CN101495404A - Method for the catalytic oxidation of sulfide to sulfate - Google Patents
Method for the catalytic oxidation of sulfide to sulfate Download PDFInfo
- Publication number
- CN101495404A CN101495404A CN200780027892.2A CN200780027892A CN101495404A CN 101495404 A CN101495404 A CN 101495404A CN 200780027892 A CN200780027892 A CN 200780027892A CN 101495404 A CN101495404 A CN 101495404A
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- Prior art keywords
- sulfide
- preferred
- vitriol
- reactor
- oxygen
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Classifications
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- 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
- C01B17/48—Sulfur dioxide; Sulfurous acid
- C01B17/50—Preparation of sulfur dioxide
- C01B17/508—Preparation of sulfur dioxide by oxidation of sulfur compounds
-
- 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
- C01B17/96—Methods for the preparation of sulfates in general
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
- D21C11/00—Regeneration of pulp liquors or effluent waste waters
- D21C11/12—Combustion of pulp liquors
- D21C11/14—Wet combustion ; Treatment of pulp liquors without previous evaporation, by oxidation of the liquors remaining at least partially in the liquid phase, e.g. by application or pressure
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/101—Sulfur compounds
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
- D21C11/00—Regeneration of pulp liquors or effluent waste waters
- D21C11/06—Treatment of pulp gases; Recovery of the heat content of the gases; Treatment of gases arising from various sources in pulp and paper mills; Regeneration of gaseous SO2, e.g. arising from liquors containing sulfur compounds
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Catalysts (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a method for catalytically oxidating sulfide (S<2->) to sulfide (SO4<2->), especially a method for catalytically oxidating alkali metal sulfides, alkaline earth metal sulfides, transition metal sulfide and ammonium sulfide to corresponding sulfide. The invention also relates to the use of the method in purifying the waste water from the preparation of barium sulfate, or paper making.
Description
The present invention relates to a kind of with sulfide (S
2-) Catalytic Oxygen changes into vitriol (SO
4 2-) method, particularly alkali metalsulphide and alkaline earth sulfide and transient metal sulfide and ammonium sulfide Catalytic Oxygen are changed into the method for corresponding vitriol.
With sodium sulphite (Na
2S) Catalytic Oxygen changes into sodium sulfate (Na
2SO
4) problem relevant with industrial technology proposed.In the chemical process of many big industries, produce the Na of aqueous solution form
2S is for example at preparation barium sulfate (BaSO
4) in promptly so.This solution is strong basicity and can partly be used for for example depilation of the animal skin of leather industry, but should be higher than other industrial requirement by the industry generation.The Na of this generation
2The common method of disposal of S solution is to mix sulfuric acid (H
2SO
4), at this moment form hydrogen sulfide (H
2S) and metabisulfite solution.This stink damp body and function oxygen changes into sulfurous gas (SO
2), and then be reprocessed into sulfuric acid (H
2SO
4).But also produce elementary sulfur when hydrogen sulfide and sulfuric acid reaction, this elementary sulfur randomly can be sneaked in the device and be caused problem thus.In addition, because the high toxicity of hydrogen sulfide has to take special safe security measures; Therefore this device Germany to observe the accident management regulations (
).
A series of suggestion that is used for sulfide oxidation known in the state of the art.
Disclose using under the non-impregnated C catalyst condition as US-A-4855123 sodium sulphite has been oxidized to polysulfide and Sulfothiorine.But the not shown method that sodium sulphite is oxidized to sodium sulfate.
US-A-5207927 discloses under the C catalyst condition of using with the metal phthalocyanine compound dipping with US-A-5470486 the sodium sulphite selective oxidation has been become sodium sulfate.At this moment to use the oxygen of hyperstoichiometry amount.The shortcoming of this method is gone back call for bids lattice expensive catalysts except that high oxygen requirement, because this dipping is easy to dialysis, so this catalyzer only has little stability.
US-A-5338463 discloses the purposes that the C catalyst that scribbles insoluble copper compound is used for sulfide oxidation is become vitriol.This catalyzer through applying also be expensive, be easy to dialysis and therefore have little stability.
