JPS6077121A - Manufacture of silica polygonal body - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION TECHNICAL FIELD This invention relates to a process for backing polycrystalline silica polymorphs (eg, silicalites and zeolites) where the silicon source is elemental silicon.

Description of the Prior Art One of the most frequently used silicon sources for the production of silicalites and crystalline aluminosilicates is silica, usually in the form of colloidal silica aqueous groups. A representative disclosure of such silicon sources is in 1977
U.S. Patent No. 4,061,72, granted December 6,
No. 4, in which amorphous silicas such as alkali metal silicates such as fumed silica, silica sol and silica dal are described as silicon sources. 198
U.S. Patent No. 4,259,3, granted March 31, 1999.
No. 06 discloses silicic acid as a silicon source.

UK Patent Application No. 2 published on 23 December 1981
, 077.709A, some special silicon sources,
Mention may be made, for example, of powdered solid silica and dissolved silica.

There are also braided aerosol silicas that can be used in reinforcing pigments for rubber, and water gun silicas and silicas made by dissolving silicas in alkali metal hydroxides or quaternary ammonia hydroxides. is listed as a silicon source. The use of organosilicon compounds as silicon sources can be combined with titanium compounds (19
UK Patent Application No. 2.071,0 published September 16, 1981
No. 71A), combination with aluminum compound (1981
French Patent No. 2,478,063 published on September 18th
), in combination with germanium compounds (UK Patent Application No. 2.023,562A, published 3 January 1980);
and combinations with iron and chromium compounds (August 8, 1980)
European Patent Application No. 0014059 published in Japan).

SUMMARY OF THE INVENTION The present invention relates to an improved method for producing silica polymorphs, including those referred to as silicalites and zeolites.
This process involves introducing silicon in the form of elemental silicon into an aqueous reaction mixture under basic conditions, usually together with a tembrate compound, and then controlling this medium at a temperature range of e.g. 7.1 voice, including heating. In a preferred embodiment, the original violet silicon is about 2
The powder has an average particle size of less than 1,000 microns, preferably less than about 350 microns. Other elements, such as aluminum, can also be introduced together with elemental silicon to be included in the polymorph.

3. Detailed Description of the Invention The term silica polymorph used herein is essentially 1001
In addition to polymorphic forms consisting of silica, about 5
It also includes polymorphs up to 0. Examples of such elements include aluminum, boron, iron, chromium, zinc, gallium, phosphorus and arsenic, which may be used alone or in combination. Elements added to the silica polymorph by conventional techniques can be introduced along with elemental silicon. If the elements to be introduced into the polymorph are or become reactive under the conditions used for the reaction, they can be added in the same form as silicon. Provisions should be made to treat the hydrogen gas formed when silicon and other elements react in this process.

US Patent M3,7, granted November 14, 1972
．． No. 02,886, U.S. Pat. No. 3,769,386, granted May 30, 1973, May 1, 1977.
No. 4,022,714, granted on October 0, 1978 and US Pat. No. 4,1, granted on October 17, 1978.
Silicon can be used to make a wide range of polymorphs, including crystalline zeolites containing elements other than silicon, such as those described in US Pat. No. 20,910.

U.S. Patent No. 4.25, granted March 31, 1981
No. 9,306 and US Pat. No. 4,357,233, granted Nov. 2, 1982, can also be produced. No. 4,283,306, granted August 11, 1981; US Pat. No. 4,061,724, granted December 6, 1977; and US Pat. No. 4,061,724, granted March 2, 1976. U.S. Patent No. 3,941
, 871:
U.S. Patent No. 4,28, granted August 25, 1981
Porosilicate as described in No. 5,919; and German Patent Application No. 2,8 published on February 7, 1980
Iron silicates such as those described in No. 31,611 can also be made according to the present invention. Other silica polymorphs will be apparent to those skilled in the art.

