JPS5921518A - Crystalline silicate and its manufacture - Google Patents

Abstract

PURPOSE:To obtain a novel crystalline silicate with superior heat and acid resistances by hydrothermally reacting an aqueous mixture having a specified composition contg. silica, alumina, OH<->, tetraalkylammonium salt, methanol, etc. CONSTITUTION:An aqueous mixture of 7.5-11.0pH contg. starting materials in >=10 molare ratio of silica/alumina, 0.1-10 molar ratio methanol/water, 5- 100 molar ratio of methanol/silica, 0.01-0.5 molar ratio of OH<-> from an inorg. source/silica and 0.01-1.0 molar ratio of tetraalkylammonium salt/silica is hydrothermally reacted at 100-300 deg.C to obtain a crystalline silicate having a composition represented by a general formula pM2/nO.Al2O3.qSiO2 (where M is an alkali metal or an alkaline earth metal, (n) is the valence of M, 0.3<=p <=3.0, and q>=10) after calcination when expressed in terms of the molar ratio. The silicate has an X-ray diffraction pattern part of which is shown in the table.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a crystalline silicate called 118I-3 and a method for producing the same, and more specifically, the present invention relates to a crystalline silicate called 118I-3 and a method for producing the same.
A crystalline silicate with a new structure that can be effectively used in
↑BI-3) and its efficient manufacturing method.

Many natural and synthetic crystalline silicates have been known, and there are various manufacturing methods. C has been proposed. These methods are usually carried out by proceeding with a hydrothermal reaction using an aqueous mixture consisting of a silica source, an alumina source, and a plucarium metal source as a raw material, but recently organic compounds such as tetraprobylammonium bromide have recently been added to this aqueous mixture. A method for producing crystalline aluminosilicate zemerite having a special crystal structure by adding 4ζ·I has been developed. For example, Japanese Patent Application Laid-Open No. 52-43800,
According to Japanese Unexamined Patent Application Publication No. 134517/1983, by adding alcohol, ZSAi-5 type zeolite Be) Poku 1. It has been described that zeta 3 type 1 diolite can be produced, and Japanese Patent Application Laid-Open No. 56-37
According to Publication No. 215, it is described that ZSM-5 and ZRM-11 type zeolites are produced by using alcohol seed crystals in combination. Furthermore, l
F Kaimei 54 1 Fi 16 (1 (in Publication No. 1 (upper alcohol and monoammonia) 1 river l~te zeolite)
・It is disclosed that it is possible to generate. Also, water is used as a solvent and I
It is also known that buJudo Z11111-17ze8lite can be obtained by synthesis using detodibutyl ammonium j'iK (US 11ηK'F No. 370997).
9ri specification 1(1).

The present inventors have developed a completely new composition and crystal 411II'.
We have carried out research to develop A'j's silicate., Ini's combination (-, methanol as solvent),
By using tetraalkyl ammonium J and salt as a crystallizing agent, a completely new crystal structure of thread crystal +/+ silicate (l5I-
3) I found that /n1i11ra is the same. The present invention was completed based on this knowledge. Sufu, [
), in the present invention, the composition expressed in molar ratio after heating to 550 °C in air] and L-2 is expressed by the general formula 1
) Δ1.0・Al, 03・qsi09---(I
)'TI (where Δft1 represents an alkali gold sheath and/or an alkaline earth metal, and Δft1 represents the valence of M.

Also, ■) and Q are selected from the following range.

(1,3$p≦3.0.q≧10), and the X-ray diffraction pattern is shown in Table 1] n) a silica source; (b) an alumira source; (C) an alkali gold dust and/or alkaline earth metal source.

(Contains (1) a tetraal-V-ammonium salt containing an alkyl group having 4 to 6 carbon atoms, and (e) methanol, and the molar ratio of each component is

Silica/Alumina〉10 Methanol/'Silica-=':+-J 'S, (/Silica 0.0 1.-
1.0 is λ-edition, Mi) Ii 175~i1. (+ aqueous 71
1. White goods, ] (10 to 300 ” Cj (te crystal 1)
) The composition is 7 expressed as a molar ratio after firing at 550°C in air at 550°C, assuming that Silic-1 reacts until 41 is formed. (T), and the pattern between the X-rays 41[()crystal ↑no1siri,', -1. The manufacturing method of 11.
1.

