US3669895A - Sodium hydrosulfite stabilization composition - Google Patents
Sodium hydrosulfite stabilization composition Download PDFInfo
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- US3669895A US3669895A US68537A US3669895DA US3669895A US 3669895 A US3669895 A US 3669895A US 68537 A US68537 A US 68537A US 3669895D A US3669895D A US 3669895DA US 3669895 A US3669895 A US 3669895A
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- sodium
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- carbonate
- water soluble
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- 239000000203 mixture Substances 0.000 title claims abstract description 51
- JVBXVOWTABLYPX-UHFFFAOYSA-L sodium dithionite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])=O JVBXVOWTABLYPX-UHFFFAOYSA-L 0.000 title claims abstract description 31
- 230000006641 stabilisation Effects 0.000 title abstract description 8
- 238000011105 stabilization Methods 0.000 title abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 30
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000000654 additive Substances 0.000 claims abstract description 18
- 229910052806 inorganic carbonate Inorganic materials 0.000 claims abstract description 16
- 229910021538 borax Inorganic materials 0.000 claims abstract description 11
- 235000010339 sodium tetraborate Nutrition 0.000 claims abstract description 11
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000004328 sodium tetraborate Substances 0.000 claims abstract description 10
- 235000006408 oxalic acid Nutrition 0.000 claims abstract description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 16
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 16
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 14
- 230000000996 additive effect Effects 0.000 claims description 8
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 8
- 235000010265 sodium sulphite Nutrition 0.000 claims description 8
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 7
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 7
- GRWZHXKQBITJKP-UHFFFAOYSA-L dithionite(2-) Chemical group [O-]S(=O)S([O-])=O GRWZHXKQBITJKP-UHFFFAOYSA-L 0.000 claims description 5
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 4
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims description 4
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical class [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 claims description 4
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 3
- 238000004061 bleaching Methods 0.000 abstract description 13
- 238000000354 decomposition reaction Methods 0.000 abstract description 11
- 230000002269 spontaneous effect Effects 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 6
- 230000000087 stabilizing effect Effects 0.000 abstract description 3
- 239000003381 stabilizer Substances 0.000 abstract description 2
- 229910004835 Na2B4O7 Inorganic materials 0.000 abstract 1
- UQGFMSUEHSUPRD-UHFFFAOYSA-N disodium;3,7-dioxido-2,4,6,8,9-pentaoxa-1,3,5,7-tetraborabicyclo[3.3.1]nonane Chemical compound [Na+].[Na+].O1B([O-])OB2OB([O-])OB1O2 UQGFMSUEHSUPRD-UHFFFAOYSA-N 0.000 abstract 1
- 238000007792 addition Methods 0.000 description 4
- 239000004615 ingredient Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- PENRVBJTRIYHOA-UHFFFAOYSA-L zinc dithionite Chemical compound [Zn+2].[O-]S(=O)S([O-])=O PENRVBJTRIYHOA-UHFFFAOYSA-L 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical class OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- KAALWRLETTYHQG-UHFFFAOYSA-M [Na+].OS(=O)S(O)=O.OS(=O)S([O-])=O Chemical compound [Na+].OS(=O)S(O)=O.OS(=O)S([O-])=O KAALWRLETTYHQG-UHFFFAOYSA-M 0.000 description 2
- 239000002671 adjuvant Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000004076 pulp bleaching Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 1
- 241000331231 Amorphocerini gen. n. 1 DAD-2008 Species 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- PQUCIEFHOVEZAU-UHFFFAOYSA-N Diammonium sulfite Chemical class [NH4+].[NH4+].[O-]S([O-])=O PQUCIEFHOVEZAU-UHFFFAOYSA-N 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical class OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- 241000218657 Picea Species 0.000 description 1
- 229920000388 Polyphosphate Polymers 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 1
- 238000005273 aeration Methods 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 1
- 150000008041 alkali metal carbonates Chemical class 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 239000001099 ammonium carbonate Substances 0.000 description 1
- 235000012501 ammonium carbonate Nutrition 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000007844 bleaching agent Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 1
