound and silicon-dioxide and/or silica precursor, for example metallic aluminium or suitable aluminate have also been used, such as alkali metal aluminate as starting raw material; And aluminum alcoholate, such as aluminum isopropylate.For example,, possiblely be, except tetraalkyl ammonium compound and silicon-dioxide and/or silica precursor, also used that for example free boric acid and/or borate and/or boric acid ester are such as triethyl borate as starting raw material if introduced boron.For example,, possiblely be, except tetraalkyl ammonium compound and silicon-dioxide and/or silica precursor, also used that titanium alcoholate for example is such as titanium ethanolate or titanium propanolate as starting raw material if introduced titanium.For example, if introduced tin, possiblely be; Except tetraalkyl ammonium compound and silicon-dioxide and/or silica precursor, also used, for example tin chloride and/or organo-metallic tin compound as starting raw material; Such as tin spirit alcoholate or inner complex, such as acetopyruvic acid tin.For example, if introduced zirconium, possible is except tetraalkyl ammonium compound and silicon-dioxide and/or silica precursor as starting raw material, also to have used, for example zirconium chloride and/or zirconium alcoholate.For example, if introduced vanadium or germanium or niobium, possible is except tetraalkyl ammonium compound and silicon-dioxide and/or silica precursor as starting raw material, also to have used, for example vanadium chloride or germanium chloride or niobium chloride.
According to another embodiment of the present invention, can add at least a seed crystal material and be used as crystallization auxiliary to mixture according to (1).The compound that can imagine the stratified material that all can causing wanted is used as seed crystal material.For synthesizing of given layered silicate; Preferably; Add layered silicate and/or tectosilicate, be used as seed crystal material, layered silicate and/or tectosilicate are from through obtaining the layered silicate that hereinafter described method obtains.Especially preferred is as seed crystal material, to add layered silicate.The typical concentration of seed crystal material is the seed crystal material of 0.1 to 5 weight %, and silicon-dioxide that exists in the mixture based on (1) or silica precursor calculate with silicon-dioxide.
The mixture that obtains carries out hydrothermal crystallization then in step (2).Preferably, mixture is transferred in the autoclave.In order Tc to be adjusted to the temperature that one or more is wanted, the further preferred autoclave that is equipped with heating and/or cooling way that uses, such as, for example, inner or indirect heating and/or cooling way, such as, for example, heating and/or cooling jacket.Simultaneously possiblely be, shift autoclave in a certain environment, such as baking oven, for example circulated air oven perhaps similarly allows synthetic mixture to keep wanting the place of temperature.
For the crystallization according to (2), synthetic mixture preferably carries out suitable stirring.Simultaneously possible is to change and carry out the crystalline reaction vessel.
According to the of the present invention first special preferred embodiment, the mixture that obtains according to (1) contains SiO
2And/or with SiO
2The silica precursor of meter, at least a tetraalkyl ammonium compound and water, its molar ratio is SiO
2: tetraalkyl ammonium compound: water is 1: (0.45-0.55): (9.5-10.5), and more preferably 1: (0.47-0.53): (9.7-10.3), more preferably 1: (0.49-0.51): (9.9-10.1).
Therefore, the invention still further relates to aforesaid method, the mixture that wherein obtains according to (1) contains SiO
2, perhaps with SiO
2The silica precursor of meter, at least a tetraalkyl ammonium compound and water, its molar ratio is SiO
2: tetraalkyl ammonium compound: water is 1: (0.45-0.55): (9.5-10.5).In addition, the present invention relates to silicate obtainable through said method or that obtain.
For the first special preferred embodiment, further preferably, the mixture of heating steps (2) reaches 8.5 to 9.5 days, and more preferably 8.5 to 9.0 days, even more preferably from 8.6 to 8.8 days.
From these specific processing condition, layered silicate preferably can obtain or obtain, and it has the X-ray diffractogram that comprises following at least reflection:
| |
Intensity (%) |
| (6.09-6.29) | (80.0-100.0) |
| (7.90-8.10) | (80.0-100.0) |
| (20.30-20.50) | (11.1-17.1) |
| (23.95-24.15) | (11.9-19.9) |
| (24.81-25.01) | (16.2-26.2) |
| (25.34-25.54) | (17.3-25.3) |
| (26.56-26.76) | (10.4-16.4) |
Wherein, 100% is relevant with the intensity at the peak of maximum in X-ray diffractogram.
In addition, the invention still further relates to a kind of layered silicate, it has the X-ray diffractogram that contains following at least reflection:
| |
Intensity (%) |
| (6.09-6.29) | (80.0-100.0) |
| (7.90-8.10) | (80.0-100.0) |
| (20.30-20.50) | (11.1-17.1) |
| (23.95-24.15) | (11.9-19.9) |
| (24.81-25.01) | (16.2-26.2) |
| (25.34-25.54) | (17.3-25.3) |
| (26.56-26.76) | (10.4-16.4) |
Wherein, 100% is relevant with the intensity at the peak of maximum in X-ray diffractogram.
For the first special preferred embodiment, further preferably, the mixture of heating steps (2) reaches 5.5 to 6.5 days, and more preferably 5.7 to 6.3 days, even more preferably from 5.9 to 6.1 days.
From these specific processing condition, layered silicate preferably can obtain or obtain, and it has the X-ray diffractogram that comprises following at least reflection:
| |
Intensity (%) |
| (5.65-5.85) | 100 |
| (18.79-18.99) | (14.10-22.10) |
| (20.62-20.82) | (14.70-22.70) |
| (22.06-22.26) | (14.30-22.30) |
| (22.95-23.15) | (17.80-27.80) |
| (23.37-23.57) | (15.10-23.10) |
| (25.93-26.13) | (15.20-25.20) |
| (31.08-31.28) | (14.30-22.30) |
Wherein, 100% is relevant with the intensity at the peak of maximum in X-ray diffractogram.
