WO1999056869A1 - Liquid-absorbent granules - Google Patents

Liquid-absorbent granules Download PDF

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Publication number
WO1999056869A1
WO1999056869A1 PCT/GB1999/001183 GB9901183W WO9956869A1 WO 1999056869 A1 WO1999056869 A1 WO 1999056869A1 GB 9901183 W GB9901183 W GB 9901183W WO 9956869 A1 WO9956869 A1 WO 9956869A1
Authority
WO
WIPO (PCT)
Prior art keywords
weight
granules
per cent
absorbent
sulphate
Prior art date
Application number
PCT/GB1999/001183
Other languages
French (fr)
Inventor
Henry Dent
George William Wallace
Original Assignee
W. Hawley & Son Limited
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.)
Filing date
Publication date
Application filed by W. Hawley & Son Limited filed Critical W. Hawley & Son Limited
Priority to AU37161/99A priority Critical patent/AU3716199A/en
Publication of WO1999056869A1 publication Critical patent/WO1999056869A1/en

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
    • B01J20/2803—Sorbents comprising a binder, e.g. for forming aggregated, agglomerated or granulated products
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
    • B01J20/043—Carbonates or bicarbonates, e.g. limestone, dolomite, aragonite
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
    • B01J20/045—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium containing sulfur, e.g. sulfates, thiosulfates, gypsum
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
    • B01J20/103—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate comprising silica
    • B01J20/106—Perlite
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
    • B01J20/12—Naturally occurring clays or bleaching earth
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
    • B01J20/28004—Sorbent size or size distribution, e.g. particle size
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
    • B01J20/28011—Other properties, e.g. density, crush strength
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
    • B01J2220/42—Materials comprising a mixture of inorganic materials

Definitions

  • the granules produced according to the present invention are an effective absorbent for spillages of oils, chemicals and other liquids.
  • the granules have the particular benefit that a major part of the raw materials for their manufacture are byproducts of other industrial operations and therefore do not require to be mined or quarried.
  • the granules are comparatively lightweight and may weigh only half the weight of other available absorbent granules, enabling them to be readily carried by any man or woman to the site of the spillage.
  • a dry powder comprising the following ingredients : -

Abstract

Liquid-absorbent granules are disclosed which comprise at least 50 per cent by weight of an absorbent industrial waste product comprising calcium carbonate or calcium sulphate, up to 50 per cent by weight of a lightweight aggregate comprising expanded perlite or exfoliated vermiculite, from 1 to 3 per cent by weight of potassium sulphate or of a cementitious binder, and from 1 to 3 per cent by weight of water. A process for the manufacture of such granules is also disclosed which comprises mixing together in solid form the absorbent industrial waste product, light weight aggregate and potassium sulphate or cementitious binder, and subsequently spraying water on to the resulting mix, in such relative proportions to yield absorbent granules of the above composition.