1st Table p4 (Table 1 (Continued)) Light q・↑: (]+l−Kα; Wavelength: 15418λ Wood according to the method of the invention (5)) Silica source, (i)
Normina source, (0 alkali metals 91. 1' / 1
, -KerunoJRe-1-Class Metal Sources'',Hi((1) Charcoal Yu(Ni number 4-r;no-)゛Ru1-RunoI(.

Tetraalkyl carbon 1-1'X (
%', and further (e) add methanol to 2111-a, 1 part of water, 1 part of sweat; n'I"I",: ii"l 4
1'! l, turn it on and heat it up to make it anti-LF-1. Here, (51) silica τtQ: ) and 1゛, ■, jr!
j'i (1lj1.l IJ huff x <, n+):
/J H) end, jinlV-:+r, t-id silica, molten 1'+'F silica f and 4, 2nd ((use'
r-kiru 1, this melt Fr 1 rinka doshideke, Na 2
(-1 mol of K2O, water glass silicate containing Si, (-1 g I. ~ 5.) mol of K2O, 1°), t
Examples include i and c.

Also, (i) A, Lumina mud and L'-Cke, (・]shide/, "It's flat for use" (, example containing (fluid acid, r A me = Uno)・, Sodium -gammaluminate, colicoid IJ', j-lumino, A.Mina, etc. are rich in C.

In the Jj method of the present invention, the ratio of water + CiR, white matter, etc.]'lumiwo' is 1%, but it is fine.
:): 1. −+ <ke silica (Ri(1p), /
A A Mina (Al, (1,) 0) Molar ratio - ('
+ n or more should be done! 1″:+’ic 4
(1-I OF+ (l is 1iy11 (Yoba;,-
5L.

7 [, (C((・)-A ⇠Punori metal wood τ and /'17 Kokea, Tono, !Resoil゛(v1 Metal source, -(I ket 1, Various things are used. In the first example, sodium hydroxide dihydroxide, etc. are used, and sodium silicate,
The supply of silica or (J-Ahemina) can also be used as sodium oxide.
.

- On the other hand, sources of alkaline earth metals include calcium nitrate, calcium chloride, etc.

Here, the alkali metals in the aqueous mixture are 6 and/-! The molar ratio of alkaline earth metal and silica is not particularly limited and may be determined as appropriate depending on various conditions, but it is preferable for 7 to 1 molar ratio (102 to 1 molar ratio). and - should.

Subsequently, -C ((1) Tetraalkylammonium salt having 4 to 6 alkyl groups (1, as a crystallizing agent -(
It is an action-j, and for Jt-composition, there is a tetrabuty A.
・Ammonium bromide, tetrabutyl ammonium iodide, tetra-amylammonium bromide de 1-hexylene strain: -2-ri v1 ride,
l-jl Kujilbumi Aanshi Niuno, PuH+ -
7 4F. 5) Ra f Tsubu J No I ammoniuno, ri 1- + rai l゛ / [What is used for 91 drops. ]Yta, -) -kite) Ranor Yruanmo, Niuuno, Kawa no yo'-)ri, crystal 1'1 Siriku- 1, no ii'!
l l(!! no past Tli'-Hide)・Uryor■ノl゛Hunmo-“Niuno,” 1 I. 11 and 7, [4), X,
Wow, it's a precursor, and it's 20 mouths. Ll'-
．． ．． ) 'j' t-ra-r A- 4 Anmi Niu J
■(, (use of [i1H silica vs. 1 ~ ( 0.0 1
・~10 (-shirusha 4), ri completed + L < ih (1
Fl 3~05 (Moha/Hiji) and - Eveki Thousand Voices, I),
, S1'- and τ, (e) Mechnaw A-mouth, the formation of the crystal 1-1 silicate produced] is contained as yi. rs゛ is・'C ('.) 'J'1. ,' Construction 1
3- ] Ji'. k (1 'l'd to crystal rl! 1 [chi-sui) - to 2 important f. ．． 1' Role So (Ryu-' plays. Go's meta, no A.'s use' I branch is relatively multi-piece 1 and -3 Qrt L. <, for example, methanol/water mo, le 01 ~ ] 0, cow 〒 0, < b. IO3-bow and -4 power, methanol/silica molar ratio 'a: 5 ~ 1 0 0, 'l
'! iIC DJ- + L < ul. 3-6
0 should be done.