- 231100000989 no adverse effect Toxicity 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000001205 polyphosphate Substances 0.000 description 1
- 235000011176 polyphosphates Nutrition 0.000 description 1
- 239000013055 pulp slurry Substances 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 235000002639 sodium chloride Nutrition 0.000 description 1
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 description 1
- 229940001584 sodium metabisulfite Drugs 0.000 description 1
- 235000010262 sodium metabisulphite Nutrition 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- 235000019832 sodium triphosphate Nutrition 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- DHCDFWKWKRSZHF-UHFFFAOYSA-N sulfurothioic S-acid Chemical compound OS(O)(=O)=S DHCDFWKWKRSZHF-UHFFFAOYSA-N 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- BSVBQGMMJUBVOD-UHFFFAOYSA-N trisodium borate Chemical compound [Na+].[Na+].[Na+].[O-]B([O-])[O-] BSVBQGMMJUBVOD-UHFFFAOYSA-N 0.000 description 1
- 239000000984 vat dye Substances 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 238000009736 wetting 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
- C01B17/00—Sulfur; Compounds thereof
- C01B17/64—Thiosulfates; Dithionites; Polythionates
- C01B17/66—Dithionites or hydrosulfites (S2O42-)
- C01B17/665—Stabilisation by additives subsequent to preparation; Dust prevention by additives
Definitions
- ABSTRACT The present discovery entails a new means for stabilizing mixtures, containing primarily sodium dithionite, from spontaneous decomposition and "ignition" by the action of water. Specifically, the invention comprises stabilization of sodium hydrosulfite against spontaneous decomposition in the presence of water, using effective quantities of additives.
- the stabilizing agents consist of oxalic acid and a water soluble inorganic carbonate. This mixture can be further improved as to stabilization and bleaching efi'ect by the addition of borax (Na B O 10 H 0). The bleaching effect may be improved by adding a water soluble inorganic sulfite.
- Sodium hydrosulfite also designated as sodium dithionite, is used in large quantities as a strong reducing medium for bleaching and the reduction of certain dyes for example groundwood pulp bleaching and vat dye reductions. Although it fulfills these purposes satisfactorily, the application of sodium hydrosulfite in these areas is deterred because of self-ignition in contact with small quantities of water leading to the rapid expansion of the decomposition, which interferes with efi'icient pulp bleaching, etc. and hinders the papermill operation in particular.
- zinc hydrosulfite (zinc dithionite), ZnS O is preferred as a bleaching agent, since it is relatively stable toward spontaneous self-decomposition under normal transport and storage conditions.
- the zinc ion is considered toxic, therefore its presence in effluents from mills is not tolerated in many instances. Therefore, the user has a choice, between sodium hydrosulfite with its undesirable decomposition characteristics and zinc hydrosulfite with its toxic characteristics, necessitating the use of prohibitively expensive removal processes for the treatment ofeffluent waters.
- sodium hydrosulfite refers herein to the article of commerce which may contain between 85 and 98 percent weight percent sodium hydrosulfite (dithionite) along with certain impurities such as sodium chloride, sodium sulfate, sodium sulfite and thiosulfate.
- Exemplary of the water soluble inorganic carbonate are the alkali metal carbonates and bicarbonates and ammonium carbonate.
- the sodium salts are preferred for economic reasons. For example: a mixture of approximately equal parts of sodium carbonate and sodium bicarbonate has been found to be satisfactory.
- Exemplary of water soluble inorganic sulfites are the alkali metal and ammonium sulfites and bisulfites, the sodium salt being preferred.
- a mixture of additives consisting of approximately equal amounts of sodium sulfite and bisulfite is preferred.
- borax With the exception of borax, it is desirable in the practice of this invention to use these ingredients in their anhydrous state. The presence of the water of crystallization in the borax has no adverse effect upon the application of this composition.
- oxalic l to-25 percent
- carbonate l to-3 percent
- borax l to-5 percent
- sulfite 0.5 to-l percent.
- the sum total ingredients aforesaid should not exceed 25 weight percent of the technical hydrosulfite content.
- composition of matter mixtures herein are compatible with the normal bleaching adjuvants such as are used in the bleaching of pulp particularly for example the complexforrning ingredients such as the polyphosphates and the various derivatives of ethylene diamine tetraacetic acid and nitrilo-triacetic acid.
- the adjuvants can be used herein by separate addition or as components of proprietary mixtures.