In addition, the invention still further relates to a kind of layered silicate, it has the X-ray diffractogram that contains following at least reflection:
| |
Intensity (%) |
| (5.65-5.85) | 100 |
| (18.79-18.99) | (14.10-22.10) |
| (20.62-20.82) | (14.70-22.70) |
| (22.06-22.26) | (14.30-22.30) |
| (22.95-23.15) | (17.80-27.80) |
| (23.37-23.57) | (15.10-23.10) |
| (25.93-26.13) | (15.20-25.20) |
| (31.08-31.28) | (14.30-22.30) |
Wherein, 100% is relevant with the intensity at the peak of maximum in X-ray diffractogram.
For the first special preferred embodiment, in addition preferably, the mixture of heating steps (2) reaches 6.7 to 7.5 days, and more preferably 6.8 to 7.3 days, even more preferably from 6.9 to 7.1 days.
Therefore, the invention still further relates to the layered silicate that can obtain or obtain through method of the present invention, the mixture that wherein obtains according to (1) contains SiO
2And/or with SiO
2The silica precursor of meter, at least a tetraalkyl ammonium compound and water, its molar ratio is SiO
2: tetraalkyl ammonium compound: water is 1: (0.45-0.55): (9.5-10.5), and wherein mixture heated 6.7 to 7.5 days according to step (2), and preferred 6.8 to 7.3 days, even more preferably 6.9 to 7.1 days.Preferably; This layered silicate obtains or can obtain through following method; The aqueous solution that wherein uses according to (1) contains diethyl-dimethyl ammonium hydroxide, triethyl ammonium hydroxide, the perhaps mixture of diethyl-dimethyl ammonium hydroxide and triethyl ammonium hydroxide; More preferably, said solution contains diethyl-dimethyl-volatile caustic.In particularly preferred embodiments, according to (2) heated mixt to 130 to 150 ℃, preferred 135 to 145 ℃.Most preferably; This layered silicate obtains or can obtain from the mixture according to (1); Said mixture is a soft silica; The mixture of diethyl-dimethyl ammonium hydroxide and water, its molar ratio are 1: (0.49-0.51): (9.9-10.1), according to (2) it was heated 164 to 172 hours down at 139 to 141 ℃.
According to the of the present invention second special preferred embodiment, the mixture that obtains according to (1) contains SiO
2And/or with SiO
2The silica precursor of meter, at least a tetraalkyl ammonium compound and water, its molar ratio is SiO
2: tetraalkyl ammonium compound: water is 1: (0.45-0.55): (12.0-13.0), and more preferably 1: (0.47-0.53): (12.3-12.9), more preferably 1: (0.49-0.51): (12.5-12.7).
Therefore, the invention still further relates to aforesaid method, the mixture that wherein obtains according to (1) contains SiO
2And/or with SiO
2The silica precursor of meter, at least a tetraalkyl ammonium compound and water, its molar ratio is SiO
2: tetraalkyl ammonium compound: water is 1: (0.45-0.55): (12.0-13.0).In addition, the present invention relates to silicate obtainable through said method or that obtain.
For the second special preferred embodiment, further preferably, the mixture of heating steps (2) reaches 7.5 to 8.5 days, and more preferably 7.7 to 8.3 days, even more preferably from 7.9 to 8.1 days.
From these specific processing condition, layered silicate preferably can obtain or obtain, and it has the X-ray diffractogram that comprises following at least reflection:
| |
Intensity (%) |
| (6.02-6.22) | 100 |
| (18.80-19.00) | (7.0-11.0) |
| (19.47-19.67) | (6.0-10.0) |
| (22.74-22.94) | (10.4-16.4) |
| (23.74-23.94) | (7.2-11.2) |
| (26.45-26.65) | (6.3-10.3) |
| (31.05-31.25) | (8.7-14.7) |
Wherein, 100% is relevant with the intensity at the peak of maximum in X-ray diffractogram.
In addition, the invention still further relates to a kind of layered silicate, it has the X-ray diffractogram that contains following at least reflection:
| |
Intensity (%) |
| (6.02-6.22) | 100 |
| (18.80-19.00) | (7.0-11.0) |
| (19.47-19.67) | (6.0-10.0) |
| (22.74-22.94) | (10.4-16.4) |
| (23.74-23.94) | (7.2-11.2) |
| (26.45-26.65) | (6.3-10.3) |
| (31.05-31.25) | (8.7-14.7) |
Wherein, 100% is relevant with the intensity at the peak of maximum in X-ray diffractogram.
According to the preferred embodiment of the inventive method, the layered silicate that in its mother liquor, comprises, separates in the suspension-s that from (2), obtains at least one step through suitable method.This separation can be passed through, for example, filters, and ultrafiltration, the means of diafiltration (diafiltration) or centrifuging are carried out, and perhaps pass through, and for example, spraying drying and mist projection granulating method are carried out.Preferably separate through spraying drying or filtering means.
Therefore, the invention still further relates to aforesaid method, it comprises in addition
(3) from the suspension-s that obtains according to (2), separate this silicate.
According to an embodiment of the inventive method, can stop through suitable quenching according to the crystallization of (2).Here, particularly preferably be, add entry in suspension-s, the temperature of said water is in and is suitable for stopping the crystalline temperature.
According to the preferred embodiment of the inventive method, carry out as stated that isolating at least a silicate is washed and/or dry.
Therefore, the invention still further relates to aforesaid method, it comprises in addition
(4) washing
And/or
(5) drying
According to the silicate that obtains according to (3).
After separating; Can then carry out at least one washing step and/or at least one drying step; Wherein possiblely be; In at least two washing lotion steps, use identical or different washing composition or detergent mixture, and at least two drying step, use identical or different drying temperature.
