CA1280584C - Compositions and method for neutralization and solidification of hazardous acid spills - Google Patents
Compositions and method for neutralization and solidification of hazardous acid spillsInfo
- Publication number
- CA1280584C CA1280584C CA000536193A CA536193A CA1280584C CA 1280584 C CA1280584 C CA 1280584C CA 000536193 A CA000536193 A CA 000536193A CA 536193 A CA536193 A CA 536193A CA 1280584 C CA1280584 C CA 1280584C
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- Canada
- Prior art keywords
- clay
- gal
- composition
- spills
- mgo
- Prior art date
- 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.)
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
- C04B28/10—Lime cements or magnesium oxide cements
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/24—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing alkyl, ammonium or metal silicates; containing silica sols
- C04B28/26—Silicates of the alkali metals
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/32—Materials not provided for elsewhere for absorbing liquids to remove pollution, e.g. oil, gasoline, fat
-
- G—PHYSICS
- G21—NUCLEAR PHYSICS; NUCLEAR ENGINEERING
- G21F—PROTECTION AGAINST X-RADIATION, GAMMA RADIATION, CORPUSCULAR RADIATION OR PARTICLE BOMBARDMENT; TREATING RADIOACTIVELY CONTAMINATED MATERIAL; DECONTAMINATION ARRANGEMENTS THEREFOR
- G21F9/00—Treating radioactively contaminated material; Decontamination arrangements therefor
- G21F9/04—Treating liquids
- G21F9/06—Processing
- G21F9/12—Processing by absorption; by adsorption; by ion-exchange
-
- 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/91—Use of waste materials as fillers for mortars or concrete
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Structural Engineering (AREA)
- Inorganic Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Engineering & Computer Science (AREA)
- High Energy & Nuclear Physics (AREA)
- Physics & Mathematics (AREA)
- Public Health (AREA)
- Health & Medical Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Processing Of Solid Wastes (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Detergent Compositions (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
ABSTRACT
This invention relates to novel composition and methods for neutralization and solidification of hazardous acidic spills. A dry particulate composition of varying reaction grades of alkaline compounds and varying grades of absorptive materials may be used to neutralize and solidify acidic spills, solidify the spills and render them harmless.
These compositions may be applied to the spills by fire-extinguisher-like delivery devices which spread the compositions on the spills from a relatively safe distance without splattering the hazardous material.
This invention relates to novel composition and methods for neutralization and solidification of hazardous acidic spills. A dry particulate composition of varying reaction grades of alkaline compounds and varying grades of absorptive materials may be used to neutralize and solidify acidic spills, solidify the spills and render them harmless.
These compositions may be applied to the spills by fire-extinguisher-like delivery devices which spread the compositions on the spills from a relatively safe distance without splattering the hazardous material.
Description
1~80584 EAC~GROUND OF THE INVENTION
1. Field of the Invention This invention relates to novel compositions and the novel methods of their use ~or neutralization and clean-up o~
hazardous acidic spills.
1. Field of the Invention This invention relates to novel compositions and the novel methods of their use ~or neutralization and clean-up o~
hazardous acidic spills.
2. Prior Art Various compositions have been known in the past to be useful for the clean-up of hazardous organic waste materials.
Some prior art references describe methods for neutralizing acid spills. Several references describe compositions for neutralizing and solidifying liquid wastes, particularly raw sewage. However, these prior art compositions and methods for acid waste neutralization entail certain disadvantages. United ~B
"
1~8058~
1 ¦¦ States Patent No. 3,994,821 (Seidenberger~ relates to the 2 1l control and clean-up of a mineral acid spill using a granular
Some prior art references describe methods for neutralizing acid spills. Several references describe compositions for neutralizing and solidifying liquid wastes, particularly raw sewage. However, these prior art compositions and methods for acid waste neutralization entail certain disadvantages. United ~B
"
1~8058~
1 ¦¦ States Patent No. 3,994,821 (Seidenberger~ relates to the 2 1l control and clean-up of a mineral acid spill using a granular
3 ~1l composition containing 36.5 to 47.5~ by weight ground marble
4 1~ chips, about 3~ to 45.5% by weight granular soda, about 16.5 to i 21.5% by weight granular magnesia and about 0.008 to 0.012% by 6 1 weight of an appropriate normally solid pH indicator. Ground 8 marble chips are composed of calcium carbonate. The granular spill control composition of this patent is employed to control 9 and clean-up substantially all of a spilled mineral acid by applying the granular composition to this spill surface from 11 the perimeter of the spill inward in a quantity sufficient to 12 absorb all the spilled acid. Although the spill is generally 13 neutralized by this granular composition, the acids having a 14 high heat of neutralization may not be completely neutralized, thus continuing to pose a threat. Further, the method of 16 1 applying this composition necessitates workers' exposure to the 17 spill.
19 United States Patent No. 4,210,460 (Seidenberger) relates to a composition for controlling and clean-up of a 21 spill of hydrofluoric acid. The composition may be in one of 22 two forms: an aqueous solution and a powdered composition.
23 The aqueous solution is composed of about 20 to 29~ by weight 24 of calcium acetate and about 71-65% by weight of water. The powdered composition is composed of about 99.90 to 99.99% by 26 weight powdered magnesia and about 0.01 to 0.1~ by weight of an 27 appropriate normally solid pH indicator. The powdered 28 magnesium oxide composition can be sprinkled onto the 29 hydrofluoric acid spill. The pH indicator will indicate by color change when an essentially safe pH condition has been - 2 - (0082W) l~B0584 1 ¦ reached. This composition also has the disadvantages of 2 I less-than total neutralization and the risk of exposure to the 3 ! spill.
4 United States Patent No. 4,207,116 (Been et al.) described a granulated absorbent material composed of cement, 6 an inorganic water-absorbing swelling agent, sand or ground 7 stone, water and, optionally, dye stuffs and other additives.
8 The composition is mixed to form a paste, the paste is allowed 9 to harden and the hardened material dried and granulated. The cement hardens with the water and acts as a skeleton-forming 11 substance which provides the granulated material with 12 hardness. The sand or ground stone acts as an inert blending 13 agent to lower the cost price of the granulated material. The 14 water-absorbing swelling agent, which can be a clay, aids in absorbing liquids such as water, oil and for absorbing smells.
16 All types of clays may be used as inorganic swelling agents 17 such as sepiolite, montmorillonite, kaolins, diatomaceous earth 18 and bentonite. This composition is contemplated for use in cat 19 litter, rather than in containing, neutralizing and solidifying hazardous acid spills.
21 United States Patent No. 3,980,558 (Thompson) relates 22 to a method foridisposing of liquid or semi-liquid waste 23 containing soluble toxic materials containing the waste and a 24 solidifying agent which consists of a hydraulic cement which will set upon standing to a contiguous rock-like solid 26 consistency. This prevents the waste from leaching. The term 27 "hydraulic cement" refers to all mixtures of lime, silica, and 28 alumina, or of lime and magnesia, silica, alumina and iron 29 oxide and cther like mixtures of ingredients. A particularly preferred mixture is Type I Portland Cement. The patent states _ (0082W) ~' ' -.
1~8058a~
l ¦ that the process of this invention is particularly useful in 2 j disposing of aqueous sludge waste from chemical p~ocesses for 3 ¦ the manufacture of phosphoric acids, particularly aqueous ,4 ¦ filter and sludges, which normally contain high levels o~
19 United States Patent No. 4,210,460 (Seidenberger) relates to a composition for controlling and clean-up of a 21 spill of hydrofluoric acid. The composition may be in one of 22 two forms: an aqueous solution and a powdered composition.
23 The aqueous solution is composed of about 20 to 29~ by weight 24 of calcium acetate and about 71-65% by weight of water. The powdered composition is composed of about 99.90 to 99.99% by 26 weight powdered magnesia and about 0.01 to 0.1~ by weight of an 27 appropriate normally solid pH indicator. The powdered 28 magnesium oxide composition can be sprinkled onto the 29 hydrofluoric acid spill. The pH indicator will indicate by color change when an essentially safe pH condition has been - 2 - (0082W) l~B0584 1 ¦ reached. This composition also has the disadvantages of 2 I less-than total neutralization and the risk of exposure to the 3 ! spill.
4 United States Patent No. 4,207,116 (Been et al.) described a granulated absorbent material composed of cement, 6 an inorganic water-absorbing swelling agent, sand or ground 7 stone, water and, optionally, dye stuffs and other additives.
