GB1586236A - Creation of Inventions and Patents with Artificial Intelligence

GB1586236A – Method for producing synthetic sodium aluminosilicate ion-exchange material from calcined kaolin clay
– Google Patents

GB1586236A – Method for producing synthetic sodium aluminosilicate ion-exchange material from calcined kaolin clay
– Google Patents
Method for producing synthetic sodium aluminosilicate ion-exchange material from calcined kaolin clay

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Publication number
GB1586236A

GB1586236A
GB26857/77A
GB2685777A
GB1586236A
GB 1586236 A
GB1586236 A
GB 1586236A
GB 26857/77 A
GB26857/77 A
GB 26857/77A
GB 2685777 A
GB2685777 A
GB 2685777A
GB 1586236 A
GB1586236 A
GB 1586236A
Authority
GB
United Kingdom
Prior art keywords
clay
sodium
process according
calcined
iron
Prior art date
1976-06-29
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)

Expired

Application number
GB26857/77A
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)

Engelhard Minerals and Chemicals Corp

Original Assignee
Engelhard Minerals and Chemicals Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
1976-06-29
Filing date
1977-06-27
Publication date
1981-03-18

1977-06-27
Application filed by Engelhard Minerals and Chemicals Corp
filed
Critical
Engelhard Minerals and Chemicals Corp

1981-03-18
Publication of GB1586236A
publication
Critical
patent/GB1586236A/en

Status
Expired
legal-status
Critical
Current

Links

Espacenet

Global Dossier

Discuss

239000004927
clay
Substances

0.000
title
claims
description
84

NLYAJNPCOHFWQQ-UHFFFAOYSA-N
kaolin
Chemical compound

O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O
NLYAJNPCOHFWQQ-UHFFFAOYSA-N
0.000
title
claims
description
39

235000012211
aluminium silicate
Nutrition

0.000
title
claims
description
25

239000005995
Aluminium silicate
Substances

0.000
title
claims
description
24

238000005342
ion exchange
Methods

0.000
title
claims
description
10

229910000503
Na-aluminosilicate
Inorganic materials

0.000
title
claims
description
8

239000000429
sodium aluminium silicate
Substances

0.000
title
claims
description
8

235000012217
sodium aluminium silicate
Nutrition

0.000
title
claims
description
8

URGAHOPLAPQHLN-UHFFFAOYSA-N
sodium aluminosilicate
Chemical compound

[Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O
URGAHOPLAPQHLN-UHFFFAOYSA-N
0.000
title
claims
description
8

239000000463
material
Substances

0.000
title
description
10

238000004519
manufacturing process
Methods

0.000
title
description
7

XEEYBQQBJWHFJM-UHFFFAOYSA-N
Iron
Chemical compound

[Fe]
XEEYBQQBJWHFJM-UHFFFAOYSA-N
0.000
claims
description
55

HEMHJVSKTPXQMS-UHFFFAOYSA-M
Sodium hydroxide
Chemical compound

[OH-].[Na+]
HEMHJVSKTPXQMS-UHFFFAOYSA-M
0.000
claims
description
30

229910052742
iron
Inorganic materials

0.000
claims
description
25

239000010457
zeolite
Substances

0.000
claims
description
23

VYPSYNLAJGMNEJ-UHFFFAOYSA-N
Silicium dioxide
Chemical compound

O=[Si]=O
VYPSYNLAJGMNEJ-UHFFFAOYSA-N
0.000
claims
description
22

HNPSIPDUKPIQMN-UHFFFAOYSA-N
dioxosilane;oxo(oxoalumanyloxy)alumane
Chemical compound

O=[Si]=O.O=[Al]O[Al]=O
HNPSIPDUKPIQMN-UHFFFAOYSA-N
0.000
claims
description
22

229910021536
Zeolite
Inorganic materials

0.000
claims
description
20

239000013078
crystal
Substances

0.000
claims
description
18

239000012535
impurity
Substances

0.000
claims
description
18

238000000034
method
Methods

0.000
claims
description
17

229910000323
aluminium silicate
Inorganic materials

0.000
claims
description
12

239000011734
sodium
Substances

0.000
claims
description
12

239000000377
silicon dioxide
Substances

0.000
claims
description
11

DGAQECJNVWCQMB-PUAWFVPOSA-M
Ilexoside XXIX
Chemical compound

C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+]
DGAQECJNVWCQMB-PUAWFVPOSA-M
0.000
claims
description
10