If carried out at least one washing step, preferably, the silicate that separated of washing is 6 to 8 up to the pH of washing water, and is preferred 6.5 to 7.5, and it is measured through the normal glass electrode.
The drying temperature here is room temperature to 180 ℃ preferably, and more preferably 75 ℃ to 170 ℃, more preferably 90 ℃ to 160 ℃, preferred especially 100 ℃ to 150 ℃.
Therefore, the invention still further relates to aforesaid method, it comprises in addition
(3) from the suspension-s that obtains according to (2), separate this silicate.And further comprise
(4) washing is 6.5 to 7.5 to the pH of the silicate that separated, and
(5) will separate and silicate that optionally washing is crossed carries out drying in 100 to 150 ℃ scope.
Spendable washing composition is, for example, water, alcohol, such as methyl alcohol, ethanol or propyl alcohol, perhaps their two kinds or more kinds of mixtures.The instance of mixture is the mixture of two kinds or more kinds of alcohol; Such as methyl alcohol and ethanol or methyl alcohol and propyl alcohol or ethanol and propyl alcohol or methyl alcohol and ethanol and propyl alcohol; The perhaps mixture of water and at least a alcohol is such as water and methyl alcohol or water and ethanol or water and propyl alcohol or water and methyl alcohol and ethanol or water and methyl alcohol and propyl alcohol or water and ethanol and propyl alcohol or water and methyl alcohol and ethanol and propyl alcohol.The mixture of preferably water or water and at least a alcohol, preferably water and ethanol, water particularly preferably can be used as unique washing composition.
According to the method for the invention, obtained a kind of silicate, especially layered silicate, the wherein optional isomorphous substitution of at least a portion Si atom of this silicate sturcture quilt.Therefore the present invention also relates to that obtain or obtainable a kind of silicate, especially layered silicate through aforesaid method, randomly, and a kind of layered silicate of isomorphous substitution.
According to another embodiment; The invention still further relates to aforesaid method; It comprises that in addition the silicate with optionally washing and/or dry mistake to separating carries out suitable aftertreatment, carries out isomorphous substitution with at least a portion Si atom in the burnt silicate with at least a suitable element thus.Preferred suitable element is selected from the group of following composition, Al, B, Fe, Ti, Sn, Ga, Ge, Zr, V, Nb and their two kinds or multiple mixture.No matter whether layered silicate is the layered silicate crossed of isomorphous substitution, this type of aftertreatment of layered silicate all can be carried out.
According to the another embodiment of the inventive method, the layered silicate that obtains according to (2) is calcined according to (6) at least one additional step.In principle, possiblely be, include the suspension-s of layered silicate, promptly contain the mother liquor of layered silicate, directly calcined.Preferably, this silicate separated from suspension-s before calcining, according to aforesaid (3).Before calcining, isolating silicate can carry out at least one aforesaid washing step (4) and/or at least one aforesaid drying step (5) from suspension-s.
The calcining that the basis (6) of the silicate that obtains according to (2) and/or (3) and/or (4) and/or (5) is carried out preferably carrying out under 700 ℃ at the most, obtains tectosilicate.More preferably, calcining temperature is 300 to 700 ℃, more preferably from 300 to 600 ℃.
Therefore; According to the preferred embodiment of the inventive method, the heating of this layered silicate is carried out under maximum 700 ℃ temperature in room temperature, and heating rate further is preferably 0.1 to 12 ℃/hour; More preferably from 1 to 11 ℃/hour, preferred especially 5 to 10 ℃/hour.
According to one of the inventive method possible embodiment, this calcining is carried out under the temperature of order step by step.In the present invention; Term " under the temperature of order step by step " refers to a calcination process; Wherein to be heated to a specified temp by incinerating silicate; Under this temperature, keep specified time, and be heated at least one other temperature, and keep this temperature to reach a specified time once more from this specified temp.If carried out calcining step by step, preferably reached 4 by incinerating silicate, more preferably reach 3, keep under preferred especially 2 temperature.
This calcining can be carried out in any suitable atmosphere, air for example, poor air (lean air), nitrogen, steam, synthetic gas or carbonic acid gas.Calcining is preferably carried out in air.
Calcining can be carried out in any device that is applicable to this purpose.This is calcined preferably at swivel pipe, banded calcining furnace, and retort furnace perhaps will be used for its device original position of hoping purposes subsequently at silicate and carry out, the Another Application occasion that for example perhaps is used to be described below as molecular sieve.Here preferred especially swivel pipe and banded calcining furnace.
According to the method for the invention, obtain a kind of silicate, especially tectosilicate.
Therefore, the invention still further relates to aforesaid method, it comprises in addition
(6) will calcine according to the silicate that (2) or (3) or (4) or (5) obtain, calcining is preferably carried out more preferably 300 to 600 ℃ under 300 to 700 ℃.
After calcining; According to another embodiment; The invention still further relates to aforesaid method, it comprises in addition burnt silicate is carried out suitable aftertreatment, thus at least a portion Si atom in the burnt silicate is carried out isomorphous substitution with at least a suitable element.Preferred suitable element is selected from the group of following composition, Al, B, Fe, Ti, Sn, Ga, Ge, Zr, V, Nb and their two kinds or multiple mixture.No matter before calcination, whether layered silicate is the layered silicate crossed of isomorphous substitution, and this type of aftertreatment of the silicate of calcination all can be carried out.Depend on the atomic type that is incorporated into lattice, can form so electronegative skeleton, it makes that for example positively charged ion being loaded into silicate becomes possibility.Especially, the structure directing reagent of ammonium ion tetra-allkylammonium, platinum, palladium, rhodium or ruthenium positively charged ion, Jinyang ion, alkali metal cation, for example sodium or potassium ion, perhaps alkaline earth metal cation, for example magnesium or calcium ion can use.