- composition of matter mixture described was thereafter applied to a hydrosulfite and the same amount of water added. This produced a comparatively lower reaction temperature and the decomposition products liberated could not be ignited with the bunsen flame.
- EXAMPLE II The following composition was used to demonstrate improved sodium hydrosulfite stability and particularly improved bleaching efficiency.
- a 3 percent consistency pulp slurry of the groundwood was treated for 45 minutes at F. at a pH of 5.0 to 5.5, the treatment being at a rate of IO lbs of hydrosulfite composition per ton of air dried groundwood pulp, aforesaid.
- the results are listed below.
- a stabilized composition of matter consisting essentially of a predetermined percent by weight of sodium hydrosulfite characterized by additives of oxalic acid and a water soluble inorganic carbonate, the percentages of weight of additives, relative to the sodium hydrosulfite, being not less than 1 percent nor more than 25 percent, said additives stabilizing the sodium hydrosulfite against spontaneous thermal decomposition.
- composition of matter of claim 1 and borax as a further additive.
- composition of matter of claim 2 and a water soluble inorganic sulfite as further additive.
- composition of matter of claim 1 wherein the inorganic carbonate is selected from the group consisting of sodiurn hydrogen carbonate and mixtures thereof and sodium carbonate as water soluble inorganic carbonates.
- composition of matter of claim 2 wherein the inorganic carbonate is selected from the group consisting of sodium hydrogen carbonate and mixtures thereof and sodium carbonate as water soluble inorganic carbonates.
- composition of matter of claim 3 wherein the inorganic carbonate is selected from the group consisting of sodium hydrogen carbonate and mixtures thereof and sodium carbonate as water soluble inorganic carbonates.
- composition of matter of claim 3 in which the water soluble inorganic sulfite is selected from the group consisting of sodium sulfite and sodium bisullite and mixtures thereof.
- composition of matter of claim 4 in which the water soluble inorganic sulfite is selected from the group consisting of sodium sulfite and sodium bisulfite and mixtures thereof.
- composition of matter of claim 1 wherein the propor tion of additives in percentage by weight to sodium hydrosulfite is:
- composition of matter of claim 9 wherein a further additive, borax, comprises in proportion by weight relative to the sodium hydrosulfite, 1-5 percent.
- composition of matter of claim 9 wherein a further additive of sulfites comprises in proportion by weight relative to the hydrosulfite 0.5-l percent.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Paper (AREA)
Abstract
The present discovery entails a new means for stabilizing mixtures, containing primarily sodium dithionite, from spontaneous decomposition and ''''ignition'''' by the action of water. Specifically, the invention comprises stabilization of sodium hydrosulfite against spontaneous decomposition in the presence of water, using effective quantities of additives, which still in no way lessen the bleaching activity that would be developed by an equivalent quantity of sodium hydrosulfite. The stabilizing agents consist of oxalic acid and a water soluble inorganic carbonate. This mixture can be further improved as to stabilization and bleaching effect by the addition of borax (Na2B4O7 1 10 H2 O). The bleaching effect may be improved by adding a water soluble inorganic sulfite.
Description
United States Patent Shastri 1 June 13, 1972 SODIUM HYDROSULFITE STABILIZATION COMPOSITION Inventor:
US. Cl ..252/188, 8/107, 23/116,
252/105 Int. Cl. ..C0lb 17/98, D2 lc 9/10 Field oISearch .252/188, 105; 23/1 16; 8/107 References Cited UNITED STATES PATENTS Primary Examiner-Leon D. Rosdoi Assistant Examinerlrwin Gluck Attorney-J. Gibson Sernmes 57] ABSTRACT The present discovery entails a new means for stabilizing mixtures, containing primarily sodium dithionite, from spontaneous decomposition and "ignition" by the action of water. Specifically, the invention comprises stabilization of sodium hydrosulfite against spontaneous decomposition in the presence of water, using effective quantities of additives. which still in no way lessen the bleaching activity that would be developed by an equivalent quantity of sodium hydrosulfite. The stabilizing agents consist of oxalic acid and a water soluble inorganic carbonate. This mixture can be further improved as to stabilization and bleaching efi'ect by the addition of borax (Na B O 10 H 0). The bleaching effect may be improved by adding a water soluble inorganic sulfite.
l1 Claim, No Drawings SODIUM HYDROSULFITE STABILIZATION COMPOSITION BACKGROUND OF THE INVENTION Sodium hydrosulfite, also designated as sodium dithionite, is used in large quantities as a strong reducing medium for bleaching and the reduction of certain dyes for example groundwood pulp bleaching and vat dye reductions. Although it fulfills these purposes satisfactorily, the application of sodium hydrosulfite in these areas is deterred because of self-ignition in contact with small quantities of water leading to the rapid expansion of the decomposition, which interferes with efi'icient pulp bleaching, etc. and hinders the papermill operation in particular.