PNEYBMLMFCGWSK-UHFFFAOYSA-N
aluminium oxide
Inorganic materials

[O-2].[O-2].[O-2].[Al+3].[Al+3]
PNEYBMLMFCGWSK-UHFFFAOYSA-N
0.000
claims
description
10

238000001354
calcination
Methods

0.000
claims
description
10

229910052708
sodium
Inorganic materials

0.000
claims
description
10

229910052783
alkali metal
Inorganic materials

0.000
claims
description
7

239000002245
particle
Substances

0.000
claims
description
7

-1
alkali metal aluminosilicate
Chemical class

0.000
claims
description
6

238000006243
chemical reaction
Methods

0.000
claims
description
6

GRWZHXKQBITJKP-UHFFFAOYSA-L
dithionite(2-)
Chemical compound

[O-]S(=O)S([O-])=O
GRWZHXKQBITJKP-UHFFFAOYSA-L
0.000
claims
description
6

239000007844
bleaching agent
Substances

0.000
claims
description
5

238000005188
flotation
Methods

0.000
claims
description
5

230000002378
acidificating effect
Effects

0.000
claims
description
4

238000004061
bleaching
Methods

0.000
claims
description
3

239000003795
chemical substances by application
Substances

0.000
claims
description
3

RTAQQCXQSZGOHL-UHFFFAOYSA-N
Titanium
Chemical group

[Ti]
RTAQQCXQSZGOHL-UHFFFAOYSA-N
0.000
claims
description
2

229910000272
alkali metal oxide
Inorganic materials

0.000
claims
description
2

239000007787
solid
Substances

0.000
claims
description
2

239000010936
titanium
Substances

0.000
claims
description
2

229910052719
titanium
Inorganic materials

0.000
claims
description
2

239000011541
reaction mixture
Substances

0.000
claims
4

229910052782
aluminium
Inorganic materials

0.000
claims
3

XAGFODPZIPBFFR-UHFFFAOYSA-N
aluminium
Chemical compound

[Al]
XAGFODPZIPBFFR-UHFFFAOYSA-N
0.000
claims
3

229910052710
silicon
Inorganic materials

0.000
claims
2

239000010703
silicon
Substances

0.000
claims
2

XUIMIQQOPSSXEZ-UHFFFAOYSA-N
Silicon
Chemical compound

[Si]
XUIMIQQOPSSXEZ-UHFFFAOYSA-N
0.000
claims
1

238000010438
heat treatment
Methods

0.000
claims
1

LIVNPJMFVYWSIS-UHFFFAOYSA-N
silicon monoxide
Chemical class

[Si-]#[O+]
LIVNPJMFVYWSIS-UHFFFAOYSA-N
0.000
claims
1

229910052814
silicon oxide
Inorganic materials

0.000
claims
1

KKCBUQHMOMHUOY-UHFFFAOYSA-N
sodium oxide
Chemical compound

[O-2].[Na+].[Na+]
KKCBUQHMOMHUOY-UHFFFAOYSA-N
0.000
claims
1

229910001948
sodium oxide
Inorganic materials

0.000
claims
1

238000005660
chlorination reaction
Methods

0.000
description
8

235000011121
sodium hydroxide
Nutrition

0.000
description
8

230000015572
biosynthetic process
Effects

0.000
description
7

239000003054
catalyst
Substances

0.000
description
6

XLYOFNOQVPJJNP-UHFFFAOYSA-N
water
Substances

O
XLYOFNOQVPJJNP-UHFFFAOYSA-N
0.000
description
6

239000007789
gas
Substances

0.000
description
5

239000000047
product
Substances

0.000
description
5

229910001868
water
Inorganic materials

0.000
description
5

IJGRMHOSHXDMSA-UHFFFAOYSA-N
Atomic nitrogen
Chemical compound

N#N
IJGRMHOSHXDMSA-UHFFFAOYSA-N
0.000
description
4

ZAMOUSCENKQFHK-UHFFFAOYSA-N
Chlorine atom
Chemical compound

[Cl]
ZAMOUSCENKQFHK-UHFFFAOYSA-N
0.000
description
4

239000004115
Sodium Silicate
Substances

0.000
description
4

GWEVSGVZZGPLCZ-UHFFFAOYSA-N
Titan oxide
Chemical compound

O=[Ti]=O
GWEVSGVZZGPLCZ-UHFFFAOYSA-N
0.000
description
4

239000000460
chlorine
Substances

0.000
description
4

229910052801
chlorine
Inorganic materials

0.000
description
4

229910052500
inorganic mineral
Inorganic materials

0.000
description
4

239000011707