Therefore the present invention also relates to by the obtainable silicate of method as stated, tectosilicate especially, and said method comprises the calcining according to (6), randomly carries out isomorphous substitution thereafter.
In many practical applications, it is molded that the user hopes to use finished layered silicate and/or tectosilicate usually, rather than the silicate of itself form.This type of mouldings is essential, especially in many industrial processes, so that for example, come to carry out easily the operation of separate substance from mixture, for example in tubular reactor.
Therefore the present invention also relates to and contains crystal as stated, the mouldings of micropore layered silicate and/or tectosilicate.The present invention also comprises and contains the mouldings of layered silicate as stated.
Generally speaking, this mouldings can comprise all imaginabale other compounds, and except layered silicate of the present invention and/or tectosilicate, its prerequisite is that it guarantees that the mouldings that obtains is applicable to the application scenario of wanting.
In the present invention, preferably, mouldings used at least a proper adhesive material in producing.In this preferred embodiment, more preferably, prepared the mixture of layered silicate and/or tectosilicate and at least a tackiness agent.Suitable binder is that all can be introduced on the basis of the physical adsorption when not having tackiness agent between will be by bonded tectosilicate particle and surpass the bonding and/or accumulative compound of the physical adsorption when not having tackiness agent in principle.The instance of this type of tackiness agent is a MOX, such as SiO
2, Al
2O
3, TiO
2, ZrO
2Or MgO, perhaps two of clay or these compounds kinds or more kinds of mixtures.As Al
2O
3Tackiness agent, special preferably clay mineral and natural or borolon, for example α-, β-; γ-, δ-, η-, κ-; χ-or θ-aluminum oxide and their inorganic or Organometallic precursor compounds, such as gibbsite (gibbsite), bayerite (bayerite); Boehmite (boehmite), pseudobochmite (pseudoboehmite) or aluminic acid tri-alkoxy ester (trialkoxyaluminate) are such as three aluminium isopropylates.Further preferred adhesive is amphiphilic cpds and the graphite with polarity and nonpolar structure division.Other tackiness agent is a clay for example, for example polynite, kaolin, wilkinite (bentonite), halloysite (halloysite), dickite (dickite), nakrite (nacrite) or anaxite.These tackiness agents can use with the form of himself.Also can use such compound within the scope of the present invention, at least one other step, form tackiness agent in the production in mouldings by these compounds.These adhesive precursor instances are tetraalkoxysilane, four titan-alkoxide acid esters, four alkoxy zirconium esters; Or the mixture of two kinds or more kinds of different tetraalkoxysilanes; Or the mixture of two kinds or more kinds of different four titan-alkoxide acid esters; Or the mixture of two kinds or more kinds of different four alkoxy zirconium esters; Or the mixture of at least a tetraalkoxysilane and at least a four titan-alkoxide acid esters; Or the mixture of at least a tetraalkoxysilane and at least a four alkoxy zirconium esters, or the mixture of at least a four titan-alkoxide acid esters and at least a four alkoxy zirconium esters, or the mixture of at least a tetraalkoxysilane and at least a four titan-alkoxide acid esters and at least a four alkoxy zirconium esters.In the present invention, can use wholly or in part by SiO
2Perhaps SiO
2The tackiness agent that precursor is formed, said precursor forms SiO at least one other step in mouldings is produced
2In this article, can use colloidal silica and so-called " wet method silicon-dioxide " and so-called " dry method silicon-dioxide ".The especially preferably unbodied silicon-dioxide of silicon-dioxide, wherein the size of silicon dioxide granule is 5-100nm for example, the surface-area of silicon dioxide granule is 50-500m
2/ g.Colloidal silica; Preferably with the form of alkaline solution and/or ammonia solution; More preferably, can be used as
or
especially and obtain with the form of ammonia solution."Wet" silica especially as such
or
to get."Dry" such as silica can be particularly
or
to get.Adhesive consumption preferably makes final mouldings have the tackiness agent of maximum 80 weight %; More preferably 5-80 weight %, more preferably 10-70 weight %, more preferably 10-60 weight %; More preferably 15-50 weight %; More preferably 15-45 weight %, preferred especially 15-40 weight % is in each case based on final mouldings gross weight meter.Term " final mouldings " expression of using in this article is from the drying that is described below and calcination stage (IV) and/or the mouldings that (V) obtains, preferably from the mouldings of (V) acquisition.
At least a other compound can mix with the mixture of tackiness agent or adhesive precursor and zeolitic material, is used for further processing and being used to form plastic material.Particularly, can preferably mention pore former here.In the methods of the invention, operable pore former is all compounds that particular bore size and/or particular bore distribution of sizes and/or particular bore volume can be provided in final mouldings.The pore former that uses in the methods of the invention preferably can be disperseed, suspended and/or is emulsifiable in the polymkeric substance in water or the aequeous solvent mixture.Preferred polymkeric substance is a polyvinyl compound; For example polyalkylene oxide such as polyethylene oxide; PS, polyacrylic ester, Rohm tech inc, polyolefine, polymeric amide and polyester, glucide be Mierocrystalline cellulose or derivatived cellulose such as methylcellulose gum for example, or sucrose or natural fiber.Other suitable pore former is, for example paper pulp or graphite.If used pore former in the preparation of the mixture in step (I); Pore former then; Preferred polymers, the content in (I) in the obtained mixture are preferably in 5～90 weight % scopes, preferably in 15～75 weight % scopes; In 25～55 weight % scopes, all be based on the amount meter of the novel tectosilicate in the mixture in the step (I) under every kind of situation.If the pore size distribution needs that will reach in order to produce can also use the mixture of two kinds or more kinds of pore formers.In the special preferred embodiment of the inventive method, be described below, in step (V), remove pore former, thereby obtain the porous mouldings through calcining.