The method comprises preparing a reaction mixture comprising water, elemental silicon, usually a template compound, and optionally a surfactant and/or dispersant at a temperature of at least 7°1, preferably between 9.5° and
@ range of 13.8 and more preferably 10.5 to 13,8
heating under hydrothermal conditions at temperatures in the range of . Silicon is obtained from a wide variety of sources including amorphous, polycrystalline and single crystal silicon in powder, wafer, rod or pellet form. The degree of subdivision, eg powder vs. pellets, significantly influences the reaction rate. Silicon produced by carbon reduction of silica is another satisfactory silicon source. The most desirable silicon source is a separate material in the manufacture of conductors. High purity silicon powder can be used to produce high purity silica polymorphs.

Alloys of silicon, such as silicon-aluminum alloys and silicon-iron alloys, are also suitable silicon sources.

Reaction time and temperature are not critical and can be similar to those conditions used in the prior art, as long as sufficient time at elevated temperature allows reaction of the silicon and formation of crystalline silica polymorphs. . Usually the reaction temperature is 10
Although it can vary between 0 and 300°C, it is preferably maintained between 140 and 200°C. The reaction time can be as long as practical, but
It is preferable not to exceed 30 to 300 hours. It is preferred to carry out the process continuously, thereby resulting in a substantial reduction in reaction #'. After separating the reaction product from the liquid, for example by filtration, it is preferably washed and dried by known techniques.

If a template is required for the production of polymorphs, a number of compounds are suitable. If it is desired to produce very pure silica polymorphs, the template must be essentially free of metals, except for alkali metals. Preferably, the template consists of an alkali ammonium cation essentially containing an alkali ammonium cation defined by the following formula, in which the R groups are the same or different and are alkyl groups containing from 1 to 6 carbon atoms. It is the basis. Preferably R is methyl, ethyl, n-propyl, n-butyl and their isomers, and mixtures thereof. Possible and preferred anions are hydroxyl and halogens, such as chlorine. Specific compounds include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, and salts corresponding to these hydroxides, in particular chloride, iodide and hyclamide, such as tetraprobil. There is ammonium gromide. The quaternary cation can be fed as such to the reaction mixture or can be formed in situ.

Other templates include alkyl amines, alcohol amines, monohydroxyalkylene realkylammonium halides, alkali and ammonium alkyl sulfonates, complex ions such as a7doamide, pentaerythritol, pennortrimethylammonium, organic diols and organic carboxylic acids. including.

Another template is a compound in which the nitrogen atom in the above formula is replaced by a phosphorus atom, and a diamine having the formula NH2(CH2)nN, where n = 2 to 12, such as ethylenediamine, hexamethylenediamine. There is. Additionally, other templated compounds will be apparent to those skilled in the art.

The basicity of the reaction medium can be controlled in several ways.

Template or template in combination with an alkyl ammonium halide or diamine, such as hexamethylenezamine, imparts basicity. Ammonium hydroxide and alkylammonium halides are also possible combinations. Alkali metal hydroxides can also be used to impart basicity, but are not preferred since additional steps are required to remove residual alkali metals from the polymorphs, which are different from the bases mentioned above.

Dispersants can be used in this method. Dispersants that do not participate in the reaction are preferred to the extent that they do not reduce the desired properties of the silica polymorph. Alcohols of 1 to 6 carbon atoms are quite suitable. Examples of such alcohols are methanol, ethanol, n-glopanol, n-butanol, n-pentanol, n-hegizanol and their isomers.

Other dispersants will be apparent to those skilled in the art. Surfactants such as ethoxylated alcohols, I-lyoxyethylene tridecyl ether, I-lyethylene glycol dilaurate, and octylphenoxypolyethoxyethanol are also used at 2-10% by weight of the reaction mixture to promote the reaction.
Can be used at concentrations of Other surfactants will be apparent to those skilled in the art.