mineral
Substances

0.000
description
4

235000010755
mineral
Nutrition

0.000
description
4

239000000376
reactant
Substances

0.000
description
4

NTHWMYGWWRZVTN-UHFFFAOYSA-N
sodium silicate
Chemical compound

[Na+].[Na+].[O-][Si]([O-])=O
NTHWMYGWWRZVTN-UHFFFAOYSA-N
0.000
description
4

229910052911
sodium silicate
Inorganic materials

0.000
description
4

VEXZGXHMUGYJMC-UHFFFAOYSA-N
Hydrochloric acid
Chemical compound

Cl
VEXZGXHMUGYJMC-UHFFFAOYSA-N
0.000
description
3

239000011248
coating agent
Substances

0.000
description
3

238000000576
coating method
Methods

0.000
description
3

230000000694
effects
Effects

0.000
description
3

238000012545
processing
Methods

0.000
description
3

239000007921
spray
Substances

0.000
description
3

239000000126
substance
Substances

0.000
description
3

238000003786
synthesis reaction
Methods

0.000
description
3

OYPRJOBELJOOCE-UHFFFAOYSA-N
Calcium
Chemical group

[Ca]
OYPRJOBELJOOCE-UHFFFAOYSA-N
0.000
description
2

VEXZGXHMUGYJMC-UHFFFAOYSA-M
Chloride anion
Chemical compound

[Cl-]
VEXZGXHMUGYJMC-UHFFFAOYSA-M
0.000
description
2

239000002253
acid
Substances

0.000
description
2

ANBBXQWFNXMHLD-UHFFFAOYSA-N
aluminum;sodium;oxygen(2-)
Chemical compound

[O-2].[O-2].[Na+].[Al+3]
ANBBXQWFNXMHLD-UHFFFAOYSA-N
0.000
description
2

238000004458
analytical method
Methods

0.000
description
2

239000011575
calcium
Substances

0.000
description
2

229910052791
calcium
Inorganic materials

0.000
description
2

229910052799
carbon
Inorganic materials

0.000
description
2

239000007795
chemical reaction product
Substances

0.000
description
2

239000000470
constituent
Substances

0.000
description
2

239000002270
dispersing agent
Substances

0.000
description
2

239000012065
filter cake
Substances

0.000
description
2

238000007885
magnetic separation
Methods

0.000
description
2

229910001510
metal chloride
Inorganic materials

0.000
description
2

229910052757
nitrogen
Inorganic materials

0.000
description
2

238000013021
overheating
Methods

0.000
description
2

238000005120
petroleum cracking
Methods

0.000
description
2

239000002002
slurry
Substances

0.000
description
2

229910001388
sodium aluminate
Inorganic materials

0.000
description
2

VZGDMQKNWNREIO-UHFFFAOYSA-N
tetrachloromethane
Chemical compound

ClC(Cl)(Cl)Cl
VZGDMQKNWNREIO-UHFFFAOYSA-N
0.000
description
2

VHUUQVKOLVNVRT-UHFFFAOYSA-N
Ammonium hydroxide
Chemical compound

[NH4+].[OH-]
VHUUQVKOLVNVRT-UHFFFAOYSA-N
0.000
description
1

OKTJSMMVPCPJKN-UHFFFAOYSA-N
Carbon
Chemical compound

[C]
OKTJSMMVPCPJKN-UHFFFAOYSA-N
0.000
description
1

UGFAIRIUMAVXCW-UHFFFAOYSA-N
Carbon monoxide
Chemical compound

[O+]#[C-]
UGFAIRIUMAVXCW-UHFFFAOYSA-N
0.000
description
1

KZBUYRJDOAKODT-UHFFFAOYSA-N
Chlorine
Chemical compound

ClCl
KZBUYRJDOAKODT-UHFFFAOYSA-N
0.000
description
1

241001092591
Flota
Species

0.000
description
1

BPQQTUXANYXVAA-UHFFFAOYSA-N
Orthosilicate
Chemical compound

[O-][Si]([O-])([O-])[O-]
BPQQTUXANYXVAA-UHFFFAOYSA-N
0.000
description
1

229910019142
PO4
Inorganic materials

0.000
description
1

238000002441
X-ray diffraction
Methods

0.000
description
1

239000003513
alkali
Substances

0.000
description
1

229910052910
alkali metal silicate
Inorganic materials

0.000
description
1

150000001340
alkali metals
Chemical class

0.000
description
1

HPTYUNKZVDYXLP-UHFFFAOYSA-N
aluminum;trihydroxy(trihydroxysilyloxy)silane;hydrate
Chemical compound