In similar preferred embodiment of the present invention, in process, add at least a paste agent (pasting agent) according to (I) preparation mixture.As paste agent, can use all to be suitable for the compound of this purpose.These preferably organically, hydrophilic polymer particularly; Like Mierocrystalline cellulose, derivatived cellulose such as methylcellulose gum, starch such as yam starch; Wallpaper is stuck with paste, polyacrylic ester, Rohm tech inc, Z 150PH, Vinylpyrrolidone polymer, polyisobutene or THF homopolymer.Therefore, especially, can use also compound as pore former as paste agent.In preferred especially the inventive method embodiment, be described below, these paste agents are removed through the calcining in the step (V), obtain the porous mouldings.
According to another embodiment of the present invention, during according to (I) preparation mixture, can add at least a acid additives.Particularly preferably be very much, can in the preferred steps that is described below (V), remove the organic acidity compound through calcining.Special optimization acid, for example formic acid, oxalic acid and/or Hydrocerol A.Also can use the mixture of two kinds or more kinds of these acidic cpds.
Interpolation order according to each component in the mixture that contains layered silicate and/or tectosilicate of (I) is not crucial.Can add at least a tackiness agent earlier; Add at least a pore former, at least a acidic cpd then; Add at least a paste agent at last, also can exchange the order of at least a tackiness agent, at least a pore former, at least a acidic cpd and at least a paste agent.
After adding tackiness agent in layered silicate and/or the tectosilicate solid (if adding above-mentioned at least a compound), according to (I) the general homogenizing 10-180 of mixture minute to it to suitable.Especially, kneader, pan mill or forcing machine are particularly preferred for homogenizing.Mixture is preferably mediated.On technical scale, the processing in pan mill is preferred for homogenizing.Homogenizing is generally carried out under the temperature between the boiling point of paste agent and normal atmosphere or a little higher than atmospheric pressure at about 10 ℃.If suitable, can add at least a above-claimed cpd subsequently.The mixture that so obtains carries out homogenizing, and preferred the kneading is up to forming extrudable plastic material.
According to more preferred of the present invention, the mixture of homogenizing carries out molded.In the present invention, preferred method of moulding be wherein in conventional forcing machine through extruding those methods of carrying out, for example obtain diameter and be preferably 1～10mm, be preferably the extrudate of 2～5mm especially.Such extrusion equipment is for example at Ullmann ' s
der Technischen Chemie; The 4th edition; The 2nd volume; The 295th page is risen, and describes to some extent in 1972.Except using screwe-type xtruder, also preferred use plunger type extruder (plunge-type extruder) carries out molded.Yet, can use all known and/or suitable kneadings and molding equipment and method to carry out moulding in principle.These especially comprise: briquetting (briquetting) promptly adds or does not add extra adhesive material and carries out mechanical compaction; Granulation (pelleting) is promptly through circumference and/or rotatablely move and compress; Sintering is promptly to wanting molded material to heat-treat.The profile of the mouldings that will make according to the present invention can be selected as required.Especially, except sphere, ellipse, right cylinder or plates also are possible.
In the present invention, preferably follow step (III) and carry out at least one drying step.
In the present invention, preferably follow step (IV) and carry out at least one calcining step.Generally speaking, calcining is carried out under 300 to 700 ℃, more preferably carries out under from 300 to 600 ℃.Calcining can be carried out in any suitable atmosphere, preferred air and/or poor air.In addition, calcining is carried out in rotary kiln and/or the banded calcining baking oven preferably at retort furnace.Possible is that in calcining step, it is constant that temperature keeps, perhaps continuous or discontinuous variation.If calcine twice or usually more times, calcining temperature can be identical or different in each step.
Therefore, the invention still further relates to the method for producing aforesaid mouldings, it comprises the steps
(I) prepare a kind of mixture, it contains aforesaid layered silicate and/or tectosilicate, perhaps obtainable by method as stated or the layered silicate and/or the tectosilicate that obtain, and optional at least a tackiness agent;
(II) mediate mixture;
(III) mixture of mediating is carried out the molded at least a mouldings that obtains;
(IV) dry this at least a mouldings;
(V) this at least a dry mouldings of crossing of calcination.
Before the drying and/or afterwards, and/or before calcining and/or afterwards, this at least a mouldings can, if suitable, with concentrating or the mixture of the Broenstedt acid of dilution or two kinds or more kinds of Broenstedt acid is handled.Suitable acid is, for example, hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid or carboxylic acid, dicarboxylicacid or oligomeric or poly carboxylic acid, such as NTA, sulphosalicylic acid or YD 30.If suitable,, at least one of carrying out with at least a Broenstedt acid carry out at least one drying step and/or at least one calcining step after handling, and it is carrying out under aforesaid condition under each situation.
According to the another embodiment of the inventive method, the mouldings that obtains according to the present invention can, for better sclerosis, carry out steam-treated, at it after, preferably carry out at least again dry with or calcine at least again.For example, after at least one drying step and at least one follow-up calcining step, the mouldings of this calcination is carried out VT, and drying once and/or is at least again calcined once at least more then.
The present invention relates to the use of silicate of the present invention in addition, and the use of particularly novel tectosilicate, and/or the use of mouldings of the present invention are as molecular sieve; Catalyzer, support of the catalyst or its tackiness agent, as sorbent material, pigment; The additive of washing composition, the additive of material of construction is used for to the coating slurry and finish paint provides thixotropic property and conduct is outside and the application of internal lubricant; As fireproofing agent, the auxiliary agent of paper product and filler in sterilization and/or mycocidal and/or herbicidal composition, are used for IX; Be used for Production of Ceramics, at polymkeric substance, electric, in optics or the electrooptics component and in switching element or the transmitter.
Preferably, layered silicate of the present invention, and/or the inventive method obtains or obtainable layered silicate; And/or tectosilicate of the present invention, useful as catalysts, support of the catalyst or its tackiness agent, sorbent material; Be used for IX, be used for Production of Ceramics, perhaps in polymkeric substance, use.