8 The composition is mixed to form a paste, the paste is allowed 9 to harden and the hardened material dried and granulated. The cement hardens with the water and acts as a skeleton-forming 11 substance which provides the granulated material with 12 hardness. The sand or ground stone acts as an inert blending 13 agent to lower the cost price of the granulated material. The 14 water-absorbing swelling agent, which can be a clay, aids in absorbing liquids such as water, oil and for absorbing smells.
16 All types of clays may be used as inorganic swelling agents 17 such as sepiolite, montmorillonite, kaolins, diatomaceous earth 18 and bentonite. This composition is contemplated for use in cat 19 litter, rather than in containing, neutralizing and solidifying hazardous acid spills.
21 United States Patent No. 3,980,558 (Thompson) relates 22 to a method foridisposing of liquid or semi-liquid waste 23 containing soluble toxic materials containing the waste and a 24 solidifying agent which consists of a hydraulic cement which will set upon standing to a contiguous rock-like solid 26 consistency. This prevents the waste from leaching. The term 27 "hydraulic cement" refers to all mixtures of lime, silica, and 28 alumina, or of lime and magnesia, silica, alumina and iron 29 oxide and cther like mixtures of ingredients. A particularly preferred mixture is Type I Portland Cement. The patent states _ (0082W) ~' ' -.
1~8058a~
l ¦ that the process of this invention is particularly useful in 2 j disposing of aqueous sludge waste from chemical p~ocesses for 3 ¦ the manufacture of phosphoric acids, particularly aqueous ,4 ¦ filter and sludges, which normally contain high levels o~
5 1 arsenic and dissolved arsenic compounds, as well as hydrogen
6 sulfide and other sulphur compounds. Although this composition
7 contains and solidifies waste, it is not essentially a
8 neutralizing composition. Further, it requires solidification
9 by mixing with the waste materials. This is impractical where there has been a spill, which does not lend itself to mixing.
11 United States Patent No. 4,518,508 (Conner) describes 12 a method for treating aqueous liquid and semi-liquid wastes by 13 solidification. The method of the invention described requires 14 that a dry water-reactive solidification agent comprising cement, a dry water absorbent material and a powdered alkali 16 metal silicate sufficient to convert the mixture into a 17 consolidated chemically and physically stable solid product are 18 added to aqueous liquid or semi-liquid waste. The waste can 19 then be solidified and set, forming a synthetic rock-like material. This composition acts to neutralize the acidity of 21 the waste in part. However, it may not render complete 22 neutralization.i Another disadvantage is that must be mixed 23 with the waste.
24 United States Patent No. 4,547,290 (Pichat~ describes a process~eor solidifying strongly acid or alkaline liquid 26 waste. According to this patent, clays can be used directly in 27 a very acidic or strongly alkaline aqueous waste to make it 28 possible to transform this waste into stable solid materials.
29 According to the invention, a clay material is dispersed in the waste by stirring, and the waste neutralized. A hydraulic ~ 4 ~ (0082W) ':., I
lZ805~3~
1 and/or calcium binder addition then follows. All types of 2 j fresh or dried clays can be used, such as pure clays, mixtures 3 ¦ including attapulgites and metal carbonates. During the , 4 ¦ neutralization process lime, ground limestone, calcium 5 ¦ carbonate base wastes, calcium silicate and/or aluminates may 6 be added, particularly to acidic wastes. The third stage of 7 the process causes the material to be capable of 8 solidification. Materials such as Portland cement may be added 9 to the pasty mass that has been formed. Again, this composition must be mixed to form a slurry in order to 11 neutralize and solidify the waste, necessitating close contact 12 with the waste. This method is therefore impractical when 13 applied to acid spills.
14 United States Patent No 3,837,872 (Conner) describes an aqueous solution of an alkaline metal silicate mixed with 16 waste material and a silicate setting agent which causes the 17 silicate and waste material to react with each other. This 18 invention relates particularly to the treatment of raw human 19 waste. Accotding to the invention, wastes are mixed with an alkaline metal silicate such as sodium silicate which, in the 21 presence of a silicate setting agent, causes the mixture to 22 undergo consolidation and solidification. The setting agents 23 include acids or acidic materials which cause gelation of the 24 silicate. Setting agents include Portland cement, lime, gypsum and calcium carbonate and aluminum, iron, magnesium nickel, 26 chromium, manganese or copper compounds. This method also has 27 the disadvantage of requiring close contact with wastes for 28 solidification as well as actual mixing. This method cannot be 29 used for spill control.
- 5 - (0082W) 1~80584 1 ~ United States Patent No. 4,297,304 (Scheffler et al.) 2 l describes a method for solidifying high and medium 3 ¦ radioactivity and/or actinide-containing aqueous waste 4 1 concentrates for fine-grained solid wastes suspended in water for final noncontaminating storage. The waste concentrates or 6 suspensions are set by evaporation to form an evaporate having 7 a water content in the range between 40 and 80 percent by 8 weight and a solid content with a metal iron and/or metal oxide 9 component between 10 and 30 percent by weight of the evaporate. The clay-like substances include silica, alumina 11 and portland cement. The metal oxides can include MgO. The pH
12 of the evaporate is then set to between 5 and 10, and kneaded 13 with a clay-like substance containing a small quantity of 14 cement or a mixture of clay-like substance with a small quantity of cement containing an additive for suppressing the 16 volatility of alkalis. Molded bodies are produced from the 17 kneaded mass, heat treated, calcined and fired. The bodies are 18 then enclosed on all sides in a dense, continuous ceramic or 19 metallic matrix. This method is not advantageous for use with acid spills: the composition must be mixed with the waste for 21 solidification.
22 Thus, prior art methods have several disadvantages 23 when applied to hazardous acidic spills. A composition which 24 can neutralize several types of acids, which can be applied from a safe distance without danger to the workers is not 26 suggested in the prior art.
29 This invention is directed to novel compositions and methods of using the compositions to neutralize and solidify - 6 - t0082W) ~ 1~ 80 58 ~
1 hazardous organic spills so as to substantially prevent the 2 spread of such a spill during neutralization and 3 I solidification. The compositions and methods of this invention 4 can be applied from a safe distance and limit the rate of neutralization. Thus allowing substantially all of the spill 6 to be reacted and neutralized.
7 The novel compositions of this invention contain the 8 following: about 0 to 80% alkaline earth Qxide, about 0 to 30~
9 alkali metal carbonate, about 0 to 10% highly absorptive silica or clay, about 5 to 30% less absorptive clay, about 0.5 to 2%
11 hydrophobic lubricant, and about 0 to 50% portland cement.
12 The alkaline earth oxides which may be used in the 13 compositions of this invention conclude, e.g., magnesium oxide 14 and calcium oxide. These components serve as neutralizing agents for the hazardous acidic spills to be treated.
16 Portland cement is a form of magnesium oxide which is 17 violently reactive and serves to neutralize acidic components 18 in hazardous acidic spills. It can, for example, neutralize 19 less reactive acids.
The alkali metal carbonate compounds used in the 21 compositions of this invention also act as neutralizing 22 agents. Preferably, potassium carbonate or sodium carbonate 23 are used. These compounds also function as solubilizing agents 24 to maintain solubility of the neutralizing bases.
Bicarbonates and sesquicarbonates may also be used in the 26 composition for these purposes.
27 Highly absorptive silicas or clays such as calcium 28 silicate are used in the compositions of this invention as 29 fibrous absorption age~ts. Calclum silicate absorbs a tremendous amount of liquid in relation to its weight. Silicas , (0082W) I B
lZ80584 1 ll and clays may also be used as absorption agents. These 2 1 absorption agents aid the neutralization reaction by absorbing 3 , some of the less acidic materials during neutralization. This 4 ;l allows the water of neutralization to continue to drive the S ¦ neutralization reaction to completion. Therefore, 6 ¦ substantially all of the acid will be neutralized and 7 l¦ solidified rather than only the most reactive acids.