O.[Al].[Al].O[Si](O)(O)O[Si](O)(O)O
HPTYUNKZVDYXLP-UHFFFAOYSA-N
0.000
description
1

239000000908
ammonium hydroxide
Substances

0.000
description
1

229910002091
carbon monoxide
Inorganic materials

0.000
description
1

239000003575
carbonaceous material
Substances

0.000
description
1

239000003153
chemical reaction reagent
Substances

0.000
description
1

239000002734
clay mineral
Substances

0.000
description
1

239000013065
commercial product
Substances

0.000
description
1

238000007796
conventional method
Methods

0.000
description
1

238000005260
corrosion
Methods

0.000
description
1

230000007797
corrosion
Effects

0.000
description
1

238000005336
cracking
Methods

0.000
description
1

238000002425
crystallisation
Methods

0.000
description
1

230000008025
crystallization
Effects

0.000
description
1

239000008367
deionised water
Substances

0.000
description
1

229910021641
deionized water
Inorganic materials

0.000
description
1

239000003599
detergent
Substances

0.000
description
1

229910001649
dickite
Inorganic materials

0.000
description
1

239000012013
faujasite
Substances

0.000
description
1

238000001914
filtration
Methods

0.000
description
1

238000005189
flocculation
Methods

0.000
description
1

230000016615
flocculation
Effects

0.000
description
1

238000009291
froth flotation
Methods

0.000
description
1

229910052621
halloysite
Inorganic materials

0.000
description
1

IXCSERBJSXMMFS-UHFFFAOYSA-N
hydrogen chloride
Substances

Cl.Cl
IXCSERBJSXMMFS-UHFFFAOYSA-N
0.000
description
1

229910000041
hydrogen chloride
Inorganic materials

0.000
description
1

NMCUIPGRVMDVDB-UHFFFAOYSA-L
iron dichloride
Chemical class

Cl[Fe]Cl
NMCUIPGRVMDVDB-UHFFFAOYSA-L
0.000
description
1

229910052622
kaolinite
Inorganic materials

0.000
description
1

230000014759
maintenance of location
Effects

0.000
description
1

239000011159
matrix material
Substances

0.000
description
1

238000005259
measurement
Methods

0.000
description
1

229910052751
metal
Inorganic materials

0.000
description
1

239000002184
metal
Substances

0.000
description
1

239000000203
mixture
Substances

0.000
description
1

230000007935
neutral effect
Effects

0.000
description
1

230000001473
noxious effect
Effects

0.000
description
1

235000021317
phosphate
Nutrition

0.000
description
1

150000003013
phosphoric acid derivatives
Chemical class

0.000
description
1

239000002244
precipitate
Substances

0.000
description
1

230000035484
reaction time
Effects

0.000
description
1

230000009257
reactivity
Effects

0.000
description
1

230000001172
regenerating effect
Effects

0.000
description
1

238000004062
sedimentation
Methods

0.000
description
1

QPILZZVXGUNELN-UHFFFAOYSA-M
sodium;4-amino-5-hydroxynaphthalene-2,7-disulfonate;hydron
Chemical compound

[Na+].OS(=O)(=O)C1=CC(O)=C2C(N)=CC(S([O-])(=O)=O)=CC2=C1
QPILZZVXGUNELN-UHFFFAOYSA-M
0.000
description
1

238000010561
standard procedure
Methods

0.000
description
1

239000007858
starting material
Substances

0.000
description
1

230000003068
static effect
Effects

0.000
description
1

239000000725
suspension
Substances

0.000
description
1

230000002194
synthesizing effect
Effects

0.000
description
1

238000013022
venting
Methods

0.000
description
1

238000005406
washing
Methods

0.000
description
1

Classifications

C—CHEMISTRY; METALLURGY

C01—INORGANIC CHEMISTRY

C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C

C01B33/00—Silicon; Compounds thereof

C01B33/20—Silicates

C01B33/26—Aluminium-containing silicates, i.e. silico-aluminates

C01B33/28—Base exchange silicates, e.g. zeolites

C01B33/2807—Zeolitic silicoaluminates with a tridimensional crystalline structure possessing molecular sieve properties; Isomorphous compounds wherein a part of the aluminium ore of the silicon present may be replaced by other elements such as gallium, germanium, phosphorus; Preparation of zeolitic molecular sieves from molecular sieves of another type or from preformed reacting mixtures