In the reaction initiated by water, a series of strongly exothermic reactions develop apparently yielding hydrogen and several sulfur-containing compounds of various oxidation states of sulfur. Small amounts of water, for example, from a drum of moist sodium dithionite, mixed with dry product in a storage bin or hopper can start a severe decomposition in the absence of significant amounts of oxygen, which, upon aeration and evolution of gases can lead to intense combustion and possibly explosion.
Various attempts have been made to reduce the sensitivity of sodium hydrosulfite to moisture by the use of additivies of various kinds, e.g., by the addition of dessicants of various compositions or through the wetting of the sodium dithionite with hydrophobic compounds. Although these additives have been partially successful, their additions generally diminish the bleaching efficiency of the product, at least in proportion to their presence.
The use with sodium hydrosulfite is therefore carried out in paper mill operations with increasing care and concern because ofthe generally humid conditions and the presence of large quantities of water in paper processing; these problems have discouraged the use of sodium dithionite in the industry.
For this reason, zinc hydrosulfite, (zinc dithionite), ZnS O is preferred as a bleaching agent, since it is relatively stable toward spontaneous self-decomposition under normal transport and storage conditions. However, the zinc ion is considered toxic, therefore its presence in effluents from mills is not tolerated in many instances. Therefore, the user has a choice, between sodium hydrosulfite with its undesirable decomposition characteristics and zinc hydrosulfite with its toxic characteristics, necessitating the use of prohibitively expensive removal processes for the treatment ofeffluent waters.
DESCRIPTION OF THE PREFERRED EMBODIMENTS The term sodium hydrosulfite (dithionite) refers herein to the article of commerce which may contain between 85 and 98 percent weight percent sodium hydrosulfite (dithionite) along with certain impurities such as sodium chloride, sodium sulfate, sodium sulfite and thiosulfate.
Exemplary of the water soluble inorganic carbonate are the alkali metal carbonates and bicarbonates and ammonium carbonate. The sodium salts are preferred for economic reasons. For example: a mixture of approximately equal parts of sodium carbonate and sodium bicarbonate has been found to be satisfactory.
Exemplary of water soluble inorganic sulfites are the alkali metal and ammonium sulfites and bisulfites, the sodium salt being preferred. A mixture of additives consisting of approximately equal amounts of sodium sulfite and bisulfite is preferred.
With the exception of borax, it is desirable in the practice of this invention to use these ingredients in their anhydrous state. The presence of the water of crystallization in the borax has no adverse effect upon the application of this composition.
In practice hereunder, the desirable ranges of use of ingredients, based upon the weight of technical sodium hydrosulfite employed, are as follows:
a. oxalic: l to-25 percent b. carbonate: l to-3 percent c. borax: l to-5 percent d. sulfite: 0.5 to-l percent.
For practical purposes, the sum total ingredients aforesaid should not exceed 25 weight percent of the technical hydrosulfite content.
By the use of this mixture herein the generation of heat due to effect of moisture develops more slowly so that the critical temperature for spontaneous decomposition is not reached.
The composition of matter mixtures herein are compatible with the normal bleaching adjuvants such as are used in the bleaching of pulp particularly for example the complexforrning ingredients such as the polyphosphates and the various derivatives of ethylene diamine tetraacetic acid and nitrilo-triacetic acid. The adjuvants can be used herein by separate addition or as components of proprietary mixtures.
EXAMPLE I In a specific experiment designed to demonstrate the stabilization of sodium hydrosulfite against spontaneous decomposition caused by moisture the following formulation of comparable bleaching efficiency proved successful.