8 1! Another absorptive clay having a slower rate of 9 i~ absorption than the calcium silicate group, such as attapulgas
11 United States Patent No. 4,518,508 (Conner) describes 12 a method for treating aqueous liquid and semi-liquid wastes by 13 solidification. The method of the invention described requires 14 that a dry water-reactive solidification agent comprising cement, a dry water absorbent material and a powdered alkali 16 metal silicate sufficient to convert the mixture into a 17 consolidated chemically and physically stable solid product are 18 added to aqueous liquid or semi-liquid waste. The waste can 19 then be solidified and set, forming a synthetic rock-like material. This composition acts to neutralize the acidity of 21 the waste in part. However, it may not render complete 22 neutralization.i Another disadvantage is that must be mixed 23 with the waste.
24 United States Patent No. 4,547,290 (Pichat~ describes a process~eor solidifying strongly acid or alkaline liquid 26 waste. According to this patent, clays can be used directly in 27 a very acidic or strongly alkaline aqueous waste to make it 28 possible to transform this waste into stable solid materials.
29 According to the invention, a clay material is dispersed in the waste by stirring, and the waste neutralized. A hydraulic ~ 4 ~ (0082W) ':., I
lZ805~3~
1 and/or calcium binder addition then follows. All types of 2 j fresh or dried clays can be used, such as pure clays, mixtures 3 ¦ including attapulgites and metal carbonates. During the , 4 ¦ neutralization process lime, ground limestone, calcium 5 ¦ carbonate base wastes, calcium silicate and/or aluminates may 6 be added, particularly to acidic wastes. The third stage of 7 the process causes the material to be capable of 8 solidification. Materials such as Portland cement may be added 9 to the pasty mass that has been formed. Again, this composition must be mixed to form a slurry in order to 11 neutralize and solidify the waste, necessitating close contact 12 with the waste. This method is therefore impractical when 13 applied to acid spills.
14 United States Patent No 3,837,872 (Conner) describes an aqueous solution of an alkaline metal silicate mixed with 16 waste material and a silicate setting agent which causes the 17 silicate and waste material to react with each other. This 18 invention relates particularly to the treatment of raw human 19 waste. Accotding to the invention, wastes are mixed with an alkaline metal silicate such as sodium silicate which, in the 21 presence of a silicate setting agent, causes the mixture to 22 undergo consolidation and solidification. The setting agents 23 include acids or acidic materials which cause gelation of the 24 silicate. Setting agents include Portland cement, lime, gypsum and calcium carbonate and aluminum, iron, magnesium nickel, 26 chromium, manganese or copper compounds. This method also has 27 the disadvantage of requiring close contact with wastes for 28 solidification as well as actual mixing. This method cannot be 29 used for spill control.
- 5 - (0082W) 1~80584 1 ~ United States Patent No. 4,297,304 (Scheffler et al.) 2 l describes a method for solidifying high and medium 3 ¦ radioactivity and/or actinide-containing aqueous waste 4 1 concentrates for fine-grained solid wastes suspended in water for final noncontaminating storage. The waste concentrates or 6 suspensions are set by evaporation to form an evaporate having 7 a water content in the range between 40 and 80 percent by 8 weight and a solid content with a metal iron and/or metal oxide 9 component between 10 and 30 percent by weight of the evaporate. The clay-like substances include silica, alumina 11 and portland cement. The metal oxides can include MgO. The pH
12 of the evaporate is then set to between 5 and 10, and kneaded 13 with a clay-like substance containing a small quantity of 14 cement or a mixture of clay-like substance with a small quantity of cement containing an additive for suppressing the 16 volatility of alkalis. Molded bodies are produced from the 17 kneaded mass, heat treated, calcined and fired. The bodies are 18 then enclosed on all sides in a dense, continuous ceramic or 19 metallic matrix. This method is not advantageous for use with acid spills: the composition must be mixed with the waste for 21 solidification.
22 Thus, prior art methods have several disadvantages 23 when applied to hazardous acidic spills. A composition which 24 can neutralize several types of acids, which can be applied from a safe distance without danger to the workers is not 26 suggested in the prior art.
29 This invention is directed to novel compositions and methods of using the compositions to neutralize and solidify - 6 - t0082W) ~ 1~ 80 58 ~
1 hazardous organic spills so as to substantially prevent the 2 spread of such a spill during neutralization and 3 I solidification. The compositions and methods of this invention 4 can be applied from a safe distance and limit the rate of neutralization. Thus allowing substantially all of the spill 6 to be reacted and neutralized.
7 The novel compositions of this invention contain the 8 following: about 0 to 80% alkaline earth Qxide, about 0 to 30~
9 alkali metal carbonate, about 0 to 10% highly absorptive silica or clay, about 5 to 30% less absorptive clay, about 0.5 to 2%
11 hydrophobic lubricant, and about 0 to 50% portland cement.
12 The alkaline earth oxides which may be used in the 13 compositions of this invention conclude, e.g., magnesium oxide 14 and calcium oxide. These components serve as neutralizing agents for the hazardous acidic spills to be treated.
16 Portland cement is a form of magnesium oxide which is 17 violently reactive and serves to neutralize acidic components 18 in hazardous acidic spills. It can, for example, neutralize 19 less reactive acids.
The alkali metal carbonate compounds used in the 21 compositions of this invention also act as neutralizing 22 agents. Preferably, potassium carbonate or sodium carbonate 23 are used. These compounds also function as solubilizing agents 24 to maintain solubility of the neutralizing bases.
Bicarbonates and sesquicarbonates may also be used in the 26 composition for these purposes.
27 Highly absorptive silicas or clays such as calcium 28 silicate are used in the compositions of this invention as 29 fibrous absorption age~ts. Calclum silicate absorbs a tremendous amount of liquid in relation to its weight. Silicas , (0082W) I B
lZ80584 1 ll and clays may also be used as absorption agents. These 2 1 absorption agents aid the neutralization reaction by absorbing 3 , some of the less acidic materials during neutralization. This 4 ;l allows the water of neutralization to continue to drive the S ¦ neutralization reaction to completion. Therefore, 6 ¦ substantially all of the acid will be neutralized and 7 l¦ solidified rather than only the most reactive acids.
8 1! Another absorptive clay having a slower rate of 9 i~ absorption than the calcium silicate group, such as attapulgas
10 ~1 clay, is also preferably used in the compositions o~ this ~ invention. Fullers earth and perlite are other examples of 12 ,¦ less absorptive clays.
13 ! By varying the rates of absorption as a result of the 14 1 different clays present in the composition, the rate of 15 ! neutralization of the unabsorbed acids may be increased. As 16 , the more reactive acids are neutralized and the proqucts 17 ~ absorbed, the less reactive acids will desorb and react with 18 remaining base. This allows the neutralization reaction to be 19 1 constantly driven to completion without reaching equilibrium.
~0 ¦ This is due to the varying availabilities of reactants.
21 j A small amount of a hydrophobic lubricating agent such 22 as magnesium stearate, sodium or aluminum stearates, tricalcium 23 ' phosphate, octoates and the like may be added to the 24 ~ compositions to aid in making the particulates of this 25 ¦ composition free-flowing. The lubricating agent acts as a 26 !1 lubricant by imparting hydrophobicity to the particles and 27 il preventing them from sticking together.
28 ¦ The compositions of this invention contain several 29 1 reactivity grades of alkaline materials, e.g. magnesium oxide.
30 ¦ This allows a controlled and complete neutralization reaction.
'i - 8 - (0082W) '~
il ' , ., lZ80S84 1 I This allows the compositions of this invention to be used to 2 neutralize a large number of acids, each of which may have a 3 I different energy requirement for neutralization. Using the 4 il compositions of this invention, more reactive acids will be 5 il neutralized quickly, thus generating a heat of neutralization 6 j which may, in turn, encourage the neutralization of less 7 1¦ reactive materials. The presence of varying reactivity grades 8 1 of magnesium oxides allows this to occur gradually.
9 ~I An example of a preferred composition according to 10 j this invention is the following: 73.79~ MgO, 5% Na~CO,,
13 ! By varying the rates of absorption as a result of the 14 1 different clays present in the composition, the rate of 15 ! neutralization of the unabsorbed acids may be increased. As 16 , the more reactive acids are neutralized and the proqucts 17 ~ absorbed, the less reactive acids will desorb and react with 18 remaining base. This allows the neutralization reaction to be 19 1 constantly driven to completion without reaching equilibrium.
~0 ¦ This is due to the varying availabilities of reactants.
21 j A small amount of a hydrophobic lubricating agent such 22 as magnesium stearate, sodium or aluminum stearates, tricalcium 23 ' phosphate, octoates and the like may be added to the 24 ~ compositions to aid in making the particulates of this 25 ¦ composition free-flowing. The lubricating agent acts as a 26 !1 lubricant by imparting hydrophobicity to the particles and 27 il preventing them from sticking together.