US-A-6017501 disclose a kind of by means of the C catalyst in three-phase fixed bed spray-type reactor with gaseous state H
2S is oxidized to the method for vitriol.H
2The solubleness of S in water is 0.1mol/L to the maximum, because dissolved H
2The little dissociation degree of S (only 10
-13Mol/L) exist as dissolved sulfide.Different therewith is the Na that forms in the aqueous solution when industrial preparation barium sulfate
2S exists with the concentration of 3mol/L at the most before oxidation, and this salt is complete dissociative.The sulfide oxidation that the unexposed wherein sulfide of US-A-6017501 exists with dissolved salt anionic form in the aqueous solution becomes the method for vitriol.
People such as Bal ' zhinmaev are at " Proceedings of 12
ThInternational Congress onCatalysis, Spain (2000) " in a kind of the use under the C catalyst SIBUNIT condition sodium sulphite (Na disclosed
2S) be oxidized to sodium sulfate (Na
2SO
4) the principle method.This catalyst screening test is carried out in the pressure reactor (reactor volume is 200ml) of intermittent operation; Once utilized the through-flow reactor of making by tetrafluoroethylene (reactor volume is 15ml) for studying mass transfer process and heat transfer process.This equipment is not suitable in technical scale to be implemented sulfide (S
2-) Catalytic Oxygen changes into vitriol (SO
4 2-), because its transformation efficiency and selectivity are not enough, in addition because because this method of loss of unreacted oxygen is expensive.
The objective of the invention is to overcome the shortcoming of prior art and a kind of method is provided, the sulfide oxidation that will be in the aqueous solution exists with the anionic form of salt by this method eshaustibility may be simple and cost is favourable mode becomes vitriol.Other purpose is that this method is the loss that the successive reaction process is carried out, used untreated catalyzer, guarantees almost completely sulfide to be changed into vitriol under highly selective and/or avoid unreacted oxygen.
Surprisingly, the present invention has solved this problem by the characteristic of main claim.Preferred embodiment is listed in the dependent claims.
Find especially unexpectedly, if in the method that is used for catalytic oxidation of sulfide is become vitriol of the present invention, the aqueous solution of sulfide is at phase reactor particularly in the fixed bed spray-type reactor, using the particularly untreated porous carbon materials of C catalyst for example can be after for the first time by this reactor to reach almost completely the transformation efficiency from sulfide to vitriol (＞99.5%) with selectivity＞99.5% with the oxygen of hyperstoichiometry amount during SIBUNIT-3.Wherein excessive oxygen is through returning.
Oxygen can be used as the mixture of gasiform pure oxygen or industrial oxygen or itself and other gas, particularly adds as pressurized air.Preferred form with industrial pure oxygen adds oxygen among the present invention.Because wherein this oxygenant is that oxygen exists with highly enriched form, so this reactor can be designed to the reactor when using pressurized air.In addition, pressurized air always must be with relatively large adding, and this is because the oxygen that exists with low concentration in pressurized air is consumed quickly; This causes the compressed-air actuated lasting compression that expends.In addition, the nitrogen that exists as main component in pressurized air has occupied catalyst surface, and has reduced its activity thus.
The preferred fixed bed spray-type of the present invention reactor is a phase reactor, and wherein gaseous state, liquid state are in contact with one another mutually with solid-state.For example it can be designed to be filled with the tubular reactor of catalyzer.
Use fixed bed spray-type reactor among the present invention because this guaranteed that simple operation and scale change, high volume transformation efficiency and more reliable the keeping (R ü ckhalt) of catalyzer.Because the narrow residence time by reaction tubes distributes and very outstanding be applied the material that thing (Substrat) concentration gradient can reach almost completely and transform.In addition, this type of reactor only has little running cost.
But the shortcoming of this type of reactor is the heat transfer characteristic of difference, must take technology measure with the optimum temperature profile in the realization response device to this.Should be not low excessively as temperature at reactor inlet, to guarantee enough speed of response.Simultaneously should be not too high in the temperature of reactor exit yet, with the formation that reduces by product with avoid catalyst aging.
As catalyzer, the present invention preferably uses untreated porous carbon materials, as the catalyzer of SIBUNIT-series, and preferred especially SIBUNIT-3.This catalyzer has high activity to become vitriol from sulfide oxidation in highly selective, have long work-ing life simultaneously.The structure of this catalyzer and characteristic description are in patent application DE-A-3912886, and its whole disclosures are integral parts of this specification sheets, and are recorded in " Proceedings of 12
ThInternational Congresson Catalysis, Spain (2000)/people such as Bal ' zhinmaev " in.