To 180 grams of commercial grade of sodium hydrosulfite the following components were added. The amount of additives comprised a total of 20 grams:
10 grams oxalic acid, anhydrous 6 grams of a carbonate comprising sodium bicarbonate and sodium carbonate in equal quantities 2 grams borax; and
2 grams of sulfites, containing respectively equal portions of sodium metabisulfite and sodium sulfite Commercial grade sodium hydrosulfite was placed in a stoppered bottle fitted with a gas evolution tube extending substantially through the stopper and with a second tube extending through the stopper to the bottom of the bottle. When 3 percent water was added through the bottom-extending tube, heat was evolved and the gas liberated was ignited when a bunsen flame was applied.
The composition of matter mixture described was thereafter applied to a hydrosulfite and the same amount of water added. This produced a comparatively lower reaction temperature and the decomposition products liberated could not be ignited with the bunsen flame.
EXAMPLE II The following composition was used to demonstrate improved sodium hydrosulfite stability and particularly improved bleaching efficiency.
l. percent sodium hydrosulfite 2. 2 percent sodium sulfite 3. 10 percent oxalic acid 4. 3 percent sodium borate 5. 5 percent sodium tripolyphosphate In an actual bleaching experiment, the product undergoing examination being spruce stone groundwood, the results below were obtained under these conditions.
A 3 percent consistency pulp slurry of the groundwood was treated for 45 minutes at F. at a pH of 5.0 to 5.5, the treatment being at a rate of IO lbs of hydrosulfite composition per ton of air dried groundwood pulp, aforesaid. The results are listed below.
(l) Brightnesses were measured on the Elrepho Electric Photo-Reflectometer using a magnesium oxide standard as l00%brightness.
I claim:
1. A stabilized composition of matter consisting essentially of a predetermined percent by weight of sodium hydrosulfite characterized by additives of oxalic acid and a water soluble inorganic carbonate, the percentages of weight of additives, relative to the sodium hydrosulfite, being not less than 1 percent nor more than 25 percent, said additives stabilizing the sodium hydrosulfite against spontaneous thermal decomposition.
2. The composition of matter of claim 1, and borax as a further additive.
3. The composition of matter of claim 2, and a water soluble inorganic sulfite as further additive.
4. The composition of matter of claim 1 wherein the inorganic carbonate is selected from the group consisting of sodiurn hydrogen carbonate and mixtures thereof and sodium carbonate as water soluble inorganic carbonates.
5. The composition of matter of claim 2 wherein the inorganic carbonate is selected from the group consisting of sodium hydrogen carbonate and mixtures thereof and sodium carbonate as water soluble inorganic carbonates.
6. The composition of matter of claim 3 wherein the inorganic carbonate is selected from the group consisting of sodium hydrogen carbonate and mixtures thereof and sodium carbonate as water soluble inorganic carbonates.
7. The composition of matter of claim 3 in which the water soluble inorganic sulfite is selected from the group consisting of sodium sulfite and sodium bisullite and mixtures thereof.
8. The composition of matter of claim 4 in which the water soluble inorganic sulfite is selected from the group consisting of sodium sulfite and sodium bisulfite and mixtures thereof.
9. The composition of matter of claim 1 wherein the propor tion of additives in percentage by weight to sodium hydrosulfite is:
A. oxalic acid 1-25 percent;
B. carbonate 1-3 percent.
10. The composition of matter of claim 9 wherein a further additive, borax, comprises in proportion by weight relative to the sodium hydrosulfite, 1-5 percent.
11. The composition of matter of claim 9 wherein a further additive of sulfites comprises in proportion by weight relative to the hydrosulfite 0.5-l percent.
* i i II
Claims (10)
- 2. The composition of matter of claim 1, and borax as a further additive.
- 3. The composition of matter of claim 2, and a water soluble inorganic sulfite as further additive.
- 4. The composition of matter of claim 1 wherein the inorganic carbonate is selected from the group consisting of sodium hydrogen carbonate and mixtures thereof and sodium carbonate as water soluble inorganic carbonates.
- 5. The composition of matter of claim 2 wherein the inorganic carbonate is selected from the group consisting of sodium hydrogen carbonate and mixtures thereof and sodium carbonate as water soluble inorganic carbonates.