28 ¦ The compositions of this invention contain several 29 1 reactivity grades of alkaline materials, e.g. magnesium oxide.
30 ¦ This allows a controlled and complete neutralization reaction.
'i - 8 - (0082W) '~
il ' , ., lZ80S84 1 I This allows the compositions of this invention to be used to 2 neutralize a large number of acids, each of which may have a 3 I different energy requirement for neutralization. Using the 4 il compositions of this invention, more reactive acids will be 5 il neutralized quickly, thus generating a heat of neutralization 6 j which may, in turn, encourage the neutralization of less 7 1¦ reactive materials. The presence of varying reactivity grades 8 1 of magnesium oxides allows this to occur gradually.
9 ~I An example of a preferred composition according to 10 j this invention is the following: 73.79~ MgO, 5% Na~CO,,
11 1 10% CaO, 5.5% attapulgas clay, 5.12% calcium silicate, and 0.5%
12 1 magnesium stearate. 45.25 pounds of this formula can
13 1 neutralize 2.95 gallons of sulfuric acid and elevate the pH to
14 1 7.30. It can also neutralize hydrochloric, nitric phosphoric,
15 , perchloric, acetic and hydrofluoric acids, inter alia.
16 1 The compositions of this invention are preferably
17 1 applied to the hazardous spills from a fire-extinguisher-like
18 ¦ vessel. They are preferably applied in the dry form in which
19 they are stored. They may be stored under pressure in a stored 0 vessel until used and/or pressurized by external gas through an 21 external expellent gas cartridge.
22 1 The size distribution of the particles of the 23 1 compositions of this invention allows them to be applied to 24 ,I spills in a "soft~ pattern, i.e. relatively spread out such that they cover a spill as it spreads without splattering the 26 1 spill and endangering handlers. The compositions should be 27 j applied from a distance of about 10 to 15 feet. The nozzle 28 ¦ velocity should be between about 30 and 50 feet/second. In 29 ¦ order to achieve this velocity, the particles should have a 30 ¦ size distribution between about-40 and +200 Tyler screen mesh 9 ~ (0082W) ;' "~
.
. , :
1'~80584 i siz~3.
, The particulate compositions of this invention may be 3 ', applied on a nitrogen gas stream. The particular specified 4 ~ size distribution will substantially assure the appropriate 5 ~1 flow rate and delivery pattern.
6 il The mode of application of the method of this 7 ¦ invention allows the control and neutralization of hazardous 8 i spills from a distance without causing splashing of the 9 hazardous materials during neutralization.
The following examples illustrate the compositions and 11 methods of this invention. Of course, they do not serve to 12 1 limit, but merely to demonstrate, the scope o~ the invention.
The following formulations were made and tested to 16 ¦ determine their suitability in the process of this invention in 17 i the following manner. Approximately two gallons (gal.) of acid 18 ¦ were mixed with about 26-30 pounds (lb) of the formulation.
19 The formulation/acid mixture was then mixed and allowed to proceed through the neutralization reaction. Ten grams of the 21 mixture was then diluted with 100 ml. deionized water. The pH
22 ~ was measured.
23 ¦ Formulations A - R set forth below were tested in this 24 ~ manner. Formulations A-R are described according to the weight 25 j percentage of each element. The term 20xlO0 indicates that 26 1 particle size distribution of MgO, as does ~Fine Grade-100".
27 1 The term ~attaclay~ indicates attapulgus clay. Silanox*is a 28 silicone-containing material available ~rom Cabot Co., ~oston, 29 Mass.
- 10 - (0082W) : * trade mark ~280584 1 !¦ The results of the testing are set forth in Table I.
2 , Table I indicates, from the left, the example number, the 3 i formulation used, the volume of acid to be neutralized, the 4 ,l initial weight of the formulation prior to discharge ~in lbs.
1 -0ZS.), the final weight of formulation actually discharged (in 6 1 lbs. -0ZS.), the percentage of formulation actually discharged, 7 I the initial pH and final pH of the formulation/acid mixture and 8 i observations concerning the test itself.
9 1 The percentage of formulation discharged indicates the 10 1 ability of the formulation to be efficiently dispersed onto the 11 ' spill. The differential in pH from the initial to the final 12 1 readings indicates the ability of the formulation to neutralize 13 ~ the spill. Table I demonstrates that the formulations of this 14 ij invention have excellent abilities to absorb and neutralize 15 I! acid spills. They are also easy to disperse over a spill from 16 1 a distance.
Formulation A: 73.39 MgO (20x100) 10.00 CaO
I 5.00 Na2CO, (dense) 21 ! 5.21 CaSiOJ
l 5.50 attaclay-coarse 22 ' i 0.50 Mg Stearate 23 ¦ Formulation B: 73.79 MgO (20x100) 10.00 CaO
24 ~ 10.00 Na2CO, dense l 5.71 CaSiOJ
25 , 0.50 Mg Stearate 26 I Formulation C: 65.00 MgO (20x100) 5.00 MgO (10-40) 27 I 15.26 CaO
5.00 Na2COJ-dense 28 ! 4.00 attaclay-coarse l 5.21 CaSiOJ
29 1 0.50 Mg Stearate - 11 - (0082W) ":
~;280S84 !
1 il FormUlation D: 62.50 MgO(20xlO0) , lO.Oo Mg Chem (10-49) 2 1 10.26 CaO
:, 5.00 Na2CO 3 -dense 3 ' 4.03 attaclay-coarse ,i 7.71 CaSiOl ,¦ 0.50 Mg Stearate 5 ~¦ Formulation E: 73.79 MgO(20xlO0) 'I 10.00 CaO
6 1l 5.00 Na2COJ-dense ~ 5.50 attaclay 7 , 5.21 CaSiO, i 0.50 Mg Stearate 8 i I Formulation F: 39.00 MgO(20xlO0) 9 j 39.00 MgO-(Fine Grade-100) l 9.00 Na2CO3-dense 10 , 10.00 attaclay-coarse l 3.00 Mg Stearate i Formulation G: 79.00 MgO(20xl00) 12 j 10.00 CaO
l 10.00 attaclay coarse 13 i 1.00 Tricalcium phosphate 14 i Formulation H: 39.00 MgO(20xl00) l 39.00 MgO(Fine Grade-100) 15 1 9.00 Na2COl-dense I 10.00 attaclay-coarse 16 ! 3.00 Tricalcium phosphate 17 Formulation I: 39.50 MgO(20xl00) 39.50 MgO(Fine Grade-100 18 10.00 CaO
5.00 NatCO3-dense 19 1 5.50 attaclay-course l 0.50 Mg Stearate ''O
Formulation K: 36.00 MgO(20xlO0) 21 36.00 MgO(Fine Grade-100) i 20.00 Na2CO 3 -dense 22 j . 5.00 Attaclay-coarse l 3.00 Tricalcium phosphate 23 .
i Formulation L: 36.00 MgO(20xlO0) 24 1 36.00 MgO(Fine Grade-100) ~ 5.00 CaO
25 ¦ 10.00 Na2CO,-dense 10.00 attaclay-coarse 26 ¦ 2.50 Tricalcium phosphate I 0.50 Silanox i Formulation M: 39.50 MgO(20xlO0) 28 39.50 MgO(Fine Grade-100) 8.00 CaO
29 5.00 Na2CO,-dense 5.00 attaclay-coarse 3.00 Tricalcium phosphate 0.50 Silanox - 12 - (0082W) .