In addition, according to layered silicate of the present invention, can be as the starting raw material of columnar silicon hydrochlorate manufacturing.
The present invention explains with reference to following embodiment, figure and table in more detail.
Description of drawings
Fig. 1 to 4 has shown the X-ray diffractogram of the exsiccant layered silicate that obtains respectively according to embodiment 1 to 4.Fig. 1 has comprised that further the figure of RUB-36 structure is used for contrast.Powder x-ray diffraction figure uses monochromatic Cu K α-1 radiation record on Siemens D-5000, wherein use the kapillary sample holder to avoid preferred orientation.Diffraction data uses from the position sensing sensing detection device of Braun and collects, and in 8-96 degree (2 θ) scope, step-length is 0.0678 degree.The exponentiate service routine Treor90 of powder pattern carries out, and (Treor90 is a common program, can freely be obtained by URL http://www.ch.incr.org/sincris-top/logiciel in enforcement in powder-X.In the drawings, be that draw along transverse axis at 2 θ angles of unit with the degree, intensity is drawn along the longitudinal axis.
Fig. 5 has shown each sem (SEM) image of the dry layered silicate that obtains according to embodiment 4.
Embodiment:
Embodiment 1: the preparation of layered silicate
Moisture diethyl-dimethyl ammonium hydroxide (20.62 weight %) solution weighing with 1139.7g; And adding beaker; Substep adds the soft silica (
) of 238.9g; Stirred the mixture 2 hours, and obtained yellowish suspension-s.
Use rotatory evaporator from the mixture that obtains, to remove 188.6g water then, stirred spissated mixture 1 hour.With the weighing of 172.5g mixture, add high-pressure digestion container (pressure digestion vessel) then, then therein under hydrothermal condition, 140 ℃ of heating 208 hours.
Through centrifugation, the silvery white luminous suspension-s that obtains is separated then, clean to pH7, and, obtain the white powder of 31.8g thus 120 ℃ of dryings 24 hours with zero(ppm) water.
The synthetic product has the reflection shown in the table 1 in X-ray diffractogram (Cu K α 1).
Table 1: the X ray color collection of illustrative plates of novel lamellar silicate
| |
Intensity (%) |
| 6.19 | 98.5 |
| 8.00 | 100.0 |
| 10.47 | 1.7 |
| 12.34 | 1.5 |
| 12.69 | 3.1 |
| 14.18 | 3.0 |
| 16.00 | 3.2 |
| 17.18 | 8.1 |
| 17.95 | 4.0 |
| 18.98 | 3.8 |
| 19.62 | 4.4 |
| 20.40 | 14.1 |
| 21.22 | 7.4 |
| 22.53 | 5.6 |
| 22.88 | 10.2 |
| 23.36 | 7.2 |
| 24.05 | 15.9 |
| 24.91 | 21.2 |
| 25.44 | 22.3 |
| 26.23 | 9.1 |
| 26.66 | 13.4 |
| 26.98 | 10.3 |
| 27.76 | 6.4 |
| 28.56 | 5.3 |
| 29.75 | 4.6 |
| 31.15 | 8.8 |
| 32.93 | 2.9 |
| 34.47 | 3.3 |
| 35.22 | 3.0 |
| 36.45 | 3.6 |
| 37.13 | 3.7 |
| 38.39 | 3.6 |
| 40.60 | 5.2 |
| 42.18 | 3.8 |
| 44.20 | 3.6 |
| 45.17 | 5.9 |
| 46.10 | 4.6 |
| 46.53 | 4.0 |
| 47.14 | 3.9 |
| 48.39 | 5.7 |
| 49.57 | 5.9 |
| 50.75 | 4.4 |
Embodiment 2: the preparation of layered silicate
Moisture diethyl-dimethyl ammonium hydroxide (20.62 weight %) solution weighing with 976.9g; And adding beaker; Substep adds the soft silica (
) of 204.7g; Stirred the mixture 1 hour, and obtained yellowish suspension-s.
Use rotatory evaporator from the mixture that obtains, to remove 161.6g water then, stirred spissated mixture 30 minutes.Then with the weighing of 121.5g mixture, add the high-pressure digestion container, therein under hydrothermal condition,, therefore obtain the white solid of pasty state then 140 ℃ of heating 144 hours.
Then the white suspension that obtains is added in the china bowl, drying is 24 hours under 120 ℃, therefore obtains the buff powder of 35.8g.
The synthetic product has the reflection shown in the table 2 in X-ray diffractogram (Cu K α 1).
Table 2: the X ray color collection of illustrative plates of novel lamellar silicate
| |
Intensity (%) |
| 5.75 | 100.00 |
| 7.95 | 4.80 |
| 10.48 | 10.70 |
| 10.85 | 7.50 |
| 11.53 | 8.10 |
| 13.05 | 6.80 |
| 13.30 | 6.50 |
| 15.17 | 7.40 |
| 15.87 | 12.10 |
| 17.17 | 11.00 |
| 18.33 | 17.40 |
| 18.57 | 17.00 |
| 18.89 | 18.10 |
| 19.97 | 15.30 |
| 20.72 | 18.70 |
| 21.16 | 15.10 |
| 21.85 | 17.50 |
| 22.16 | 18.30 |
| 22.40 | 16.30 |
| 23.05 | 22.80 |
| 23.47 | 19.10 |
| 24.43 | 14.00 |
| 24.71 | 16.00 |
| 25.16 | 12.20 |
| 26.03 | 20.20 |
| 26.94 | 15.60 |
| 27.37 | 12.70 |
| 27.99 | 12.70 |
| 28.87 | 11.20 |
| 29.25 | 13.40 |
| 30.31 | 13.30 |
| 30.87 | 14.40 |
| 31.18 | 18.30 |
| 33.75 | 7.60 |
| 34.43 | 9.20 |
| 36.34 | 7.30 |
| 37.00 | 7.60 |
| 37.93 | 7.50 |
| 39.24 | 7.10 |
| 39.72 | 7.80 |
| 40.88 | 6.90 |
| 42.07 | 8.60 |
| 43.03 | 7.30 |
| 44.64 | 7.70 |
| 45.83 | 8.50 |
| 48.60 | 8.10 |
Embodiment 3: the preparation of layered silicate
Moisture diethyl-dimethyl ammonium hydroxide (20.62 weight %) solution weighing with 1628.2g; And adding beaker; Substep adds the soft silica (
) of 341.2g; Stirred the mixture 2 hours, and obtained yellowish suspension-s.