C01B33/2815—Zeolitic silicoaluminates with a tridimensional crystalline structure possessing molecular sieve properties; Isomorphous compounds wherein a part of the aluminium ore of the silicon present may be replaced by other elements such as gallium, germanium, phosphorus; Preparation of zeolitic molecular sieves from molecular sieves of another type or from preformed reacting mixtures of type A (UNION CARBIDE trade name; corresponds to GRACE’s types Z-12 or Z-12L)

Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS

Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC

Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS

Y10S423/00—Chemistry of inorganic compounds

Y10S423/24—LTA, e.g. A, alpha, ZK-4, ZK-21, ZK-22

Description

– PATENT SPECIFICATION l) – 1 586 236
2 7 J u N e ( 21) Application No ‘ 26857177 ( 22) Filed 27 June 1977 ( 19) ( 31) Convention Application No 700862 ( 32) Filed 29 Juue 1976 in ( 33) United States of America (US) ( 44) Complete Specification published 18 March 1981 ‘ ( 51) INT CL 3 C Oi B 33/28 ( 52) Index at acceptance C 1 A 421 524 CE D 10 D 31 G 13 G 13 D 10 G 50 M 7-P 10 ( 71) Inventors MPHILLIP JAMESON and:
FRED R HUEGE ( 54) METHOD FOR PRODUCING SYNTHETIC SODIUM ALUMINOSILICATE ION-EXCHANGE MATERIAL FROM CALCINED KAOLIN’ CLAY ( 71) We, ENGELHARD MINERALS AND CHEMICALS CORPORATION, a corporation organized and existing ‘under the laws of the State of Delaware, United States of America, of Menlo Park, Edison, New Jersey, United States of America, do hereby declare the invention, for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement: –
This invention is directed to the synthesis of hydrated alkali metal silicate ion-exchange material in the form of white crystals using discolored ion-contaminated naturally occurring kaolin clay as a source of alumina and silica.
There is currently interest in using certain sodium aluminosilicate ion-exchange materials in detergent compositions-e g see Belgian Patent Specification No 814,874.
The preferred sodium aluminosilicate ionexchange material has the formula Na,2 (A 10 Si O 2)2 27 H 2 O which corresponds to the formula of sodium zeolite A as described in U S Patent Specification No.
2,882,243 The ion-exchange builder material may be produced, according to the Belgian patent, from high purity sodium aluminate, sodium silicate, sodium hydroxide and water It is well known that zeolitic aluminosilicates such as sodium zeolite A can be obtained at relatively low cost by using minerals as sources of silica and/or alumina.
Kaolin clay calcined to the so-called ‘metakaolin” state or condition is an example and it is useful when reacted with sodium hydroxide solution as the source of both silica and alumina in the production of zeolite A.
Obviously a sodium aluminosilicate product used as a builder in a washing composition intended for consumer use must have a white, bright appearance in order to satisfy aesthetic demands Petroleum cracking catalysts must be low in iron, When a synthetic crystalline aluminosilicate zeolite is present as a constituent of such catalyst, it is desirable to use a zeolite that has a low iron content The following patent specifications des 50 cribe methods for producing finely divided crystals of hydrated sodium ‘ aluminosilicates such as those known as zeolites’A and X from calcined kaolin clay, and sodium hydroxide ‘solution: U S 3,185,544, U S 55 3,114,603.
Methods for removing iron impurities from calcined kaolin clay by high temperature chlorination are known in the art and are described in several patent specifications 60 of which the following are exemplary: U S.
3,236,606, U S 3,816,093.
Russian Patent Specification No 199,127 describes a method for producing a calcined clay product of improved color and purity 65 The kaolin is calcined at 900 to 1000 C, chlorinated with chlorine and hydrogen chloride in a fluidized bed at 600 to 700 C, and ‘the calcined clay is leached, with a solution of caustic soda Titania and iron 70 are removed along with silica.
To the best of our knowledge, it has not been possible prior to our invention to produce white crystals of zeolitic alkali metal aluminosilicates from calcined clay even 75 when the original clay, prior to calcination, had been extensively purified by means such as flotation or magnetic separation to remove discrete colored impurities and has undergone extensive conventional chemical bleach 80 treatment to remove iron impurities For example, we attempted to produce crystals of sodium zeolite A using as a reactant a material produced-by calcining commercial high brightness paper coating grades of 85 kaolin clay These coating clays had been produced by subjecting impure kaolin clay to froth flotation to remove discrete colored impurities and after flotation iron stain was removed from the clay by a conventional 90 dithionite bleach treatment The coating clays had brightness values of about 90 percent (as determined by the well-known TAP Pl procedure) However, after they had e:
es t 1,586,236 been calcined to reactive (metakaolin) condition and reacted with sodium hydroxide solution, the fine crystals of sodium zeolite A that were produced had a brightness of only 70 percent Moreover, it was found that the brightness of the starting clay could not be used to predict the brightness of the crystalline sodium aluminosilicate reaction product.
Thus, we succeeded in producing crystals that had a brightness of 80 percent from starting clays having a brightness below 90 percent However, crystals having a desired brightness of 90 percent or above could not be obtained from any of the commercially available kaolin clays we tested.