i2130~84 1 ¦ Formulation N: 49.00 MgO~20xlOO) , 29.00 MgO(Fine Grade-100) 2 ~i g.oo Na2CO3-dense ii 10.00 attaclay-coarse 3 ~¦ 3.00 Magnesium Stearate , 4 ,,! Formulation P: 36.50 MgO~20xlOO) I 36.5D ~Q~Fine ~ade-l~O) 5 ~ 5.00 CaO
i 9.00 NazCO,-dense 6 ~ 12.50 attaclay-coarse l 0.50 Magnesium Stearate i Formulation Q: 36.50 MgO(20xlOO) 8 ! 36.50 MgO(Fine Grade-100) ~ 5.00 CaO
9 ¦ 9.00 NazCO3-dense I 12.50 attaclay-coarse 10 j D.50 Magnesium Stearat~e 11 ¦ Formulation Q: 31.50 MgO(20xlOO) i 31.50 MgO(Fine Grade-100) 12 ' 4.00 CaO
! 7.50 Na 2 CO 3 -dense 13 1 25.00 attaclay-coarse I 0.50 Magnesium Stearate I
23 j 2245 ~
I - 13- (008~w~
::`
1;~80S~3A
ExamDle ~1 yolume Wt. Agent Wt. Discharge % Dicharge DH~i) vH~f) Observations 1 A H2504 2 gal. 26-3 26-3 97.0 0.99 ô.ô5 Very hard 2 Z A H2504 2 gal, 27-0 26-9 98.4 0.86 a.57 Hard After agitation on 3 5 min from applicati on 14 3 B H250~ 2 gal, 30-0 28-7 94.8 0.82 9.26 Liquid left in pant, but absorbed after agitation 6 4 C H~504 2 gal, 30-0 29-9 98.5 0.98 9.26 Absorbed with stirring 7 5 D H250, 2 gal. 22-14 21-12 95.1 0.31 ô.34 Good deal of 8 remalning 9 6 A H2504 2 gal. 24-1 23-9 97.9 0.52 8.82 good solid 7 E HCl 2.5 gal. 25.0 24-12 99.0 6.00 8.81 semi-solid 0 hrs, can be 11 shoveled 8 E HCl 2 gal. 29-0 27-14 96.1 9.39 9.46 Absorbed with 12 agitation 13 9 E HCl 2 gal. 27-0 26-S 97.4 ô.90 9.14 Poor set 10 E H2504 2 gal. 29-0 27-10 95-3 0.52 9.35 Good 14 ll E H2S04 2 gal. 29-12 29-4 98.3 0.52 9.07 Grandular 12 E H3PO4 2 gal. 29-0 28-6 97-9 5.02 7.87 Easy to pick 16 13 G H3PO4 2 gal. 30-0 28-4 94.2 4.79 5.59 Some 17 remai n i ng mixing 18 14 H H2504 2 gal. 28-0 26-11 absorption 1 9 501 id ls H HCl 2 gal. 27-12 25-15 93.5 9.03 9.08 Soupy. but hardens in 24 21 hrs.
22 16 H H3PO4 2 gal. 28-8 27-4 95.6 4.96 6.74 Good 17 H HNO3 2 gal. 28-0 26-4 93.8 9.16 9.37 Good 23 18 H HCOOH 2 gal. 26-0 24-14 95.7 4.39 9.60 Good 24 19 H CH~CO~H 2 gal. 28-0 26-10 95.1 5.84 9.32 Good
22 1 The size distribution of the particles of the 23 1 compositions of this invention allows them to be applied to 24 ,I spills in a "soft~ pattern, i.e. relatively spread out such that they cover a spill as it spreads without splattering the 26 1 spill and endangering handlers. The compositions should be 27 j applied from a distance of about 10 to 15 feet. The nozzle 28 ¦ velocity should be between about 30 and 50 feet/second. In 29 ¦ order to achieve this velocity, the particles should have a 30 ¦ size distribution between about-40 and +200 Tyler screen mesh 9 ~ (0082W) ;' "~
.
. , :
1'~80584 i siz~3.
, The particulate compositions of this invention may be 3 ', applied on a nitrogen gas stream. The particular specified 4 ~ size distribution will substantially assure the appropriate 5 ~1 flow rate and delivery pattern.
6 il The mode of application of the method of this 7 ¦ invention allows the control and neutralization of hazardous 8 i spills from a distance without causing splashing of the 9 hazardous materials during neutralization.
The following examples illustrate the compositions and 11 methods of this invention. Of course, they do not serve to 12 1 limit, but merely to demonstrate, the scope o~ the invention.
The following formulations were made and tested to 16 ¦ determine their suitability in the process of this invention in 17 i the following manner. Approximately two gallons (gal.) of acid 18 ¦ were mixed with about 26-30 pounds (lb) of the formulation.
19 The formulation/acid mixture was then mixed and allowed to proceed through the neutralization reaction. Ten grams of the 21 mixture was then diluted with 100 ml. deionized water. The pH
22 ~ was measured.
23 ¦ Formulations A - R set forth below were tested in this 24 ~ manner. Formulations A-R are described according to the weight 25 j percentage of each element. The term 20xlO0 indicates that 26 1 particle size distribution of MgO, as does ~Fine Grade-100".
27 1 The term ~attaclay~ indicates attapulgus clay. Silanox*is a 28 silicone-containing material available ~rom Cabot Co., ~oston, 29 Mass.
- 10 - (0082W) : * trade mark ~280584 1 !¦ The results of the testing are set forth in Table I.
2 , Table I indicates, from the left, the example number, the 3 i formulation used, the volume of acid to be neutralized, the 4 ,l initial weight of the formulation prior to discharge ~in lbs.
1 -0ZS.), the final weight of formulation actually discharged (in 6 1 lbs. -0ZS.), the percentage of formulation actually discharged, 7 I the initial pH and final pH of the formulation/acid mixture and 8 i observations concerning the test itself.
9 1 The percentage of formulation discharged indicates the 10 1 ability of the formulation to be efficiently dispersed onto the 11 ' spill. The differential in pH from the initial to the final 12 1 readings indicates the ability of the formulation to neutralize 13 ~ the spill. Table I demonstrates that the formulations of this 14 ij invention have excellent abilities to absorb and neutralize 15 I! acid spills. They are also easy to disperse over a spill from 16 1 a distance.
Formulation A: 73.39 MgO (20x100) 10.00 CaO
I 5.00 Na2CO, (dense) 21 ! 5.21 CaSiOJ
l 5.50 attaclay-coarse 22 ' i 0.50 Mg Stearate 23 ¦ Formulation B: 73.79 MgO (20x100) 10.00 CaO
24 ~ 10.00 Na2CO, dense l 5.71 CaSiOJ
25 , 0.50 Mg Stearate 26 I Formulation C: 65.00 MgO (20x100) 5.00 MgO (10-40) 27 I 15.26 CaO
5.00 Na2COJ-dense 28 ! 4.00 attaclay-coarse l 5.21 CaSiOJ
29 1 0.50 Mg Stearate - 11 - (0082W) ":
~;280S84 !
1 il FormUlation D: 62.50 MgO(20xlO0) , lO.Oo Mg Chem (10-49) 2 1 10.26 CaO
:, 5.00 Na2CO 3 -dense 3 ' 4.03 attaclay-coarse ,i 7.71 CaSiOl ,¦ 0.50 Mg Stearate 5 ~¦ Formulation E: 73.79 MgO(20xlO0) 'I 10.00 CaO
6 1l 5.00 Na2COJ-dense ~ 5.50 attaclay 7 , 5.21 CaSiO, i 0.50 Mg Stearate 8 i I Formulation F: 39.00 MgO(20xlO0) 9 j 39.00 MgO-(Fine Grade-100) l 9.00 Na2CO3-dense 10 , 10.00 attaclay-coarse l 3.00 Mg Stearate i Formulation G: 79.00 MgO(20xl00) 12 j 10.00 CaO
l 10.00 attaclay coarse 13 i 1.00 Tricalcium phosphate 14 i Formulation H: 39.00 MgO(20xl00) l 39.00 MgO(Fine Grade-100) 15 1 9.00 Na2COl-dense I 10.00 attaclay-coarse 16 ! 3.00 Tricalcium phosphate 17 Formulation I: 39.50 MgO(20xl00) 39.50 MgO(Fine Grade-100 18 10.00 CaO
5.00 NatCO3-dense 19 1 5.50 attaclay-course l 0.50 Mg Stearate ''O
Formulation K: 36.00 MgO(20xlO0) 21 36.00 MgO(Fine Grade-100) i 20.00 Na2CO 3 -dense 22 j . 5.00 Attaclay-coarse l 3.00 Tricalcium phosphate 23 .
i Formulation L: 36.00 MgO(20xlO0) 24 1 36.00 MgO(Fine Grade-100) ~ 5.00 CaO
25 ¦ 10.00 Na2CO,-dense 10.00 attaclay-coarse 26 ¦ 2.50 Tricalcium phosphate I 0.50 Silanox i Formulation M: 39.50 MgO(20xlO0) 28 39.50 MgO(Fine Grade-100) 8.00 CaO
29 5.00 Na2CO,-dense 5.00 attaclay-coarse 3.00 Tricalcium phosphate 0.50 Silanox - 12 - (0082W) .