Details are as follows for theme of the present invention:
-be used for catalytic oxidation of sulfide is become the method for vitriol;
-catalytic oxidation of sulfide is become the method for vitriol by means of gaseous oxidizer;
-be used for catalytic oxidation of sulfide is become the method for vitriol, wherein this is reflected in the phase reactor that contains catalyzer, preferably in containing the fixed-bed reactor of catalyzer, particularly preferably in carrying out in the fixed bed spray-type reactor that contains catalyzer;
-be used for catalytic oxidation of sulfide is become the method for vitriol, wherein sulfide and vitriol are present in the aqueous solution;
-be used for catalytic oxidation of sulfide is become the method for vitriol, wherein this sulfide exists with dissolved salt anionic form;
-be used for catalytic oxidation of sulfide is become the method for vitriol, wherein this vitriol exists with dissolved salt anionic form;
-be used for catalytic oxidation of sulfide is become the method for vitriol, wherein this method is moved in the successive reaction mode;
-be used for catalytic oxidation of sulfide is become the method for vitriol, wherein use untreated porous carbon materials as catalyzer;
-be used for catalytic oxidation of sulfide is become the method for vitriol, wherein use SIBUNIT-3 as catalyzer;
-be used for catalytic oxidation of sulfide is become the method for vitriol, be 99-99.999% wherein in selectivity, under the preferred 99.5-99.99% situation, the transformation efficiency that sulfide changes into vitriol is 99-99.999%, preferred 99.5-99.99%;
-be used for catalytic oxidation of sulfide is become the method for vitriol, wherein sulfide is alkali metalsulphide, preferred sodium sulphite and/or potassium sulphide;
-be used for catalytic oxidation of sulfide is become the method for vitriol, wherein sulfide is alkaline earth sulfide, preferred magnesium sulfide and/or sulfurated lime;
-be used for catalytic oxidation of sulfide is become the method for vitriol, wherein sulfide is ammonium sulfide;
-be used for catalytic oxidation of sulfide is become the method for vitriol, wherein sulfide is transient metal sulfide;
-be used for catalytic oxidation of sulfide is become the method for vitriol, wherein the concentration of this sulfide solution is 0.1-3mol/L, preferred 0.3-2mol/L, preferred especially 0.5-1.5mol/L;
-be used for catalytic oxidation of sulfide is become the method for vitriol, wherein use oxygen as oxygenant;
-be used for catalytic oxidation of sulfide is become the method for vitriol, wherein oxygen is the gaseous state adding as industrial pure oxygen;
-be used for catalytic oxidation of sulfide is become the method for vitriol, wherein oxygen with other gaseous state mixture of ingredients in be gaseous state and add;
-be used for catalytic oxidation of sulfide is become the method for vitriol, wherein oxygen adds with the pressurized air form;
-be used for catalytic oxidation of sulfide is become the method for vitriol, wherein oxygen uses with the hyperstoichiometry ratio with respect to sulfide;
-be used for catalytic oxidation of sulfide is become the method for vitriol, wherein stoichiometric factor n (O
2)/n (S
2-) be 1-10, preferred 1.5-8, preferred especially 2-6, very particularly preferably 3-5;
-be used for catalytic oxidation of sulfide is become the method for vitriol, wherein the oxygen that does not consume is sent back in this method again;
-be used for catalytic oxidation of sulfide is become the method for vitriol, be 1 with the ratio that turns back to the vitriol in the reactor wherein: 2-1: 20, preferred 1: 5-1: 15, preferred especially 1: 7-1: 12 by the vitriol of discharging in the method;
-be used for catalytic oxidation of sulfide is become the method for vitriol, wherein be used for guaranteeing high liquid load and be used to make along the minimized sulfate liquor that turns back to reactor of the thermal insulation warming of catalyst filling, and mix with sulfide solution through heat exchanger cooling;
-being used for catalytic oxidation of sulfide is become the method for vitriol, the heat energy that wherein produces in heat exchanger is used for other method;
-be used for catalytic oxidation of sulfide is become the method for vitriol, wherein the temperature of oxidizing reaction is 90-170 ℃, preferred 105-155 ℃, preferred 115-145 ℃ especially;
-be used for catalytic oxidation of sulfide is become the method for vitriol, wherein reactor inlet temperature is 90-150 ℃, preferred 100-140 ℃, preferred 110-130 ℃ especially;
-be used for catalytic oxidation of sulfide is become the method for vitriol, wherein the reactor outlet temperature is 110-170 ℃, preferred 120-160 ℃, preferred 130-150 ℃ especially;
-be used for catalytic oxidation of sulfide is become the method for vitriol, wherein the pressure of oxidizing reaction is the 1-50 crust, preferred 5-25 crust, preferred especially 12-18 crust;
-be used for becoming the method for vitriol to be used to purify the waste water that is loaded with sulfide catalytic oxidation of sulfide, preferably from the purposes of the waste water of preparation barium sulfate and/or papermaking;
-being used for becoming the method for vitriol to be used to obtain the purposes of vitriol catalytic oxidation of sulfide, described vitriol can be used in the production method, is preferred for producing in the barium sulfate;
Fig. 1 example illustration illustrates and is used to implement the schematic diagram of device that is used for catalytic oxidation of sulfide is become the method for vitriol of the present invention, but the present invention is not subject to this.