The present invention provides a process for producing crystals of an ion-exchange crystalline alkali metal aluminosilicate from kaolin clay containing iron impurity, the process comprising calcining the clay to metakaolin condition, chlorinating the calcined clay in a gas-solid reaction at a temperature in the range of 600 to 980 WC to volatilize iron impurities from the clay, and reacting the chlorinated calcined clay with a source of alkali metal oxide and optionally additional sources of silica and alumina to produce said alkali metal aluminosilicate ‘ It is believed that, whereas small amounts of iron colored impurities in the clay matrix or otherwise occluded in the structure of the clay mineral have a minimal effect on the brightness of the clay, when the clay is calcined and then used as a reactant in the synthesis of a zeolitic aluminosilicate the iron becomes finely disseminated throughout the crystalline reaction product and has a discoloring effect that is materially more pronounced than when such impurities were originally occluded in the structure of the clay particles We have found that iron impurities in clay that cannot be removed by conventional methods are, however, amenable to removal by volatilization as a chloride when the clay is calcined to socalled “metakaolin” state or condition, this permitting the production of good purity synthetic metalloaluminosilicates from calcined kaolin clay The specified chlorination temperature range permits retention of the metakaolin form during the chlorination step The calcination to metakaolin form and the chlorination of the resulting calcined material are preferably both carried out in the temperature range of 600 to 980 WC.
In’ one preferred embodiment of the invention the chlorinated calcined clay is used as the sole source of silica and alumina, and zeolite A is crystallized In other embodiments zeolite A is crystallized using the chlorinated calcined clay as the major source of both silica and alumina, synthetic sources of silica and/or alumina such as sodium silicate and sodium aluminate being used along with the calcined clay In still other preferred embodiments ion-exchange zeolites such as zeolites X or Y which have higher Si O 2/A 12,0 molar ratios than zeolite A are prepared by using the chlorinated calcined clay and an additional source of silica and/ 70 or alumina.
The term “metakaolin” as used herein is described in U S Patent Specification
No 3,338,672.
All brightness values quoted herein were 75 obtained with an ELREPHO meter using TAPP Pl standard method T-646 m-54 Reflectance to light at 457 millimicrons is used in making brightness measurements.
The starting clay, which may be a soft or 80 hard kaolin clay crude, should preferably be refined at least to the extent that gross impurities are removed Superficial iron stain may be removed by chemical bleach using, for example, a dithionite salt at an acidic 85 p H Acid grades of bleached clay may be preferred when synthesizing fine metalloaluminates as a finely divided precipitate, for example particles in the range of 1 to 15 microns These grades are obtained by de 90 watering acid flocculated clay pulps such as the pulps produced during conventional dithionite (hydrosulfite) bleaching of kaolin clay to remove superficial iron stain These pulps can be dewatered by filtration, produc 95 ing acidic filter cakes which are washed, dried and pulverized Alternatively the washed filter cakes can be dispersed in water to form slurries which are dried in spray dryers When using spray dried grades of 100 kaolin clay, it may be necessary to avoid the use of conventional clay dispersants such as sodium silicate, sodium hydroxide or sodium condensed phosphates since these materials may cause undesirable fluxing during cal 105 cination and/or chlorinization Ammonium hydroxide is a recommended dispersant for the production of spray dried kaolin clay used as a starting material for the synthesis of finely divided crystals of zeolitic alumino 110 silicate When a product having premium brightness is desired, discrete titania mineral particles and/or those of iron should also be removed from the clay before the clay is calcined Known means such as froth flota 115 tion, selective flocculation, magnetic separation or combinations of such processing steps may be employed to remove discrete impurities (such as colored titaniferous and iron impurities) associates with kaolin clay 120 Normally such beneficiation is carried out while the clay is in the form of a neutral or alkaline slurry or suspension After beneficiation the clay may be acidified, bleached and dewatered It is within the scope of the 125 invention, however, to use unbleached clay which has not undergone such beneficiation.
The iron content of a typical bleached, beneficiated soft kaolin clay (expressed as Fe 2 a 0) is generally in the range of 0 2 per 130 1,586,236 cent to 0 3 percent based on the weight of the clay after being calcined to anhydrous condition at 980 WC So-called “gray” kaolins usually analyze 0 7 to 0 9 percent by weight Fe 2 08 after beneficiation and bleaching.
The purified starting clay is composed predominantly of a mineral of the kaolin family, for example kaolinite, halloysite, nacrite or dickite These are hydrated crystalline aluminosilicates of the approximate empirical formula A 120 2 Si O 2 2 H 20 (except for certain halloysites which contain more water).
As mentioned, the clay must be calcined to a substantially anhydrous condition before metal impurities are volatilized as chloride and this calcination must usually be carried out at a temperature of 600 to 980 WC in order to ensure that the calcined clay is in metakaolin condition This reaction is strongly endothermic Preferred calcination temperatures are in the range of 650 to 800 C with time varying with the equipment used At temperatures above 800 C.