i2130~84 1 ¦ Formulation N: 49.00 MgO~20xlOO) , 29.00 MgO(Fine Grade-100) 2 ~i g.oo Na2CO3-dense ii 10.00 attaclay-coarse 3 ~¦ 3.00 Magnesium Stearate , 4 ,,! Formulation P: 36.50 MgO~20xlOO) I 36.5D ~Q~Fine ~ade-l~O) 5 ~ 5.00 CaO
i 9.00 NazCO,-dense 6 ~ 12.50 attaclay-coarse l 0.50 Magnesium Stearate i Formulation Q: 36.50 MgO(20xlOO) 8 ! 36.50 MgO(Fine Grade-100) ~ 5.00 CaO
9 ¦ 9.00 NazCO3-dense I 12.50 attaclay-coarse 10 j D.50 Magnesium Stearat~e 11 ¦ Formulation Q: 31.50 MgO(20xlOO) i 31.50 MgO(Fine Grade-100) 12 ' 4.00 CaO
! 7.50 Na 2 CO 3 -dense 13 1 25.00 attaclay-coarse I 0.50 Magnesium Stearate I
23 j 2245 ~
I - 13- (008~w~
::`
1;~80S~3A
ExamDle ~1 yolume Wt. Agent Wt. Discharge % Dicharge DH~i) vH~f) Observations 1 A H2504 2 gal. 26-3 26-3 97.0 0.99 ô.ô5 Very hard 2 Z A H2504 2 gal, 27-0 26-9 98.4 0.86 a.57 Hard After agitation on 3 5 min from applicati on 14 3 B H250~ 2 gal, 30-0 28-7 94.8 0.82 9.26 Liquid left in pant, but absorbed after agitation 6 4 C H~504 2 gal, 30-0 29-9 98.5 0.98 9.26 Absorbed with stirring 7 5 D H250, 2 gal. 22-14 21-12 95.1 0.31 ô.34 Good deal of 8 remalning 9 6 A H2504 2 gal. 24-1 23-9 97.9 0.52 8.82 good solid 7 E HCl 2.5 gal. 25.0 24-12 99.0 6.00 8.81 semi-solid 0 hrs, can be 11 shoveled 8 E HCl 2 gal. 29-0 27-14 96.1 9.39 9.46 Absorbed with 12 agitation 13 9 E HCl 2 gal. 27-0 26-S 97.4 ô.90 9.14 Poor set 10 E H2504 2 gal. 29-0 27-10 95-3 0.52 9.35 Good 14 ll E H2S04 2 gal. 29-12 29-4 98.3 0.52 9.07 Grandular 12 E H3PO4 2 gal. 29-0 28-6 97-9 5.02 7.87 Easy to pick 16 13 G H3PO4 2 gal. 30-0 28-4 94.2 4.79 5.59 Some 17 remai n i ng mixing 18 14 H H2504 2 gal. 28-0 26-11 absorption 1 9 501 id ls H HCl 2 gal. 27-12 25-15 93.5 9.03 9.08 Soupy. but hardens in 24 21 hrs.
22 16 H H3PO4 2 gal. 28-8 27-4 95.6 4.96 6.74 Good 17 H HNO3 2 gal. 28-0 26-4 93.8 9.16 9.37 Good 23 18 H HCOOH 2 gal. 26-0 24-14 95.7 4.39 9.60 Good 24 19 H CH~CO~H 2 gal. 28-0 26-10 95.1 5.84 9.32 Good
20 H HC104 2 gal. 28-0 26-8 94.6 5.97 9.30 Good
21 I H2504 ~ 2 gal. 29-0 26-14 92.7 1.05 9.43 Good 26 22 H HCl04 2 gal. 26-0 24-8 94.23 8.23 8.90 Excellent 27 23 I HCl 2 gal. 30-0 28-16 mixing 28 24 ~ H3PO~ 2 gal. 30-0 28-6 94.6 5.27 7.36 Absrbed in ~, .~
1~805~a~
, ExamDle ~S~g YQ~um~ Wt. Agent Wt. D;scharoe X O;charge Q~L~ pH~f) Observations 1 1 25 I HNOJ 2 ga7. 30-0 38-10 95.4 9.14 9.29 Mild rxn;
2 ~ good solid .! 26 I CH~COOH 2 gal. 30-0 28-6 94.6 9.62 9.72 Very good 3 ~¦ and reaction 4 ~¦ 27 I HCOOH 2 gal. 30-0 28-8 95-0 5.23 0.55 Some post I reaction when 5 ~I mixed ,¦ 28 I HClO~ 2 gal. 30-0 Z8-2 93.8 8.48 9.06 Very good 6 1 absorption , 29 H H2504 2 gal. 28-0 20 71.4 0.06 8.76 Poor 7 ¦ 30 H H2504- 2 gal. 28-0 26-4 93.8 1.30 9.39 Good 8 ¦ 31 H HCl 2 gal. 28-0 26-0 92.9 9-05 9.17 Saupy 9 32 H H3 PO4 2 gal. 28-0 26-8 94.6 5.06 8.83 Good l 33 H H2SO4 2 gal. 26-8 26-0 96.2 1.35 1.19 Good 1 0 ! 34 H H25O4 2 gal. 28-0 26-7 94.4 1.01 9.47 Good 1 absorption;
11 1 high I reactivity 2 ! 35 H HCl 2 gal. 28-0 25-8 91.1 8.81 9.18 Good reaction ~'¦ 36 H H3PO4 2 gal. 28-0 26-6 94.2 absorption ! with mixing 1 4 ¦ 37 K H25O4 2 gal. 28-O 26-2 characteris-1 5 tics 1 6 38 K H2SO4 2 gal. 28-0 26-4 93.8 8.83 9.27 Soupy l 39 K H3PO4 2 gal. 28-0 25-11 ~1.8 5.19 9.05 Good 1 7 40 H HNO3 2 gal. 28-0 22-0 78.6 9.19 9.40 Some 1 8 liquid 1 9 41 H CH3COOH 2 gal. 28-0 26-8 94.6 5.84 9.34 Very fast rxn 42 H HCOOH 2 gal. 28-0 26-4 93.8 4.96 9.44 All liquidO absorbed 43 H HC104 2 gal. 28-0 27-1 96.4 2.60 9.01 Some 21 remaining liquid 2 2 1 44 L H25O4 2 gal. 28-0 27-1 96.6 1.23 9.31 Liquid left l after 2 3 ¦ discharge-l silanox no 2 4 ! good l 45 L HCl 2 gal. 28-0 26-5 94.û 9.09 932 Good rxn. and 25 ¦ , min.
26 1 46 L H3PO4 2 gal. 28-0 26-16 95.1 5.13 7.69 Mild rxn l silanox 1 hinders 2 7 absorption 28 47 I H,SO4 2 gal. 30-0 28-11 95.6 1.36 9.12 Very mild rxn , I
, - 15 - (û082W~
~280S84 Example Acid Volume Wt. Aaent Wt, Discharg~ Y Dicharae pH(il DH(f) Observations 48 I HCl 2 gal. 3û-0 28-10 95.4 9.21 9.44 Slow rxn. and 2 absorpt ion 49 M HCl Z gal. 28-0 26-10 95.0 9.21 9.28 Good rxn.
3 tics 4 50 N H2504 2 gal. 28-0 Z6-15 96.2 1.25 9.48 Good 51 N HCl 2 gal. 28-0 26-7 94.4 8.90 8.97 Soupy 6 5Z P H,SO. 2 gal. 30-0 28-13 than "N"
7 53 P HCl Z gal. 30-0 Z8-10 95.4 9.Z9 9.41 Good mild r~n.
8 54 O H3PO. 2 gal. 30-0 Z8-11 absor ption 55 ~ HNO~ 2 gal. 30-0 Z9-1 96.9 9.06 9.ûl Mild to 9 moderat e r~n.