The mixture that obtains is put into the high-pressure digestion container, placed 24 hours, subsequently under hydrothermal condition, 140 ℃ of heating 192 hours.The silvery white luminous suspension-s that obtains has 12.57 pH value.
Through suction filtration, the separate solid reaction product is at first washed with filtrating then, and using 9 liters of zero(ppm) water to wash then and leading up to electricity is 105 μ s/cm.Then with product 120 ℃ of dryings 24 hours, obtain the white powder of 205.0g thus.
The synthetic product has the reflection shown in the table 3 in X-ray diffractogram (Cu K α 1).
Table 3: the X ray color collection of illustrative plates of novel lamellar silicate
| |
Intensity (%) |
| 6.12 | 100.0 |
| 7.97 | 3.1 |
| 10.44 | 4.0 |
| 11.09 | 2.3 |
| 12.28 | 2.4 |
| 12.97 | 2.6 |
| 13.65 | 2.6 |
| 16.04 | 4.4 |
| 16.78 | 5.8 |
| 17.43 | 5.3 |
| 18.46 | 5.2 |
| 18.90 | 9.0 |
| 19.57 | 8.0 |
| 20.09 | 7.4 |
| 20.61 | 7.2 |
| 22.44 | 7.8 |
| 22.84 | 13.4 |
| 23.84 | 9.2 |
| 24.15 | 7.6 |
| 24.76 | 4.3 |
| 25.39 | 7.0 |
| 26.10 | 7.8 |
| 26.55 | 8.3 |
| 27.39 | 4.5 |
| 27.87 | 4.9 |
| 28.48 | 5.8 |
| 29.32 | 4.6 |
| 29.64 | 4.6 |
| 31.15 | 11.7 |
| 31.58 | 4.9 |
| 32.85 | 2.7 |
| 34.24 | 2.2 |
| 35.07 | 3.3 |
| 36.38 | 3.3 |
| 36.97 | 3.8 |
| 38.06 | 2.6 |
| 39.12 | 2.7 |
| 39.77 | 2.7 |
| 40.73 | 3.5 |
| 42.00 | 3.5 |
| 43.38 | 3.1 |
| 43.89 | 3.2 |
| 45.00 | 3.1 |
| 45.57 | 3.2 |
| 48.02 | 3.8 |
| 48.90 | 4.1 |
Embodiment 4: the preparation of layered silicate
Moisture diethyl-dimethyl ammonium hydroxide (20.62 weight %) solution weighing with 651.6g; And adding beaker; Substep adds the soft silica (
) of 136.5g; Stirred the mixture 1 hour, and obtained yellowish suspension-s.
Use rotatory evaporator from the mixture that obtains, to remove 107.8g water then, stirred spissated mixture 30 minutes, obtain the suspension-s of pH 15.14 then.
With the weighing of 171.4g mixture, add the high-pressure digestion container, therein under hydrothermal condition,, obtain the pasty solid in solution of pH 14.45 then 140 ℃ of heating 168 hours.
Then through suction filtration, the separate solid reaction product, using 2.5 liters of zero(ppm) water to wash that electricity leads is 45.4 μ s/cm.Then with product 120 ℃ of dryings 24 hours, obtain the white powder of 24.9g thus.
Claims (22)
1. one kind contains the preparation method of the layered silicate of silicon and oxygen at least, and it comprises
(1) provides and contain silicon-dioxide and/or at least a silica precursor; Water, at least a tetraalkyl ammonium compound and at least a alkali, and the mixture of optional at least a suitable seed crystal material; Said tetraalkyl ammonium compound is selected from the group of following composition; The diethyl-dimethyl ammonium compound, the mixture of triethyl ammonium methyl compound and diethyl-dimethyl ammonium and triethyl ammonium methyl compound;
(2) will under autogenous pressure (hydrothermal condition), be heated to 120 ℃ to 160 ℃ according to the mixture that (1) obtains, reach 5 to 10 days, obtain containing the suspension-s of this layered silicate.
2. the method for claim 1; The aqueous solution that wherein uses according to (1) contains diethyl-dimethyl ammonium hydroxide; Triethyl ammonium hydroxide, the perhaps mixture of diethyl-dimethyl ammonium hydroxide and triethyl ammonium hydroxide, preferably diethyl-dimethyl ammonium hydroxide.
3. claim 1 or 2 method, the SiO that the mixture that wherein obtains according to (1) contains
2And/or with SiO
2The silica precursor of meter, the molar ratio of at least a tetraalkyl ammonium compound and water is SiO
2: tetraalkyl ammonium compound: water is 1: (0.3-0.7): (9-15), and more preferably 1: (0.4-0.6): (9-15), more preferably 1: (0.45-0.55): (9-15).
4. each method of claim 1 to 3, the SiO that the mixture that wherein obtains according to (1) contains
2And/or with SiO
2The silica precursor of meter, the molar ratio of at least a tetraalkyl ammonium compound and water is SiO
2: tetraalkyl ammonium compound: water is 1: (0.45-0.55): (9.5-10.5).