Description

LIQUID-ABSORBENT GRANULES
The present invention relates to absorbent granules suitable for cleaning up spillages of oils, chemicals or other liquids and to a process for the manufacture of such granules.
There are many granules available on the market for cleaning up liquid spillages. Most such granules are of naturally occurring minerals, for example sepiolite, attapulgite, bentonite or olivine, which are obtained by mining or quarrying at sites throughout the world.
It is an object of the present invention to provide an alternative form of absorbent granules, which is environmentally friendly in that it uses waste materials rather than such specially mined minerals. The invention further includes a process for the manufacture of these absorbent granules, by means of which such granules may be more economically produced than by prior such processes for the production of absorbent granules. Other advantageous features of the novel process and product will be apparent from the following description.
The absorbent granules according to the present invention comprise : -
(a) at least 50 per cent by weight of an absorbent industrial waste product comprising calcium carbonate -2- or calcium sulphate;
(b) up to 50 per cent by weight of a lightweight aggregate comprising expanded perlite or exfoliated vermiculite;
(c) from 1 to 3 per cent by weight of potassium sulphate or of a cementitious binder; and
(d) from 1 to 3 per cent by weight of water.
The process according to the present invention comprises mixing together in solid form said absorbent industrial waste product, said lightweight aggregate and said potassium sulphate or cementitious binder and subsequently spraying water on to the resulting mix, in such relative proportions as to yield absorbent granules of the foregoing composition.
In the foregoing absorbent granules and in the process for producing them, the weight of the absorbent industrial waste product comprising calcium carbonate or calcium sulphate preferably amounts to from 70 per cent to 80 per cent of the weight of the granules . The weight of the lightweight aggregate preferably amounts to from 30 per cent to 20 per cent, and the weight of the potassium sulphate or cementitious binder preferably amounts to from 1.5 to 2.5 per cent, of the weight of the granules.
In carrying out the process according to the present invention, the quantity of water sprayed on to the solid mix preferably lies within the range from 3 to 10 per cent of the weight of the solid mix, more preferably from 3 to 7 per cent of that weight. A proportion of the water evaporates from the resulting wet mix but, as a result of absorption of water into the mix, the retained percentage of water lies within the specified range of 1 to 3 per cent of the weight of the produc . Further mixing together of the solid components in the presence of the added water allows the materials to agglomerate and thereby together to form dry absorbent granules. Preferably the size of the resulting granules lies within the range from 1 to 10mm, more preferably from 2 to 6mm. Preferably the granules also contain some fines of a particle size below 1mm. The quantity of such fines preferably amounts to up to 1 per cent, preferably up to 5 per cent, by weight of the product.
The absorbent industrial waste product which is the primary component of the liquid-absorbent granules according to the present invention may for example be of calcium carbonate obtained as a by-product in the crushing and milling of limestone, or of calcium sulphate in the form of a by-product arising in the manufacture of hydrofluoric and in the most recent processes for producing ozone-friendly gases. Large quantities of these by-products are usually disposed of in landfill sites, in particular when the by-product in question is a very fine material having a size of less than 150 microns. Such very fine materials are of particular value as a component of the absorbent granules according to the present invention.
The lightweight aggregate which is the second component of the absorbent granules of the present invention is an expanded perlite or an exfoliated vermiculite. Perlite and vermiculite are minerals which occur naturally throughout the world and which are subsequently subjected to a heating process to yield the expanded or exfoliated product, which typically has a density from 30 to 180kg/m3.
The lightweight aggregate acts as a seed about which the industrial waste product agglomerates . This agglomeration and the bonding of the waste product to the aggregate is greatly assisted by the potassium sulphate, which acts as an accelerator, or by the cementitious binder. The choice between using potassium sulphate on the one hand and a cementitious binder on the other should take account of the chemical nature of the industrial waste product which is the main component of the granules . When the waste product is exclusively calcium sulphate or comprises that compound as a major part of the waste product, for example in the form of equal amounts of calcium sulphate and calcium carbonate, then it is preferred to use potassium sulphate. However, when the waste product is exclusively or mainly calcium carbonate, then the use of a cementitious binder is preferred. The binder may, for example, be a sulphate-resistant cement or starch.
The granules produced according to the present invention are an effective absorbent for spillages of oils, chemicals and other liquids. The granules have the particular benefit that a major part of the raw materials for their manufacture are byproducts of other industrial operations and therefore do not require to be mined or quarried. The granules are comparatively lightweight and may weigh only half the weight of other available absorbent granules, enabling them to be readily carried by any man or woman to the site of the spillage.
The process according to the invention has the important advantage that the components of the granules do not require to be heated in order to bond them together. The inclusion of potassium sulphate accelerator or of a cementitious binder makes the use of heat unnecessary, thereby saving a valuable resource which must otherwise be expended.
In use, the liquid-absorbent granules according to the invention are placed upon the spilled material and allowed to absorb that material until they become saturated. Absorption begins immediately and then, after saturation, the granules may be left for a period to allow them to dry, whereafter they may be lifted for disposal as landfill. The fines present in the product assist in the complete removal of the spillage and ensure that no person or vehicle can slip on the cleaned area. - 5 -
The larger particles may then absorb the bulk of the spilled liquid while the fines remove the residue.
The invention will now be further described and illustrated by means of the following Example, which describes, by way of example only, one preferred form of the process and product according to the present invention and wherein percentages are by weight.
Example
A dry powder was formed comprising the following ingredients : -
Absorbent industrial waste calcium sulphate: 74 per cent
Expanded perlite: 25 per cent
Potassium sulphate: 1 per cent
These ingredients were blended in a low-shear drum rotating at 3 rpm for 15 minutes and then a fine spray of water amounting to about 5 per cent of the weight of the dry mix was added to the mix during continued blending over a period of a further 45 minutes. Dry absorbent granules of an average particle size of approximately 5mm were formed.
The density of the initial waste calcium sulphate was approximately 1000kg/m3 and that of the perlite was approximately 100kg/m3. In this Example, the density of the product granules was approximately 350 to 450kg/m3. By varying the densities of the chosen starting materials and by varying their relative proportions in the mix, finished granules having densities within the range 250 to 750kg/m3, preferably of the order of 350 to 500kg/m3, may be made. A 20-litre bag of such a preferred product will weigh about 10kg, which weight is within or below the requirements of United Kingdom Health and Safety Executive regulations for manually- carried or manually-lifted bags.
In use, the granules are spread upon the spilled liquid material and the material is absorbed until the saturation point is reached. The granules may then be left to dry out until their outer surface is dry. In this form, if necessary mixed with other materials, they may safely be disposed of by land-fill.