56 Q CH3COOH 2 gal. 30-0 29-0 96.7 9.10 9.99 Good 1 0 absorption 11 57 O HCOOH 2 gal. 30-0 Z8-7 94.8 4.51 9.49 Mild 58 O HCLO. 2 gal. 30-0 Z8-0 93.3 8.85 9.Z6 Very good 12 mild 13 59 R HCl Z.5 gal. 28-4 24-13 87.8 9.13 9.44 Liquid 16 remaining
1~805~a~
, ExamDle ~S~g YQ~um~ Wt. Agent Wt. D;scharoe X O;charge Q~L~ pH~f) Observations 1 1 25 I HNOJ 2 ga7. 30-0 38-10 95.4 9.14 9.29 Mild rxn;
2 ~ good solid .! 26 I CH~COOH 2 gal. 30-0 28-6 94.6 9.62 9.72 Very good 3 ~¦ and reaction 4 ~¦ 27 I HCOOH 2 gal. 30-0 28-8 95-0 5.23 0.55 Some post I reaction when 5 ~I mixed ,¦ 28 I HClO~ 2 gal. 30-0 Z8-2 93.8 8.48 9.06 Very good 6 1 absorption , 29 H H2504 2 gal. 28-0 20 71.4 0.06 8.76 Poor 7 ¦ 30 H H2504- 2 gal. 28-0 26-4 93.8 1.30 9.39 Good 8 ¦ 31 H HCl 2 gal. 28-0 26-0 92.9 9-05 9.17 Saupy 9 32 H H3 PO4 2 gal. 28-0 26-8 94.6 5.06 8.83 Good l 33 H H2SO4 2 gal. 26-8 26-0 96.2 1.35 1.19 Good 1 0 ! 34 H H25O4 2 gal. 28-0 26-7 94.4 1.01 9.47 Good 1 absorption;
11 1 high I reactivity 2 ! 35 H HCl 2 gal. 28-0 25-8 91.1 8.81 9.18 Good reaction ~'¦ 36 H H3PO4 2 gal. 28-0 26-6 94.2 absorption ! with mixing 1 4 ¦ 37 K H25O4 2 gal. 28-O 26-2 characteris-1 5 tics 1 6 38 K H2SO4 2 gal. 28-0 26-4 93.8 8.83 9.27 Soupy l 39 K H3PO4 2 gal. 28-0 25-11 ~1.8 5.19 9.05 Good 1 7 40 H HNO3 2 gal. 28-0 22-0 78.6 9.19 9.40 Some 1 8 liquid 1 9 41 H CH3COOH 2 gal. 28-0 26-8 94.6 5.84 9.34 Very fast rxn 42 H HCOOH 2 gal. 28-0 26-4 93.8 4.96 9.44 All liquidO absorbed 43 H HC104 2 gal. 28-0 27-1 96.4 2.60 9.01 Some 21 remaining liquid 2 2 1 44 L H25O4 2 gal. 28-0 27-1 96.6 1.23 9.31 Liquid left l after 2 3 ¦ discharge-l silanox no 2 4 ! good l 45 L HCl 2 gal. 28-0 26-5 94.û 9.09 932 Good rxn. and 25 ¦ , min.
26 1 46 L H3PO4 2 gal. 28-0 26-16 95.1 5.13 7.69 Mild rxn l silanox 1 hinders 2 7 absorption 28 47 I H,SO4 2 gal. 30-0 28-11 95.6 1.36 9.12 Very mild rxn , I
, - 15 - (û082W~
~280S84 Example Acid Volume Wt. Aaent Wt, Discharg~ Y Dicharae pH(il DH(f) Observations 48 I HCl 2 gal. 3û-0 28-10 95.4 9.21 9.44 Slow rxn. and 2 absorpt ion 49 M HCl Z gal. 28-0 26-10 95.0 9.21 9.28 Good rxn.
3 tics 4 50 N H2504 2 gal. 28-0 Z6-15 96.2 1.25 9.48 Good 51 N HCl 2 gal. 28-0 26-7 94.4 8.90 8.97 Soupy 6 5Z P H,SO. 2 gal. 30-0 28-13 than "N"
7 53 P HCl Z gal. 30-0 Z8-10 95.4 9.Z9 9.41 Good mild r~n.
8 54 O H3PO. 2 gal. 30-0 Z8-11 absor ption 55 ~ HNO~ 2 gal. 30-0 Z9-1 96.9 9.06 9.ûl Mild to 9 moderat e r~n.
56 Q CH3COOH 2 gal. 30-0 29-0 96.7 9.10 9.99 Good 1 0 absorption 11 57 O HCOOH 2 gal. 30-0 Z8-7 94.8 4.51 9.49 Mild 58 O HCLO. 2 gal. 30-0 Z8-0 93.3 8.85 9.Z6 Very good 12 mild 13 59 R HCl Z.5 gal. 28-4 24-13 87.8 9.13 9.44 Liquid 16 remaining
22
23
24 ~ . - 16 - (0082~
1~80S8~
1 Sample sieve distributions for the variant 2 formulations are set forth in Table II. The distributions may 3 vary slightly according to the particular example. The 4 formulation is indicated at the left. The "Bulk" column indicates the median size of the particular. The "Sieve"
6 columns indicate the size of the sieve used to measure the 7 particle distribution.
9 Formulation Bulk 20 40 100 200 335 Pan 0 H 105 1.5 30.6 51.610;9 3.6 1.9 I 99 1.4 26.9 45.6 8.8 3.0 13.9 11 M 106 trace 23.4 45.011.5 10.4 9.4 1~
l7 2g - 17 - (0082W)
1~80S8~
1 Sample sieve distributions for the variant 2 formulations are set forth in Table II. The distributions may 3 vary slightly according to the particular example. The 4 formulation is indicated at the left. The "Bulk" column indicates the median size of the particular. The "Sieve"
6 columns indicate the size of the sieve used to measure the 7 particle distribution.
9 Formulation Bulk 20 40 100 200 335 Pan 0 H 105 1.5 30.6 51.610;9 3.6 1.9 I 99 1.4 26.9 45.6 8.8 3.0 13.9 11 M 106 trace 23.4 45.011.5 10.4 9.4 1~
l7 2g - 17 - (0082W)
Claims (9)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A composition for neutralizing and solidifying hazardous acidic spills comprising about 1 to 80% alkaline earth oxide, 0 to 30% alkali metal carbonate, 0 to 10% highly absorptive silica or clay, 5 to 30% less absorptive clay, 0.5 to 2% hydrophobic lubricant agent and o to 50% portland cement.
2. A composition according to claim 1 comprising magnesium oxide, calcium oxide, sodium carbonate, attapulgas clay, calcium silicate and magnesium stearate.
3. A composition according to claim 1 wherein said akaline earth oxide is magnesium oxide in coarse- and fine-grade forms.
4. A composition according to claim 1 comprising about 74% magnesium oxide, about 10% calcium oxide, about 5% sodium carbonate, about 5% calcium silicate, about 5.5% attapulgas clay and about 0.50% magnesium stearate.
5. A composition according to claim 1 comprising about 31 to about 39% coarse-grade MgO, about 31 to about 39% fine-grade MgO, between about 5 and about 9% sodium silicate, between about 5 and about 10% attapulgas clay and between about 1 and about 3 percent tricalcium phosphate.
6. A composition according to claim 1 comprising about 31.5% coarse grade MgO, about 31.5% fine-grade MgO, about 4%
CaO, about 7.5% Na2CO3, about 25% attapulgas clay and about 0.5% magnesium stearate.
- 18 - (0082W)
CaO, about 7.5% Na2CO3, about 25% attapulgas clay and about 0.5% magnesium stearate.
- 18 - (0082W)
7. A method of neutralizing and solidifying hazardous acidic spills comprising applying a composition to the spill comprising about 0 to 80% alkaline earth oxide, 0 to 30% alkali metal carbonate, 0 to 10% highly absorptive silica or clay, 5 to 30% less absorptive clay, 0.5 to 2% hydrophobic lubricant agent and 0 to 50% portland cement, thus causing neutralization and solidification.
8. A method according to claim 7 wherein said application is accomplished by delivering said composition to said spill under pressure of a nitrogen gas propellant in a fire-extinguisher-like delivery device.
9. A composition according to claim 1 which is in the form of dry particles having a size distribution between about -40 and +200 Tyler screen mesh size range.