5. the method for claim 4, wherein heating reaches 8.5 to 9.5 days according to the mixture of (2).
6. the method for claim 4, wherein heating reaches 5.5 to 6.5 days according to the mixture of (2).
7. the method for claim 4, wherein heating reaches 6.7 to 7.5 days according to the mixture of (2).
8. each method of claim 1 to 3, the SiO that the mixture that wherein obtains according to (1) contains
2And/or with SiO
2The silica precursor of meter, the molar ratio of at least a tetraalkyl ammonium compound and water is SiO
2: tetraalkyl ammonium compound: water is 1: (0.45-0.55): (12.0-13.0).
9. the method for claim 8, wherein heating reaches 7.5 to 8.5 days according to the mixture of (2).
10. each method of claim 1 to 9, wherein according to (2), heated mixt is to 130-150 ℃, preferably 135-145 ℃.
11. each method of claim 1 to 10 wherein according to (1), is used soft silica.
12. each method of claim 1 to 11 wherein contains at least one provenance of at least a element in addition according to the mixture of (1), said element is adapted at carrying out in the layered silicate isomorphous substitution of at least a portion Si atom, and said element is preferably selected from the group of following composition; Al, B, Fe; Ti, Sn, Ga; Ge, Zr, V and Nb.
13. each method of claim 1 to 12, it comprises in addition
(3) from the suspension-s that obtains according to (2), separate this silicate, and optionally further comprise
(4) washing the silicate that separated, is 6.5 to 7.5 to pH preferably, and/or
(5) preferably in 100 to 150 ℃ TR, the silicate that separated and optionally washing is crossed is carried out drying.
14. the method for claim 13, it comprises that further the silicate with optionally washing and/or dry mistake to separating carries out aftertreatment, thus at least a portion Si atom in the layered silicate is carried out isomorphous substitution with at least a suitable element, and said element is preferably selected from the group of following composition; Al, B, Fe; Ti, Sn, Ga; Ge, Zr, V and Nb.
15. each method of claim 1 to 14, it comprises in addition
(6) will calcine according to the silicate that (2) or (3) or (4) or (5) obtain, calcining is preferably carried out more preferably 300 to 600 ℃ under 300 to 700 ℃.
16. the method for claim 15, it further comprises burnt silicate is carried out aftertreatment, thus at least a portion Si atom in the burnt silicate is carried out isomorphous substitution with at least a suitable element, and said element is preferably selected from the group of following composition; Al, B, Fe; Ti, Sn, Ga; Ge, Zr, V and Nb.
17. the layered silicate that can obtain according to each method of claim 1 to 14.
18. a layered silicate, its X-ray diffractogram comprise reflection at least as follows:
Wherein, 100% is relevant with the intensity at the peak of maximum in X-ray diffractogram.
19. a layered silicate, its X-ray diffractogram comprise reflection at least as follows:
Wherein, 100% is relevant with the intensity at the peak of maximum in X-ray diffractogram.
20. a layered silicate, its X-ray diffractogram comprise reflection at least as follows:
Wherein, 100% is relevant with the intensity at the peak of maximum in X-ray diffractogram.
21. the tectosilicate that can obtain according to the method for claim 15 or 16.
22. according to the layered silicate of claim 17 to 20 or according to the application of the tectosilicate of claim 21; It is as molecular sieve, catalyzer, support of the catalyst or its tackiness agent, and sorbent material is used for IX; Be used for Production of Ceramics, perhaps in polymkeric substance, use.
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Cited By (2)
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| WO2014060982A3 (en) * | 2012-10-19 | 2014-06-12 | Basf Se | Catalyst for the Conversion of Syngas to Olefins and Preparation Thereof |
| CN108996514A (en) * | 2018-07-20 | 2018-12-14 | 东北大学 | The method of chlorite crystal is prepared under a kind of hydrothermal condition |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0172715A2 (en) * | 1984-08-14 | 1986-02-26 | Mobil Oil Corporation | Process for deactivation of a zeolite |
| US6756030B1 (en) * | 2003-03-21 | 2004-06-29 | Uop Llc | Crystalline aluminosilicate zeolitic composition: UZM-8 |
| US20050065016A1 (en) * | 2003-09-23 | 2005-03-24 | Lewis Gregory J. | Crystalline aluminosilicates:UZM-13, UZM-17, UZM-19 and UZM-25 |
| CN1997591A (en) * | 2004-04-13 | 2007-07-11 | 巴斯福股份公司 | Microporous tectosilicate and method for the production thereof |
-
2010
- 2010-03-03 CN CN201080010370.3A patent/CN102341349B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0172715A2 (en) * | 1984-08-14 | 1986-02-26 | Mobil Oil Corporation | Process for deactivation of a zeolite |
| US6756030B1 (en) * | 2003-03-21 | 2004-06-29 | Uop Llc | Crystalline aluminosilicate zeolitic composition: UZM-8 |
| US20050065016A1 (en) * | 2003-09-23 | 2005-03-24 | Lewis Gregory J. | Crystalline aluminosilicates:UZM-13, UZM-17, UZM-19 and UZM-25 |
| CN1997591A (en) * | 2004-04-13 | 2007-07-11 | 巴斯福股份公司 | Microporous tectosilicate and method for the production thereof |
| US20080000354A1 (en) * | 2004-04-13 | 2008-01-03 | Basf Aktiengesellschaft | Microporous Tectosilicate and Method for the Production Thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014060982A3 (en) * | 2012-10-19 | 2014-06-12 | Basf Se | Catalyst for the Conversion of Syngas to Olefins and Preparation Thereof |
| CN108996514A (en) * | 2018-07-20 | 2018-12-14 | 东北大学 | The method of chlorite crystal is prepared under a kind of hydrothermal condition |
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| CN102341349B (en) | 2015-09-16 |
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