Claims

-7-CLAIMS
1. Absorbent granules comprising:
(a) at least 50 per cent by weight of an absorbent industrial waste product comprising calcium carbonate or calcium sulphate;
(b) up to 50 per cent by weight of a lightweight aggregate comprising expanded perlite or exfoliated vermiculite;
(c) from 1 to 3 per cent by weight of potassium sulphate or of a cementitious binder; and
(d) from 1 to 3 per cent by weight of water.
2. Granules according to claim 1, wherein the weight of the absorbent industrial waste product comprising calcium carbonate or calcium sulphate amounts to from 70 per cent to 80 per cent of the weight of the granules.
3. Granules according to claim 1 or 2, wherein the weight of the lightweight aggregate amounts to from 30 per cent to 20 per cent of the weight of the granules.
4. Granules according to any one of the preceding claims, wherein the weight of the potassium sulphate or cementitious binder amounts to from 1.5 to 2.5 per cent of the weight of the granules .
5. Granules according to any one of the preceding claims, wherein the size of the resulting granules lies within the range from 1 to 10mm.
6. Granules according to claim 5, wherein the size of the resulting granules lies within the range from 2 to 6mm.
7. Granules according to any one of the preceding claims, wherein the granules also contain some fines of a particle size below 1mm.
8. Granules according to claim 7, wherein the quantity of fines amounts to up to 1 per cent by weight of the product.
9. Granules according to claim 8, wherein the quantity of fines amounts to up to 5 per cent by weight of the product.
10. Granules according to any one of the preceding claims, wherein the binder is a sulphate-resistant cement or starch.
11. Absorbent granules substantially as hereinbefore described.
12. A process for the manufacture of absorbent granules comprising:
(a) at least 50 per cent by weight of an absorbent industrial waste product comprising calcium carbonate or calcium sulphate;
(b) up to 50 per cent by weight of a lightweight aggregate comprising expanded perlite or exfoliated vermiculite;
(c) from 1 to 3 per cent by weight of potassium sulphate or of a cementitious binder; and
(d) from 1 to 3 per cent by weight of water,
the process comprising mixing together in solid form said absorbent industrial waste product, said lightweight aggregate and said potassium sulphate or cementitious binder and subsequently spraying water on to the resulting mix, in such relative proportions as to yield absorbent granules of the foregoing composition.
13. A process according to claim 12, wherein the weight of the absorbent industrial waste product comprising calcium carbonate or calcium sulphate amounts to from 70 per cent to 80 per cent of the weight of the granules.
14. A process according to claim 12 or 13, wherein the weight of the lightweight aggregate amounts to from 30 per cent to 20 per cent of the weight of the granules .
15. A process according to any one of claims 12 to 14, wherein the weight of the potassium sulphate or cementitious binder amounts to from 1.5 to 2.5 per cent of the weight of the granules .
16. A process according to any one of claims 12 to 15, wherein the quantity of water sprayed on to the solid mix lies within the range from 3 to 10 per cent of the weight of the solid mix.
17. A process according to claim 16, wherein the quantity of water sprayed on to the solid mix lies within the range from 3 to 7 per cent of the weight of the solid mix.
18. A process for the manufacture of absorbent granules, the process substantially as hereinbefore described.
PCT/GB1999/001183 1998-05-06 1999-05-04 Liquid-absorbent granules WO1999056869A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU37161/99A AU3716199A (en) 1998-05-06 1999-05-04 Liquid-absorbent granules