In the method of the present invention, these (a), (b), (
c), (d), and (e) ingredients by adding water (・).
This is made into an aqueous mixture 7 and reacted. Here, the molar ratio of hydroxyl Jt;/silica in the reaction system water 1 <1 mixture should be ()01 to 0.5. Ru. Furthermore, when reacting the aqueous mixture, it is sufficient to heat the aqueous mixture to a temperature 1, 5 and for a time necessary to generate crystalline silicate, but specifically, the reaction temperature is 100 to 300°C, preferably 120 to 200°C. It is sufficient to react at C for 5 hours to 10 days, preferably for about 10 hours/5 days. There are no particular restrictions on the pressure, and it is usually carried out under autogenous pressure. In addition, the reaction system was properly stirred 1 to 11; The γ atmosphere may be replaced with an inert gas if necessary. In addition, the reaction system σ month (( is neutral to alkaline, usually rl 7.5 to 1
1. It should be adjusted to a range of 8.0 to 10.5.

1- The crystallization reaction described above always proceeds in the presence of ((1) the crystallizing agent which is the component) and a large amount of methanol, and if the conditions of Gonere are not added by π, the desired crystallinity will not be achieved. It is not possible to obtain a silicate at °C.In this reaction, ゛C,1
．． In the mixture of each component II [1' [ordinal 1], there is no limit to the bias. Kame-rod in the water,
(1))-Alumino"σ(;1(・r'. (r-1)
Fart J quality agent, 7 carbon number 4 to 6L'7) Putraalkylammonium containing Al and V group, τ11
, Combined 51, Crocker, in water (C plus water fl: ?
77;
- After the above crystallization reaction, wash with water and further], 2 (1"
*2 If dried, the composition expressed by the general formula (1) will be A.

and between the zsM11
F5
−． ) 1, heat resistance 1'), acid resistance 14), 11% each (1) Conversion resistance of mechanical compound raw materials, 1, 4% l:. [13 Adhesives, etc. 4)
1-For tongue ℃・[:2. 1, Therefore, the crystal 1' of the present invention (silicate is a petroleum oil fertilizer.rj oil chemical-
It is widely or effectively used in one field of industry).

Next, we will explain the present invention to 1J↓Example.
Tomorrow.

Example 1 111:ffi acid')-A peniuno, (18 hydrate salt)9.
79. A solution consisting of 17.6 mt of acid (9.7%), 2529 mt of butylammonium bromide and 100 mt of water was mixed with Solution A, 17.6 mt of acid (9.7%), 17.6 mt of water glass (8 J, Ox 29
．． Q wt%, Nn209, 4 wt%, water 61.
6 wt%) 211'll' and 96 d of water to make 13 liquids and 5. Gradually drop part A and part 3 in 50ml of water at the same time -1=? 11', then add ul to 8
5, and further methanol 376 m/! Add 71L to 1~. Subsequently, the obtained water ti mixture was mixed with 11
Pour into a volumetric container and stir for 17 minutes.
0”C.

The reaction was carried out under autogenous pressure for 20 hours. After cooling the reaction mixture, the product was washed 5 times with 1.5e of water. The solids were then separated by filtration and heated at 120 °C for 6
-C55, (1 liter of crystalline silicate (■ 5
I-3) was obtained. The composition (molar ratio) of this product is 0.
16 NagO'0.82 (TJ3A), 0-Al2
O3'61.7S1.0.・It was 4.8 B,,0. Here, TBA refers to a tetrabutyl ammonium group. The X-ray diffraction pattern of this crystalline silicone is shown in FIG.

Example 2 Actual Mlj Adding to Example 1, (■(mad acid aluminum
(18 people ti, j) RO-1-8,89 added, t,', K Ml (; Perform the same operation as in 11.1 / +s+-3) II
Ta. ■11 of the second contract (・[4 ratio), 0, 5
5, Nn, 0・(l117 (Go'+3A), (1
・A, l , 0 , ・31.138IO, ・4, I
It was J-+20.