- 19 - (0082W)
- 19 - (0082W)
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US85913286A | 1986-05-02 | 1986-05-02 | |
| US06/859,132 | 1986-05-02 | ||
| US2984787A | 1987-03-31 | 1987-03-31 | |
| US07/029,847 | 1987-03-31 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1280584C true CA1280584C (en) | 1991-02-26 |
Family
ID=25330129
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000536193A Expired - Fee Related CA1280584C (en) | 1986-05-02 | 1987-05-01 | Compositions and method for neutralization and solidification of hazardous acid spills |
Country Status (18)
| Country | Link |
|---|---|
| EP (1) | EP0273045A4 (en) |
| JP (1) | JPH01500018A (en) |
| AU (1) | AU591993B2 (en) |
| CA (1) | CA1280584C (en) |
| DE (1) | DE3790211T1 (en) |
| DK (1) | DK692787A (en) |
| ES (1) | ES2029757A6 (en) |
| FI (1) | FI875747A (en) |
| GB (1) | GB2201029B (en) |
| GR (1) | GR870680B (en) |
| IL (1) | IL82350A0 (en) |
| NL (1) | NL8720242A (en) |
| NO (1) | NO875499L (en) |
| NZ (1) | NZ220149A (en) |
| PH (1) | PH23851A (en) |
| SE (1) | SE8705208L (en) |
| WO (1) | WO1987006758A1 (en) |
| ZA (1) | ZA873125B (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| IL82349A0 (en) * | 1986-05-02 | 1987-10-30 | Wormald Us Inc | Novel compositions and method for neutralization and solidification of hazardous alkali spills |
| US4990188A (en) * | 1988-12-19 | 1991-02-05 | Rhone-Poulenc Basic Chemicals Co. | Anti-slip composition |
| FR2685226A1 (en) * | 1991-12-18 | 1993-06-25 | Sol Cie | METHOD FOR STABILIZING AND SOLIDIFYING DOMESTIC GARBAGE INCINERATION PRODUCTS, PRODUCTS RESULTING FROM THE PROCESS, AND PRODUCTS THEREOF FOR ITS IMPLEMENTATION |
| EP0571970A1 (en) * | 1992-05-27 | 1993-12-01 | Michael J. Runow | Method and composition for neutralizing hazardous material spills |
| DE4412633C1 (en) * | 1994-04-13 | 1995-08-17 | Degussa | Preventing sulphur tri:oxide mist forming from oleum esp. spillage |
| DE19541479C1 (en) | 1995-11-07 | 1997-03-13 | Poligrat Holding Gmbh | Processing and solidification of phosphoric acid-contg. solns. |
| JP2007190494A (en) * | 2006-01-19 | 2007-08-02 | Okutama Kogyo Co Ltd | Waste water treatment agent and waste water treatment method |
| FR2998577B1 (en) * | 2012-11-28 | 2015-04-24 | Prevor Internat | DEPOLLUTION COMPOSITION AND USE THEREOF |
Family Cites Families (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3090749A (en) * | 1959-01-30 | 1963-05-21 | Ansul Chemical Co | Fire extinguisher compositions for metal fires |
| US3196106A (en) * | 1961-10-04 | 1965-07-20 | Minerals & Chem Philipp Corp | Method for purifying radioactive waste liquid |
| CA965966A (en) * | 1970-01-08 | 1975-04-15 | Jesse R. Conner | Land improvement with waste materials |
| US4095988A (en) * | 1974-07-19 | 1978-06-20 | Vyskumny Ustav Inzenierskych Stavieb | Self hardening suspension for foundation engineering purposes |
| DE2455316A1 (en) * | 1974-11-22 | 1976-05-26 | Werner Fuelling | Binder for incidently released aggressive liquids or oils - contg. granulated foundry pumice and slaked lime |
| US3980558A (en) * | 1975-07-07 | 1976-09-14 | Browning-Ferris Industries, Inc. | Method of disposing sludges containing soluble toxic materials |
| US3994821A (en) * | 1975-10-22 | 1976-11-30 | J. T. Baker Chemical Company | Spill control composition and use thereof |
| US4210460A (en) * | 1975-10-22 | 1980-07-01 | J. T. Baker Chemical Company | Spill control composition and use thereof |
| DE2726087C2 (en) * | 1977-06-10 | 1978-12-21 | Kernforschungszentrum Karlsruhe Gmbh, 7500 Karlsruhe | Process for the final disposal-ready, environmentally friendly solidification of "and moderately radioactive and / or actinide-containing, aqueous waste concentrates or of fine-grained solid waste suspended in water |
| US4299722A (en) * | 1978-04-21 | 1981-11-10 | Stock Equipment Company | Introduction of fluent materials into containers |
| US4207116A (en) * | 1978-05-04 | 1980-06-10 | Bepro B.V. | Granulated material and process for the production of granulated materials |
| EP0005902A1 (en) * | 1978-05-18 | 1979-12-12 | Imperial Chemical Industries Plc | Self-setting or water-settable isocyanate compositions and methods for their formation |
| GB2050388B (en) * | 1979-05-02 | 1983-02-09 | Ici Ltd | Compositions for treating chemical spillages |
| HU180394B (en) * | 1980-11-21 | 1983-02-28 | Magyar Szenhidrogenipari | Process and equipment for the neutralization of acid tar and for getting it from conserving tanks |
| FR2545387B1 (en) * | 1983-05-03 | 1987-01-09 | Philippe Pichat | PROCESS FOR THE SOLIDIFICATION OF LIQUID WASTE OF HIGH ACIDITY OR ALKALINITY |
| US4518508A (en) * | 1983-06-30 | 1985-05-21 | Solidtek Systems, Inc. | Method for treating wastes by solidification |
-
1987
- 1987-04-28 IL IL82350A patent/IL82350A0/en unknown
- 1987-04-29 PH PH35200A patent/PH23851A/en unknown
- 1987-04-30 GR GR870680A patent/GR870680B/en unknown
- 1987-04-30 ZA ZA873125A patent/ZA873125B/en unknown
- 1987-04-30 ES ES8701306A patent/ES2029757A6/en not_active Expired - Lifetime
- 1987-04-30 NZ NZ22014987A patent/NZ220149A/en unknown
- 1987-05-01 JP JP62503205A patent/JPH01500018A/en active Pending
- 1987-05-01 DE DE19873790211 patent/DE3790211T1/de not_active Ceased
- 1987-05-01 GB GB8730352A patent/GB2201029B/en not_active Expired
- 1987-05-01 NL NL8720242A patent/NL8720242A/en unknown
- 1987-05-01 EP EP19870903553 patent/EP0273045A4/en not_active Withdrawn
- 1987-05-01 AU AU74809/87A patent/AU591993B2/en not_active Ceased
- 1987-05-01 WO PCT/US1987/001014 patent/WO1987006758A1/en not_active Application Discontinuation
- 1987-05-01 CA CA000536193A patent/CA1280584C/en not_active Expired - Fee Related
- 1987-12-29 FI FI875747A patent/FI875747A/en not_active IP Right Cessation
- 1987-12-30 SE SE8705208A patent/SE8705208L/en not_active Application Discontinuation
- 1987-12-30 NO NO875499A patent/NO875499L/en unknown
- 1987-12-30 DK DK692787A patent/DK692787A/en not_active Application Discontinuation
Also Published As
| Publication number | Publication date |
|---|---|
| SE8705208D0 (en) | 1987-12-30 |
| EP0273045A4 (en) | 1988-09-07 |
| IL82350A0 (en) | 1987-10-30 |
| PH23851A (en) | 1989-11-23 |
| NO875499L (en) | 1988-02-24 |
| WO1987006758A1 (en) | 1987-11-05 |
| AU591993B2 (en) | 1989-12-21 |
| GR870680B (en) | 1987-09-02 |
| EP0273045A1 (en) | 1988-07-06 |
| GB8730352D0 (en) | 1988-02-24 |
| DK692787A (en) | 1988-03-01 |
| AU7480987A (en) | 1987-11-24 |
| GB2201029B (en) | 1989-12-20 |
| FI875747A0 (en) | 1987-12-29 |
| NZ220149A (en) | 1989-10-27 |
| DK692787D0 (en) | 1987-12-30 |
| ES2029757A6 (en) | 1992-09-01 |
| FI875747A (en) | 1987-12-29 |
| ZA873125B (en) | 1988-04-27 |
| NL8720242A (en) | 1988-04-05 |
| GB2201029A (en) | 1988-08-17 |
| DE3790211T1 (en) | 1988-07-14 |
| SE8705208L (en) | 1987-12-30 |
| JPH01500018A (en) | 1989-01-12 |
| NO875499D0 (en) | 1987-12-30 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKLA | Lapsed |