The oxygen of carrying secretly in this sulfide solution and the liquid stream is cocurrent flow and closely contacts with catalyst surface, and actual oxidizing reaction takes place on catalyst surface.
After the liquid stream percolation was crossed catalyzer, this liquid stream left with the reactor outlet 7 of dissolved vitriol through the reactor lower end.Because becoming vitriol by sulfide oxidation is strong heat release, the heat exchanger 8 so this liquid stream is flowed through, the heat that produces in heat exchanger is discharged through cold water materials flow 9/10, and can utilize for other method.Take out the little part logistics 11 of sulfate liquor behind the heat exchanger, and from the method circulation, remove thus.This sulfate liquor can be used further to other preparation method, for example is used to prepare barium sulfate.The bigger part materials flow 12 of this sulfate liquor merges with sulfide solution materials flow 1, and sends into reactor through inlet again.This undiluted sulfide solution materials flow is through preheating thus, and also through to a certain degree dilution, so that, should when oxidizing reaction, reach optimum temps (90-170 ℃), do not surpass this optimum temps at reactor exit on the other hand for catalyzer on the one hand at the reactor inlet place.The high liquid load that this can keep reactor need not to add in addition liquid simultaneously, and this causes unnecessarily diluting metabisulfite solution to be discharged.In addition, can make the pressure-losses in the system remain low.
The excessive oxygen that should not consume in reaction separates with liquid stream below by gas/liquid separation at catalyst filling, and discharges and send into from the reactor top with the oxygen that newly adds from reactor.After repeatedly flowing through, reach OTR completely thus.In addition, also can make the pressure-losses in the system remain low.
Exemplarily provide relevant operating parameter below, and the present invention is not subject to this.
Embodiment 1:
Oxygenant: oxygen (100%, industry)
Pressure p=15 crust
Reactor inlet temperature T=120 ℃
Reactor outlet temperature T=140 ℃
V (Na
2S-solution)=and 50L/h, contain and return 1/9
C (Na
2S-solution)=0.77mol/L
Stoichiometric factor N (O
2)/n (Na
2S)=4
Transformation efficiency/selectivity:＞99.5%/＞99.5%
The comparative example 1: the stoichiometric factor N (O of reduction
2)/n (Na
2S)
Oxygenant: oxygen (100%, industry)
Pressure p=15 crust
Reactor inlet temperature T=120 ℃
Reactor outlet temperature T=140 ℃
V (Na
2S-solution)=and 50L/h, contain and return 1/9
C (Na
2S-solution)=0.77mol/L
Stoichiometric factor N (O
2)/n (Na
2S)=2
Transformation efficiency/selectivity:＞99.5%/about 60%
The comparative example 2: the pressure of reduction
Oxygenant: oxygen (100%, industry)
Pressure p=10 crust
Reactor inlet temperature T=120 ℃
Reactor outlet temperature T=140 ℃
V (Na
2S-solution)=and 50L/h, contain and return 1/9
C (Na
2S-solution)=0.77mol/L
Stoichiometric factor N (O
2)/n (Na
2S)=2
Transformation efficiency/selectivity:＞99.5%/about 65%
The comparative example 3: the oxygen partial pressure of reduction
Oxygenant: oxygen (100%, industry)
Pressure p=10 crust
Reactor inlet temperature T=120 ℃
Reactor outlet temperature T=140 ℃
V (Na
2S-solution)=and 50L/h, contain and return 1/9
C (Na
2S-solution)=0.77mol/L
Stoichiometric factor N (O
2)/n (Na
2S)=2
Transformation efficiency/selectivity: about 92%/about 17%
Compare with comparative example 1-3, embodiment 1 shows that obviously it is conclusive that the selection of correct operating parameter is used the economy of method.