Example 3 In Example 1, Tetragjirubuun! -2-Uno・
Instead of broma f-do, use de l-cyamyl-)inmoniuno...i3dite25ri(・Other than that, it is real noi 1.
1 Example 1) - Perform the same operation as (;1), then convert crystalline silic-1 (ISl, -: () to qr+ /, -6 Composition of this product (1,000 ratio) (,■ , (1,4!l Na2O
・(]52 (TAA), O-Al, 0.' 62.
! i SiO, -4,3Jt20 was set. Here, 'T' AA represents a 5-tocy-amilian-uno group.

Figure 1 'ini (7J flii J)'', if
itt fJ] Figure 1 is obtained with actual hand warmer example 1'k,
v1'i item i'L '/') '/' -1 of X
Inter-line IfF pattern 4. - Indication "J" where 〇 indicates the angle of incidence.

% R' + Applicant: New Fuel Oil Development Technology Research Association Procedures Amendment-) (Voluntary) July 5, 1915B □ 'V Toki ('I Agency Director Kazuhiro Reisugi Tono t-1! display) Waiting 11 Showa 57-130629 2. Name of the invention (Crystal)-1 Silicates and their manufacturing method・Special applicant New fuel oil development technology research Kinudai 4th generation 1113 people 1 [] 4 411-1-10, Chuo-l-Nukyo, Tokyo 5? 'llI Positive object clear i: m i, s + paste Fl' Claims (Details of the lock and invention + 1i (It's explanation C) Column 6 Contents of amendment (2) Line 802 of the specification 1-hydroxyl group/silica-
[101~0.5J is ``hydroxide ion/silica -0.0
1 to [5 (however, excluding hydroxide ions from organic salt yarns)
” -1.

(3) On page 13, lines 3 and 4, [-hydroxyl group] was not corrected to 1-hydroxyl ion [2].

(4) There is 1 on page 13, line 5. ” and “-Furthermore,” “'fr, in this case, the number of moles of hydroxyl ion is calculated by excluding all the hydroxyl ions produced by adding a specific base]2.” Join all.

(5) U on page 15, line 8, then -1 and 1+1 H,
<150% sulfuric acid between 1 and 13.0! i' plus -1
join.

(below)') □, II', tTR Ao・艮 range tit? f
irt"c 550 c in the furnace, after forming the molarization r hoe 12^ composition, the general formula pM2n O" A1203 "qs
1o2 (where M is alkali metal and /1'ft
: indicates an alkaline earth metal, 12, and n indicates the valence of M.

4, p+q is selected from the following range.

0.5≦p≦3.0. q≧IL1i, and the X-ray diffraction pattern is 11, 20
+[1,2 Moderate 10,06 + 0.2 Slightly strong 7,4
8 ten [], 2 weak 6.7 A
3:f, ], ]15 weak 6, 39- (115
Weak 6.02±O215 Weak 574±(115 Weak 5.590(115 Weak 5.01+115 Weak 4,63 +(
115 Weak いgon韮■澗J'' ISHI41SHIKETA- 4,3s-J2 1115 Weak 4.28±[110 Weak 4.02±[1,1[] Weak
Iro, B7" 2 [110 Very strong, 8 Roshi (Llo strong, 5.7
7± (11,1[]
Medium 4j, j degree 5.73± (110 slightly strong 3.66± [1,10 out of 411 degree 1 3.50± and 107 weak Iro,
45”2 0.07
Weak 3.32shi0.07 Weak 3
．． A crystalline silicate characterized in that it has an i content of 06±[107 less than 2.99±[107 less than 2.95±[1,07 less].

(2) (a) silica source, (b) alumina source, (C)
alkali metal and/or alkaline earth metal source, (d
) a detraalkylammonium salt having an argyl group having 4 to 6 carbon atoms; and (e) a methanol-containing L, and the ratio of each liV, 11% is Silica/'-γ Lumina 21D Methanol/Water = T11 ~1゜Methanol/Silica-5~100 Tetraargylmonium Hanawa/Silica=0.01
An aqueous mixture with a plt of 7.5 to 1tD that is ~1.0,
100 to 30 () 'C': Composition expressed in molar ratio after 550 tons of odor-C sintering in air, with a sign that the reaction is active until crystalline silicate is produced at 'C': However, the general formula is pMy7nO"A40s"
qs io.

(In the formula, M← represents an alkali metal and 7 or alkaline earth metal 1., i~, and n represents the valence of M.