- 6. The composition of matter of claim 3 wherein the inorganic carbonate is selected from the group consisting of sodium hydrogen carbonate and mixtures thereof and sodium carbonate as water soluble inorganic carbonates.
- 7. The composition of matter of claim 3 in which the water soluble inorganic sulfite is selected from the group consisting of sodium sulfite and sodium bisulfite and mixtures thereof.
- 8. The composition of matter of claim 4 in which the water soluble inorganic sulfite is selected from the group consisting of sodium sulfite and sodium bisulfite and mixtures thereof.
- 9. The composition of matter of claim 1 wherein the proportion of additives in percentage by weight to sodium hydrosulfite is: A. oxalic acid 1-25 percent; B. carbonate 1-3 percent.
- 10. The composition of matter of claim 9 wherein a further additive, borax, comprises in proportion by weight relative to the sodium hydrosulfite, 1-5 percent.
- 11. The composition of matter of claim 9 wherein a further additive of sulfites comprises in proportion by weight relative to the hydrosulfite 0.5-1 percent.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US6853770A | 1970-08-31 | 1970-08-31 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3669895A true US3669895A (en) | 1972-06-13 |
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ID=22083197
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US68537A Expired - Lifetime US3669895A (en) | 1970-08-31 | 1970-08-31 | Sodium hydrosulfite stabilization composition |
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| Country | Link |
|---|---|
| US (1) | US3669895A (en) |
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3933676A (en) * | 1974-04-08 | 1976-01-20 | Ventron Corporation | Stabilized aqueous solutions of sodium borohydride |
| US3985674A (en) * | 1974-12-10 | 1976-10-12 | Virginia Chemicals Inc. | Stabilized sodium dithionite solutions |
| US4066390A (en) * | 1973-08-15 | 1978-01-03 | Christie Nick J | Stable hydrosulfite compositions |
| US4092154A (en) * | 1976-09-02 | 1978-05-30 | American Chemical & Refining Co., Inc. | Aluminum containing precipitating agent for precious metals and method for its use |
| US4100098A (en) * | 1976-10-26 | 1978-07-11 | Olin Corporation | Stabilized solutions of sodium dithionite |
| US4357256A (en) * | 1979-03-13 | 1982-11-02 | Mitsubishi Gas Chemical Company, Inc. | Sodium hydrosulfite composition |
| EP0140218A3 (en) * | 1983-10-14 | 1987-05-20 | Basf Aktiengesellschaft | Stable, inert organic liquid-containing sodium dithionite compositions and their use |
| US4676961A (en) * | 1984-02-22 | 1987-06-30 | Basf Aktiengesellschaft | Stabilized water-containing sodium dithionite formulations which have been rendered alkaline |
| EP0677022A4 (en) * | 1992-12-31 | 1995-11-29 | ||
| US20100132898A1 (en) * | 2007-04-24 | 2010-06-03 | Basf Se | Process for the production of bleached wood particles and pale to white wood-base materials |
| CN102926186A (en) * | 2012-10-12 | 2013-02-13 | 濮阳宏业汇龙化工有限公司 | Powerful reduced powder |
| CN103552991A (en) * | 2013-10-23 | 2014-02-05 | 中盐安徽红四方股份有限公司 | Novel continuous large dropwise adding technological method in sodium hydrosulfite production |
| WO2016173884A1 (en) * | 2015-04-29 | 2016-11-03 | Basf Se | Stabilization of sodium dithionite by means of various additives |
| CN107938398A (en) * | 2017-11-14 | 2018-04-20 | 五邑大学 | A kind of oxalic acid rongalite combination of acidic reduction cleaner, its preparation method and its application |
| US20210292167A1 (en) * | 2018-05-17 | 2021-09-23 | ESSECO S.r.l. | Process for the Stabilisation of Hydrosulphite |
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| US2516321A (en) * | 1948-09-10 | 1950-07-25 | Rohm & Haas | Dry, stabilized sodium dithionite composition |