Although the relative proportions of the reactants can vary over a very wide range, K! (81), template compound (T5, water (H2O
) and any surfactant (S), alcohol (A)
When expressed as a molar ratio, the relative capacity of elements (E) other than silicon is generally Si/H20 of 0.005 to 0.25 and preferably 0.01 to o, os; T/S i of 0. O
1 to 10 and preferably 0.1 to 1; A/) (2o is 0
~5 and preferably 0.02~1:] 1% Si is O~
1; S/'H20 is 0 to 0.15 and preferably 0
．． 0001 to 0.001. Mixtures of silicon, template and alcohol are within the scope of this invention. Premature solid formation that occurs in high ionic strength systems can be minimized by methods known in the art, such as by dilution.

The following examples, summarized in Table 1, are illustrative of the FJA and are not intended to be limiting. Parts and percentages are by weight unless otherwise indicated. The following abbreviations were used in the example batters: TENQH - Tetraethylammonium hydroxide - 4O t aqueous solution TPNBr = Tetraprobylammonium gromide TPNCl = Tetranolobyl ammonium chloride TPNOH = f ) 77' Lobylammonium hydroxide - 40% aqueous solution I (MD, = hexamethylene diamine - 85% aqueous solution TMNOH = f) A) Chilua/monium hydroxide - 25% aqueous solution ETOH = ethanol MEOH = methanol NA = not analyzed Examples 1-17 Reactions shown The body was stirred vigorously at 25°C to form a slurry. For template added to an aqueous solution, record the solution weight in ft. The resulting slurry was processed in an autoclave equipped with a stirrer and a heating jacket and capable of controlling pressure.

In Examples 1.2, 3, 7, 8, 12.14 and 17, 3
16 stainless steel, Hastelloy nHN for Examples 4, 5.1011.13 and 16, Hastelloy C for Example 6
In M and Example 15, autoclay FF made of titanium was used.

Close the autoclay and stir (approximately 100 to 200 r
pm) L,, slowly adjust the temperature of the contents to 9160.
The temperature was raised to 160° C. and maintained at 160° C. with stirring for the time indicated except when evacuated to prevent the pressure from exceeding 37.4 atm.

In Example 9, each material was filled into Teflon bottles, the bottles were placed in an autoclave, and the contents of the bottles were not agitated during the reaction.

The solid crystalline product was collected by filtration, washed three times with the same volume of water as the solid, and dried at 95° C. in a honey atmosphere. A sample was taken, heated at 25 to 550°C in air while increasing the temperature at a rate of 5°C/min, and held at about 550°C in air for about 4 hours.
Obtained a line diffraction pattern. X@diffraction measurements were performed using a scintillation counter and an irradiated 12.5 meter with a thickness of 3 s + m.
Ph1lli equipped with compensation slit containing gourd sample
On the pi diffractometer, 40 kevN 40
It was performed using Cuka radiation at mA. /Mother turns are listed in the summer table with reference symbols, and are shown in numbers ■ to X■. The calcined products were analyzed for aluminum and iron and boron in Examples 16 and 17, respectively.

Example 18 A mixture of elemental silicon and 310 g of water was heated with stirring in a glass vessel complete with a reflux condenser. When the temperature of the contents of the container reaches '72℃, 110g
A solution of sodium hydroxide and tetrapropylammonium chloride in water was added over 3 hours while maintaining the temperature at 72°C. Next, the temperature 'f was raised to 90°C,
It was held at that temperature for 16 hours. The contents of the container were transferred to an autoclave (316s8) and processed as in Examples 1-17. The results are summarized in Table 1.