'1''f's p and q are selected from the following range.

[Top 3 ≦ p ≦ 3.0. q ≧ 10) and the X-ray diffraction pattern is the lattice plane 1) LL
Interval −±Φ〜 Relative intensity.

1 1, 2 +, l,) 20, 2
Medium 11106±11
2 Slightly strong lattice spacing d(X)
Relative strength 7,48 + [1,2 weak 6.74±(115 weak &39±l115 weak 6.
02±1115 Weak 5.74±0.15
Weak 5.5900. 15
5.01±0.15 Weak 4.63±O15 Weak 4.68±0.15 Weak 4.2
8-1=0.10 weak 4.02 plus 13
．． 10 weak 5.87shi010
Very +:, Ili 3.83 + [110 Strong 3.77 ± [110 Moderate 3.76 ± 0.10 Slightly strong, 66 ± [
110 middle 1] 3- 3.50 1.107 weak 3.45±0
．． 07 Weak 6.32± (107 Weak 5.06-t (1 [ko 7
Weak 17.99 + [IO7 Weak

Claims (1)

[Claims] (1) The composition expressed in molar ratio after firing at 550°C in air has the general formula p, 1O-A1203.qsto. (In the formula, M represents an alkali metal and/or an alkaline earth metal [7, n represents the valence of M. In addition, p + q is selected from the following range: 03≦I]≦3.0 q≧10), and the X-ray diffraction pattern is 11,20 +0.2
Moderate 10.06 02 Slightly strong 7.48±02 Weak 674±015
Weak 6.39-, 15
Weak 6.02±015
Weak 1 lattice plane fail (1('A) Japanese 1 strength 57
4th grader 015 weak 5.59+0.15
Weak (・5.01 +(1,
15 weak 4.63 + (1,15 weak 438015 ≦) ℃・428 two 〇 1 () weak 4
．． 02 +(+, ], O weak 3, 87 +0.10 Very strong ℃・3.8
3+0.10 strong 377: 010
Moderate 3.73+0.10! - or strong 3, 6
6-1- (1,, 4' in 1l-1f-1 3.51
B-0()7 Weak 3, 45:l: 0. (17 Weak 3.32 + 0.07 Weak 3.06 〇 (17 Weak 299 ± 0.07 Weak 2.95 ± ()07 Weak ℃...Crystalline Silifut characterized by being expressed. f21 ( a) Silica source, (b) Alumina source, (C
) an alkali metal and/or alkaline earth metal source;
(d) Tetraal- having an alkyl group having 4 to 6 carbon atoms
V ammonium salt and (e) methanol,
And the molar ratio of aged is: silica/'alumina≧10, methanol/water=01-10, methanol/silica-5-100, hydroxyl group/silica-0,01-05, detraalyl ammonium salt/silica=001-1,
The aqueous mixture of 75-11.0 rivers is 100-3
The composition expressed in molar ratio after firing at 550°C in air, characterized by reacting until crystalline silicate is produced at 00'C, is given by the general formula p M
27.1C1・A, l, O,・q 5in2 (in the formula, M
represents an alkali metal and/or an alkaline earth metal, and n represents the valence of M. Further, p and q are selected from the following range. 03≦))≦30. q≧10), and the X-ray diffraction pattern is
i (] (in) Comparison/1 strength 1.1.20-
〇 2 1 junior high school student (
10, ()G + 0.2 Yaku] territory i
(・7.48+02 weak 6.74
+0.15 a little less ℃・6.3
941.1.15 Weak 6.02:I
=0.15 weak ℃・5.7
4+0.1 5 pieces)
) ℃・5.59 +(1,], 5
Weak 50 工”2 () 15
Weak (・4.63 +0.15
Weak ℃・4318 Sat 015 Weak 428 Shi 010 Weak 402+010 Weak (・3.
87- 〇10 Strong against non-hatake 3.83 +〇, IQ strong 3, 77 +t-11
0 Moderate 373±01() Slightly strong ℃・3.66+0
．． 10 Moderate 3.5 (Lf: Q, 0
7 Weak lattice spacing d(3)
Relative strength 345±007 weak 332:
l-007 weak 3 ()l2007 weak ℃・2,,99 +(1,07 weak 2.95 +(1,07 weak) A method for producing crystalline silicate.