Manufacture of zeolite ZSM-5

in previous issues, a selection of the more interesting patents that have been published recently is given below under the headings: synthesis, catalysis, separation processes, detergents and miscellaneous applications. As

J.A. Barton

Novel

et al. 4, 1986;

Fr. Appl.

May

28,

Synthesis

of zeolite

E. W. Valyocsik Mobil Oil Corp. U.S.4.639.360, Jan.

1985

5, 1987;

Appl.

Aug.

26,

1985

1987;

Appl.

Oct.

28,

uniform,

finely divided

P. Knop; B. Nell; W. VEB Chemiekombinat E. Ger. 238,605, Aug. fine

zeolites

having

1985

of ZSM-5

H. Takasaki; T. Maruoka; Shikoku Chemicals Corp. Jpn Kokai Tokkyo Koho 1985

using

an

26,

crystallization alkyl phenols

teolite

in and

from

the presence ethoxylated

of and

humus

K. Shiba 86,295,224,

Dec.

26,

1986;

Appl.

June

T. R. Cannan Union Carbide PCT Int. Appl.

zeolite

20,

1986

M = ions

of

ZSM-5 Co. Appl.

Ltd. Jul.

15, 1985

of crystalline

aluminosilicate

S. Asaoka; H. Kudo; R. Endo et a/ Chiyoda Chemical Engineering and Construction Jpn Kokai Tokkyo Koho 87,17,014, Jan. 26,1987;

Co. Appl.

Ltd. July

12, 1985

Crystalline aluminosilicates are manufactured by hydrothermal synthesis of an aqueous mixture containing SiOz, A1203, alkali metal salts and choline compounds at conditions in which the choline compounds do not decompose or evaporate. A small portion of the product containing aluminosilicate crystals is recycled as crystallization seeds in the synthesis.

Synthesis

of crystalline

S. Kai Asahi Chemical Industry Jpn Kokai Tokkyo Koho Crystalline pared from A1203 source the presence

aluminosilicate

Co. Ltd. 87.36.017,

Feb.

17, 1987;

Appl.

Aug.

6, 1985

aluminosilicate useful as high-activity catalyst is prean aqueous mixture containing Si02 source material, material and alkali metal source material by heating in of > = l.of lower alkyl urea and lower alkyl thiourea.

U-202 Crystalline

Corp. 87,00,158,

Jan.

15,

1987;

U.S.

Appl.

July

8, 1985

Crystalline omega-type synthetic zeolites, i.e. U-202, characterized by their X-ray diffraction pattern have a composition: (1.0 f 0.5) Mu,0.A1203.xSi02.yH20, where M = > 1 of H, NH4, alkali metal, alkaline earth metal, transition metal, or rare earth lanthanide metal cation; n = valence of M; x = 3-20; y = O-20. A method for the preparation of the zeolites is described.

ZEOLITES,

Mar.

24,

Humus (humic acid, fulvic acid, humine, nitrohumic acid), which is obtained from organic soil or coal, is mixed with SiO+ontaining material, A1203-containing material, alkali metal oxide and water, and treated to give ZSM-5 zeolite. The reaction mixture contains 60-97 water and 0.001-10 wt.% humus, and mol ratios of Si02:A1203 > = 8, and Mu,O:SiOz 0.01-0.35 (M = alkali or alkaline earth metal ion, n = valence of M).

Crystalline

Appl.

Highly crystalline ZSM-5 zeolites are manufactured by hydrothermal synthesis of an aqueous mixture containing SiOz, A1203 and alkali metal salts and not containing any organic additives. A small amount of the product crystals is recycled as crystallization seeds in the synthesis of further crystals but having a different SiOz/A1203 ratio from that of the seeds.

Synthesis

1985

a composition:

PWN~.~~.dG03. (SiOh-3.0 are prepared by hydrothermal 1,3-butyleneglycol, ethoxylated sulphonated cocoa fatty acid.

Manufacture

June

of zeolite

S. Asaoka; H. Kudo; R. Endo et al. Chiyoda Chemical Engineering and Construcrion Jpn Kokai Tokkyo Koho 87.17.015, Jan. 26, 1987;

zeolites

Roscher et al. Bitterfeld 27, 1986; Appl.

zeolite

T. Maejima; Y. Tagaya et a/. Kogyo K.K. Tokkyo Koho 87,03,014, Jan. 9, 1987;

Manufacture

High-SiOz ZSM-5 zeolite is prepared hydrothermally organic sulphonic acid, e.g., N-2-hydroxyethylpiperazine-N-2ethanesulphonic acid, as the anionic templating agent.

86

Mar.

The novel zeolite has a composition: (0.8-l.S)Mz,O.A1203. (10-lOOISiO2. (WO)H20 (where group I and group II, and n = the valence of the ion), and a given range of interplanar spacing.

EM-5

27,

crystalline

S. Sakurada; Toa Nenryo Jpn Kokai

Zeolitic borosilicates of the pentasil type having a composition: (&1)Mu,0:B203:xSi02 (M = cation of valence n; x = 20-1000) also containing F, are prepared hydrothermally from a reaction mixture of pH < 10.5, containing water, a Si02 source, a B203 source, a mobilizing agent containing F- ions, and a structuring agent selected from Pr4N+ and Pr4P+.

Uniformly

EM-5 T. Blumenthal

zeolites

J. L. Guth; H. Kessler; R. Wey lnstitut Fraryais du Petrole PCT Int. Appl. 86,07,045, Dec.

Highly

of zeolite

Hydrothermal synthesis of zeolite ZSM-5 is carried out without the use of an organic templating agent by adding an acid and an acid aluminium salt to the reaction mixture after the onset of crystallization. The added Al compound may act as an inorganic template. The resulting zeolite has exceptionally high Si content.

SYNTHESIS Borosilicate

Synthesis

l-l. P. Rieck; M. Schott; Hoechst A.-G. Ger. Offen. 3,530,404,

1988, Vol8,

January

aluminosilicate

B. Yamada; Y. Noguchi; Toray Industries Inc. Jpn Kokai Tokkyo Koho

zeolite

M. Kimura 87,36,018,

Feb.

17,1987;

Appl.

Aug.

9, 1985

Crystalline aluminosilicate zeolite is prepared from an aqueous reaction mixture containing a SiOp source, an A1203 source, an alkali metal source and poly(oxyalkylene)diamine (av.mol.wt. lOO-10,000) having a general formula H2N(CH*),0Z,(CH2),NH2 (Z = poly(oxyalkylene) group, n = 1, 2, or 3, m = integer).