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB9809493.1 1998-05-06
GB9809493A GB9809493D0 (en) 1998-05-06 1998-05-06 Liquid-absorbant granules

Publications (1)

Publication Number Publication Date
WO1999056869A1 true WO1999056869A1 (en) 1999-11-11

Family

ID=10831414

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/GB1999/001183 WO1999056869A1 (en) 1998-05-06 1999-05-04 Liquid-absorbent granules

Country Status (3)

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AU (1) AU3716199A (en)
GB (1) GB9809493D0 (en)
WO (1) WO1999056869A1 (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007056634A2 (en) * 2005-11-03 2007-05-18 Michael Heiman Perlite composition and method of making the same
US11345877B2 (en) * 2016-09-08 2022-05-31 Morehouse School Of Medicine Cleaning composition, method of making and use thereof

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3673095A (en) * 1970-07-20 1972-06-27 Ralph H Archer Oil and grease absorbing composition comprising sphagnum moss, calcined gypsum and perlite
DE3021377A1 (en) * 1980-06-06 1981-12-17 Gebr. Knauf Westdeutsche Gipswerke, 8715 Iphofen Expanded perlite granulate coated with sulphate or silicate - and used as adsorbent, esp. for excretions from small domestic animals such as cats
DE3633027A1 (en) * 1986-09-29 1988-06-16 Walter Kraemer Process and apparatus for the continuous preparation of mineral granules from gypsum-containing materials and use of the granules obtained
US4925826A (en) * 1987-04-24 1990-05-15 Firma Gipswerk Embsen Gmbh & Co. Baustoffproduktion Kg Method of producing an adsorbent from bloating minerals and calcium sulfate hemihydrate
US5035804A (en) * 1990-09-17 1991-07-30 Clnzall Corporation Oil spill water treatment
FR2722112A1 (en) * 1994-07-08 1996-01-12 Inst Francais Du Petrole Desulphurisation of gases

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3673095A (en) * 1970-07-20 1972-06-27 Ralph H Archer Oil and grease absorbing composition comprising sphagnum moss, calcined gypsum and perlite
DE3021377A1 (en) * 1980-06-06 1981-12-17 Gebr. Knauf Westdeutsche Gipswerke, 8715 Iphofen Expanded perlite granulate coated with sulphate or silicate - and used as adsorbent, esp. for excretions from small domestic animals such as cats
DE3633027A1 (en) * 1986-09-29 1988-06-16 Walter Kraemer Process and apparatus for the continuous preparation of mineral granules from gypsum-containing materials and use of the granules obtained
US4925826A (en) * 1987-04-24 1990-05-15 Firma Gipswerk Embsen Gmbh & Co. Baustoffproduktion Kg Method of producing an adsorbent from bloating minerals and calcium sulfate hemihydrate
US5035804A (en) * 1990-09-17 1991-07-30 Clnzall Corporation Oil spill water treatment
FR2722112A1 (en) * 1994-07-08 1996-01-12 Inst Francais Du Petrole Desulphurisation of gases

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007056634A2 (en) * 2005-11-03 2007-05-18 Michael Heiman Perlite composition and method of making the same
WO2007056634A3 (en) * 2005-11-03 2007-11-29 Michael Heiman Perlite composition and method of making the same
US7736574B2 (en) 2005-11-03 2010-06-15 Michael Heiman Perlite composition and method of making the same
US11345877B2 (en) * 2016-09-08 2022-05-31 Morehouse School Of Medicine Cleaning composition, method of making and use thereof

Also Published As

Publication number Publication date
AU3716199A (en) 1999-11-23
GB9809493D0 (en) 1998-07-01

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