there is a possibility of local overheating Which could impair the reactivity of the calcined clay Rotary calciners are useful, as are fluidized bed calciners It is necessary to remove the off-gases containing water volatilized from the clay during calcination before the clay is chloridized since water evolved during chlorination will interfere with the formation of metal chlorides in subsequent processing.
It is not necessary to cool the clay discharged from the calciner before it is treated at elevated temperature with a gas capable of reacting with impurities, especially iron in the clay For economic reasons it is preferable not to cool the clay between calcination and chloridization Suitable chloridizing agents known in the art include chlorine, hydrochloric acid and carbon tetrachloride A carbonaceous material such as carbon monoxide or carbon may be introduced during chlorination in known manner to accelerate the formation of iron chlorides.
Means are provided for venting the off-gases which include metal chlorides formed during chloridization Chloridization can be carried out in static bed, rotary or fluidized bed furnaces equipped with means to minimize leakage of noxious gases and for removing off-gases The furnace should be lined with corrosion-resistant material The chloridization is carried out at a temperature above 600 C, for example 750 C to 850 C, in order to achieve sufficiently rapid reaction.
An upper limit of chloridization temperature is about 980 C since local overheating may occur at higher temperature Preferably, the Fe 2 03 analysis of the chloridized clay is below 0 1 percent by weight.
After chloridization is complete, residual chloridizing agent may be swept from the treated clay by passing air or nitrogen through the clay The treated clay is cooled to at least a temperature below about 100 C.
before it is used as a reactant to form the zeolite crystals.
When the calcined clay is employed to 70 produce zeolite A it must be in metakaolin condition and thus the temperature of the clay during chlorination must be in the range of 600 to 980 C Reaction conditions such as described in U S 3,114,603 (supra) may 75 be used to synthesize sodium zeolite A.
When synthetic faujasite (such as zeolite X) is to be produced, additional sources of alumina and silica must be employed with the metakaolin, as is known in the art 80 Reference is made to U S 3,185,544 For example, the metakaolin may be reacted with sodium hydroxide solution and sodium silicate to produce crystals of zeolite X Low iron synthetic faujasites produced in accord 85 ance with this invention can be valuable when used as a constituent of a cracking catalyst, such as the catalysts of U S.
3,140,249 to Plank et al Low iron content of petroleum cracking catalysts is desirable 90 because iron has an undesirable effect on the regenerating characteristics of the catalysts, as is known in the art.
After crystallization of the desired sodium aluminosilicate is completed, the crystals 95 should be washed free of alkali and they can be dried mildly, for example at a temperature of about 100 C.
The following example of the production of high brightness crystals of sodium zeolite 100 A from kaolin clay is given for illustrative purposes and is not to be considered as limiting the invention to the particular reaction conditions and processing equipment used O Example
The starting clay was a pulverized acid grade of high purity hydrated kaolin clay.
The hydrated clay was a commercial product 110 (ASP 170) having a brightness of 90 percent and containing 90 percent by weight of particles finer than 2 microns (equivalent spherical diameter) The clay was produced by “Ultraflotation” (as described in U S 115 Patent Specification 2,990,958) to remove discrete colored titanium and iron impurities.
After flotation the clay was bleached in an acidic pulp with a dithionite bleach reagent.
Iron content (Fe 2,) was 0 33 percent 120 (anhydrous weight basis).
A vertical tube furnace was loaded with a charge of 1800 g of the hydrated clay The furnace was turned on and the bed was fluidized with nitrogen during the preheat 125 period (about 1-1 hours) The temperature of the clay charge was controlled at about 800 C to assure formation of metakaolin.
When the charge was at temperature, chlorine gas ( 90 percent N 2 and 10 percent 130 1,586,236 C 12) was introduced at a rate of 100 cc /min.
for a total chlorination period of 8 hours.
The chlorine treated clay analyzed 0 05 percent Fe 203, and had a brightness’ of 96 8 percent Acid-soluble A 1203 content was 44 8 percent, indicating the calcined clay was in metakaolin condition.
The chlorine treated calcined clay ( 140 g) was added to 1260 g of sodium hydroxide solution ( 10 percent weight) and heated to F while being agitated The molar ratio of the reactants was as follows: 1 i Na 2 O:
1.0 A 120 2 Si O 2:40 H 2 O The reaction time (crystallizing time) was 5 hours at 180 F.
Samples were taken at hourly intervals to determine zeolite formation as determined by X-ray diffraction.
After 5 hours of crystallizing time, the sample was filtered and washed with deionized water The sample was dried overnight at 160 F.
Product analysis was as follows:
Brightness, %o 95 2 Average particle size, microns (as determined by sedimentation) 3 1 H 2 O, % (determined at 800 C) 18 30 Free alkalinity, % 0 02 p H 10 3 Calcium exchange capacity 330 calcium exchange capacity is reported as mg Ca CO 3/gm product (anhydrous)