| US3054658A (en) * | 1959-12-07 | 1962-09-18 | Du Pont | Thermally stabilized sodium hydrosulfite compositions |
| US3353909A (en) * | 1962-12-22 | 1967-11-21 | Basf Ag | Thermally stabilized alkali metal dithionates |
| US3468623A (en) * | 1965-03-19 | 1969-09-23 | Koninkl Nl Zout Ind Nv | Dry stabilized dithionite compositions |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US2516321A (en) * | 1948-09-10 | 1950-07-25 | Rohm & Haas | Dry, stabilized sodium dithionite composition |
| US3054658A (en) * | 1959-12-07 | 1962-09-18 | Du Pont | Thermally stabilized sodium hydrosulfite compositions |
| US3353909A (en) * | 1962-12-22 | 1967-11-21 | Basf Ag | Thermally stabilized alkali metal dithionates |
| US3468623A (en) * | 1965-03-19 | 1969-09-23 | Koninkl Nl Zout Ind Nv | Dry stabilized dithionite compositions |
Cited By (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4066390A (en) * | 1973-08-15 | 1978-01-03 | Christie Nick J | Stable hydrosulfite compositions |
| US3933676A (en) * | 1974-04-08 | 1976-01-20 | Ventron Corporation | Stabilized aqueous solutions of sodium borohydride |
| US3985674A (en) * | 1974-12-10 | 1976-10-12 | Virginia Chemicals Inc. | Stabilized sodium dithionite solutions |
| US4092154A (en) * | 1976-09-02 | 1978-05-30 | American Chemical & Refining Co., Inc. | Aluminum containing precipitating agent for precious metals and method for its use |
| US4100098A (en) * | 1976-10-26 | 1978-07-11 | Olin Corporation | Stabilized solutions of sodium dithionite |
| US4357256A (en) * | 1979-03-13 | 1982-11-02 | Mitsubishi Gas Chemical Company, Inc. | Sodium hydrosulfite composition |
| EP0140218A3 (en) * | 1983-10-14 | 1987-05-20 | Basf Aktiengesellschaft | Stable, inert organic liquid-containing sodium dithionite compositions and their use |
| US4676961A (en) * | 1984-02-22 | 1987-06-30 | Basf Aktiengesellschaft | Stabilized water-containing sodium dithionite formulations which have been rendered alkaline |
| EP0677022A4 (en) * | 1992-12-31 | 1995-11-29 | ||
| US20100132898A1 (en) * | 2007-04-24 | 2010-06-03 | Basf Se | Process for the production of bleached wood particles and pale to white wood-base materials |
| US8784607B2 (en) * | 2007-04-24 | 2014-07-22 | Basf Se | Process for the production of bleached wood particles and pale to white wood-base materials |
| CN102926186A (en) * | 2012-10-12 | 2013-02-13 | 濮阳宏业汇龙化工有限公司 | Powerful reduced powder |
| CN102926186B (en) * | 2012-10-12 | 2014-05-14 | 濮阳宏业汇龙化工有限公司 | Powerful reduced powder |
| CN103552991A (en) * | 2013-10-23 | 2014-02-05 | 中盐安徽红四方股份有限公司 | Novel continuous large dropwise adding technological method in sodium hydrosulfite production |
| WO2016173884A1 (en) * | 2015-04-29 | 2016-11-03 | Basf Se | Stabilization of sodium dithionite by means of various additives |
| KR20170140239A (en) * | 2015-04-29 | 2017-12-20 | 바스프 에스이 | Stabilization of sodium dithionite by various additives |
| US10850982B2 (en) | 2015-04-29 | 2020-12-01 | Basf Se | Stabilization of sodium dithionite by means of various additives |
| CN107938398A (en) * | 2017-11-14 | 2018-04-20 | 五邑大学 | A kind of oxalic acid rongalite combination of acidic reduction cleaner, its preparation method and its application |
| US20210292167A1 (en) * | 2018-05-17 | 2021-09-23 | ESSECO S.r.l. | Process for the Stabilisation of Hydrosulphite |
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| Date | Code | Title | Description |
|---|---|---|---|
| AS | Assignment |
Owner name: VIRGINIA CHEMICALS INC., A CORP. OF DE. Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNOR:VIRGINIA CHEMICALS INC., A CORP. OF MAINE;REEL/FRAME:003938/0131 |
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| AS | Assignment |
Owner name: HOECHST CELANESE CORPORATION, A CORP. OF DE Free format text: MERGER;ASSIGNOR:VIRGINIA CHEMICALS INC.;REEL/FRAME:005025/0662 Effective date: 19881107 |