Example 19 A mixture of elemental silicon, tetrapropylammonium bromide and water (385I) was heated with stirring in a glass vessel equipped with a reflux condenser.
When 3°C was reached, sodium hydroxide solution was added over 30 minutes, then the contents temperature was increased to 99°C and at this temperature 1
It was held for 9 hours. Autoclave the contents (3168B
) and treated in the same manner as in Examples 1-17. The results are summarized in Table 1. The products made according to the invention can be used in substantially the same way as polymorphs of similar composition made by different methods. Applications of silicon in various forms including polymorphs include:
Catalysts for alkylation, hydrogenolysis, methylation, etc.
With drying adsorbent, molecular sheet and ion exchange O 133 10 54 l1 196 10 53 102 385 55 ■ 292 1.069 NA ■ 96 343 135 118 447 67 'lX 101 484 60 105 1.208 50 X 100 2. 122 10 86 1.31 (ch) NA 142 1.10 (ch) 49' A 53 XI[[24NA I3.8
, mixed with 65gt silicon powder d6 reaction degree 180℃ e・reaction temperature 190℃ f, average particle size of about 27μm g, average particle size of about 11μm iron powder mixed with silicon powder, average particle size About 1.0 g of boron powder with a diameter of about 2 microns is mixed with silicon powder, iron content of the fired product is 8,756 ppmj, boron content of the fired product is 6,129 ppmk, about 509
Pluronic Grid (LIOI + Trademark)
was added as a surfactant, average particle size was approximately 88 microns, sodium hydroxide was added to 9.28.17, average particle size was 88 to 149 microns, and 409 was added to an aqueous solution of 50 hydroxide. (X) 11.20 80 4.27 14 10.08 48 4.10 3 9.77 14 4.02 5 9.02 1 3.86 100 8.05 <1 3.82 64 7.47 1 3. 76 39 6.72 7 3.72 50 6.39 13 3.66 29 6.02 19 3.50 5 5.74 9 3.45 11 5.57 10 3.36 10 5.38 3 3.32 14 5.16 2 3.26 4 5.01 7 3.15 3 4.89 <1 3.05 12 4.63 6 3.00 18 4.37 8 2.95 7 ■Table 11.24 90 4. 10 3 10.04 49 4.02 6 9.76 15 3.87 100 9.06 . 1 3.83 62 8.10 <1 3.72 58 7.48 1 3.65 21 6.72 9 3.50 6 6.39 15 3.45 11 6.03 18 3.40 4 5.75 9 3.36 9 5.58 13 3.31 15 5.38 4 3.26 5 5.16 2 3.18 3 5.05 6 3.15 3 4.99 8 3.06 10 4.63 6 3. 00 22 4.3B 9 2.96 11 4.28 13 No. ■ Table 11.08 5 2.90 6 6.78 27 2.69 4 5.79 79 2.57 1 5.55 60 2.51 13 4 .80 29 2.42 <1 4.41 28 2.36 15 4.30 3 2.27 22 3.93 37 2.23 14 3.71 92 2.16 5 3.40 43 2.12 3 3. 26 100 2.00 <1 3.21 16 2.02 2 3.05 13 1.97 4 2.94 11 1.94 9 Chapter V Table 11.73 29 3.07 2 10.18 8 2.86 14 7.12 3 2.74 2 6.10 4 2.69 2 5.85 9 2.62 2 5.26 (12,48(1 4,92<1 2.43 2 4.20 100 2.38 3 3.90 70 2.34 4 3.63 <1 2.23 2 3.46 (12,15<1 3.37 2 2.10 6 3.16 (12,064) Table 11.08 67 4. 35 7 9.92 42 3.83 100 7.42 1 3.70 44 6.67 5 3.47 3 6.34 4 3.33 8 5.97 15 3.16 1 5.56 10 3.04 5 5.34 2 2.97 14 4.99 6 2.85 1 4.60 2 2.77 <1 Table 1 11.15 81 4.26 14 1-0.02 51 4.08 3 9.70 12 4.01 6 9.00 1 3.86 100 8.05 (13,8282 7,4513,7543 7,12 (13,7258 6,7163,6539 6,37133,496 6,00183,4412 5,71113, 405 5,57153,3511 g, 3s 3 3.31 14 5.15 2 3.25 5 5.00 7 3.17 3 4.88 (13,144 4,6263,0516 4,4622,9818 4,368 Table 1 11.17 1 3.21 8 9.09 2 3.15 3 B, 31 3 3.05 13 6.82 9 2.95 13 6.59 4 2.86 1 6.28 6 2.79 3 5.80 47 2.71 2 5.55 46 2.61 <1 5.35 2 2.51 9 4.81 32 2.42 2 4.56 6 2.36 12 4.43 28 2.27 24 4.30 13 2.23 6 4.00 25 2.16 3 3.94 44 2.12 4 3.71 100 2.06 <1 3.58 5 2.02 <1 3.41 45 1.97 3 3.27 71 1.94 4 Chapter ■ Table 11.64 24 3.07 2 10.05 8 2.85 14 7.11 2 2.72 1 6.05 4 2.62 1 5.82 8 2.52 (1 5,24(12,471 5,02(12,422 4,8712,373 4,191002,344 3,87672,241 3,6142,096 3,4412,063 3,362 MX Table 11.11 55 3.85 100 10.03 48 3.71 38 7.47 (13,482 6,7233,349 6,3723,25<1 6.01 13 3.18 <1 5.58 9 3.06 6 5. 02 6 2.99 13 4.60 2 2.86 1 4.36 5 2.80 <1 4.25 2 Table X 11.12 59 4.36 7 9.99 33 4.26 12 9,. 73 11 4.08 3 9.03 1 4.01 6 8.06 (13,86100 7,46 (1,3,8267 7,14<1 3.75 36 6.71 5 3.72 50 6.36 10 3.65 32 6.01 12 3.49 6 5.72 8 3.44 11 5.58 11 3.35 10 5.37 2 3.31 12 5.1? 1 3.25 5 5.04 5 3.18 3 4.99 6 3.14 4 4.86 (13,0612 4,6252,9814 d(S) Relative strength d(X) Uni!!11.10
82 4.08 3 9.97 53 4.01 6 8.95 1 3.86 100 8.12 (13,8174 7,43 (13,7541 6,6973,7263 6,35153,642B 5.97 20 3 .49 6 5.70 11 3.44 14 5.56 14 3.35 11 5.36 4 3.31 16 5.13 3 3.24 5 4.99 9 3.17 3 4.61 6 3.13 3 4.36 10 3.04 13 4.25 15 2.98 25 No. 11.21 100 4.0S 10.06 61 4.0] 9.75 18 3.87 9.04 1 3.82 8 .09 (13,72 7,4723,66 6,7193,63 6,36163,60 6,00233,49 5,71123,44 5,58153,35 5,3733,31 5,1623,26 5,04B 3 .19 4.99 10 3.14 4.89 1 3.05 4.61 7 2.99 4.36 10 2.96 4.26 15 Relative intensity 00 6 5 4 2 3 6 1 6 4