Claims (9)

WHAT WE CLAIM IS: –

1 A process for producing crystals of an ion-exchange crystalline alkali metal aluminosilicate from kaolin clay containing iron impurity, the process comprising calcining the clay to metakaolin condition, chlorinating the calcined clay in a gas-solid reaction at a temperature in the range of 600 to 980 C to volatilize iron impurities from the clay, and reacting the chlorinated calcined clay with a source of alkali metal oxide and optionally additional sources of silica and alumina to produce said alkali metal aluminosilicate.

2 A process according to claim 1 wherein finely divided particles of synthetic crystalline sodium aluminosilicate zeolite are prepared by heating an aqueous alkaline reaction mixture consisting essentially of oxides of aluminum, silicon and sodium until finely divided zeolite crystals form the major portion of said aluminum and silicon oxides being provided by the inclusion in the reaction mixture of finely divided particles of the chlorinated calcined clay.

3 A process according to claim 2 wherein finely divided crystals of sodium zeolite A are formed.

4 A process according to claim 3 wherein the chlorinated calcined clay is the sole source of oxides of aluminum and silicon in the reaction mixture and sodium hydroxide is the sole source of sodium oxide.

A process according to claim 3 or 4 wherein the reaction mixture is formed by slurrying the chlorinated calcined clay in sodium hydroxide solution of about 10 weight percent concentration.

6 A process according to any preceding claim wherein the calcined clay is chlorinated at 750 to 850 C.

7 A process according to any preceding claim wherein the kaolin clay for calcination is obtained by removing discrete colored titanium and iron-bearing impurities from naturally-occurring hydrated kaolin clay by flotation and bleaching the flotation beneficiated clay with a dithionite bleach in an aqueous acidic medium.

8 A process for producing crystals of ion-exchange crystalline alkali metal aluminosilicate, the process being substantially as hereinbefore described in the Example.

9 Crystals of iron-exchange crystalline alkali metal aluminosilicate obtained by a process according to any of claims 1 to 8.
REDDIE & GROSE, Agents for the Applicants, 16 Theobalds Road, London WC 1 X 8 PL.
Printed for Her Majesty’s Stationery Office by Burgess & Son (Abingdon), Ltd -1981.
Published at The Patent Offlce, 25 Southampton Buildings, London, WC 2 A l AY, from which copies may be obtained:
: ‘:
:, : i

GB26857/77A
1976-06-29
1977-06-27
Method for producing synthetic sodium aluminosilicate ion-exchange material from calcined kaolin clay

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1982-08-16
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Preparation of zeolites

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PROCESS FOR PRODUCING LOW IRON ZEOLITHIC ALUMINUM SILICATES

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METHOD FOR PRODUCING ZEOLITH A FROM KAOLIN

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Process for the halogen modification of aluminophosphate molecular sieves and a product so produced

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