Claims (1)

[Claims] 1. Introducing elemental silicon and a template compound into an aqueous reaction medium at a temperature of 100 to 300°C while maintaining the − of the medium in the range of 9.5 to 13.8. A method of making a silica polymorph comprising heating until the polymorph is formed. 2. The method of claim 1, wherein the silicon is a powder with a particle size of about 2000 microns or less. 3. The method according to claim 2, wherein the temperature is maintained at 140 to 200°C. 4. The method of claim 3, wherein the silicon powder has a particle size of about 100 microns or less. 5. Process according to claim 1, characterized in that aluminum is present in the reaction medium before the formation of the polymorph. 6. The method of claim 1 which features boron in the reaction medium before the formation of the polymorph 7. The method of claim 1 which features iron in the reaction medium before the formation of the polymorph The method described in paragraph 1. 8. The method according to claim 1, characterized in that aluminum, boron, iron and mixtures thereof p. 9. The method according to claim 1, characterized by an aluminum-silicon alloy. 10. A nonionic surfactant is present in the reaction medium;
A method according to claim 2. 11. The template compound consists essentially of an alkylammonium cation defined by the formula (wherein the groups represented by R are the same or different and are selected from alkyl groups of 1 to 6 carbon atoms) , the method according to claim 1. 12. Claim 11, wherein the cation is selected from tetracylobylammonium, tetramethylammonium, natho-2-butylammonium, and mixtures thereof.
The method described in section.