Claims (26)
1. method that is used for catalytic oxidation of sulfide is become vitriol, it is characterized in that, sulfide and vitriol all exist with the form of dissolved salt anionic in the aqueous solution, and this is reflected in the phase reactor that contains catalyzer, preferably in containing the fixed-bed reactor of catalyzer, particularly preferably in carrying out by means of gaseous oxidizer in the fixed bed spray-type reactor that contains catalyzer.
2. the method for claim 1 is characterized in that, this method is moved in the successive reaction mode.
3. claim 1 or 2 method is characterized in that, use untreated porous carbon materials as catalyzer.
4. claim 1-3 method one of at least is characterized in that, uses SIBUNIT-3 as catalyzer.
5. claim 1-4 method one of at least is characterized in that, is 99-99.999% in selectivity, and under the situation of preferred 99.5-99.99%, the transformation efficiency that described sulfide changes into vitriol is 99-99.999%, preferred 99.5-99.99%.
6. claim 1-5 method one of at least is characterized in that described sulfide is alkali metalsulphide, preferred sodium sulphite and/or potassium sulphide.
7. claim 1-5 method one of at least is characterized in that described sulfide is alkaline earth sulfide, preferred magnesium sulfide and/or sulfurated lime.
8. claim 1-5 method one of at least is characterized in that described sulfide is ammonium sulfide.
9. claim 1-5 method one of at least is characterized in that described sulfide is transient metal sulfide.
10. claim 1-9 method one of at least is characterized in that the concentration of described sulfide solution is 0.1-3mol/L, preferred 0.3-2mol/L, preferred especially 0.5-1.5mol/L.
11. claim 1-10 method one of at least is characterized in that, with oxygen as oxygenant.
12. claim 1-11 method one of at least is characterized in that, oxygen is gaseous state as industrial pure oxygen and adds.
13. claim 1-11 method one of at least is characterized in that, oxygen with other gaseous state mixture of ingredients in be gaseous state and add.
14. claim 1-11 or 13 method one of at least is characterized in that oxygen adds with the pressurized air form.
15. claim 1-14 method one of at least is characterized in that, oxygen with respect to sulfide with hyperstoichiometry than using.
16. claim 1-15 method one of at least is characterized in that stoichiometric factor n (O
2)/n (S
2-) be 1-10, preferred 1.5-8, preferred especially 2-6, very particularly preferably 3-5.
17. claim 1-16 method one of at least is characterized in that the oxygen of Xiao Haoing is not sent back in this method again.
18. claim 1-17 method one of at least is characterized in that, is 1 by vitriol of discharging in this method and the ratio that turns back to the vitriol in the reactor wherein: 2-1: 20, preferred 1: 5-1: 15, preferred especially 1: 7-1: 12.
19. claim 1-18 method one of at least is characterized in that, turns back to sulfate liquor in the reactor heat exchanger of flowing through.
20. claim 1-19 method one of at least is characterized in that the heat energy that produces is used for other method in heat exchanger.
21. one or multinomial method is characterized in that among the claim 1-20, the temperature of oxidizing reaction is 90-170 ℃, preferred 105-155 ℃, and preferred 115-145 ℃ especially.
22. claim 1-21 method one of at least is characterized in that reactor inlet temperature is 90-150 ℃, preferred 100-140 ℃, and preferred 110-130 ℃ especially.
23. claim 1-22 method one of at least is characterized in that the reactor outlet temperature is 110-170 ℃, preferred 120-160 ℃, and preferred 130-150 ℃ especially.
24. claim 1-23 method one of at least is characterized in that, the pressure of oxidizing reaction is the 1-50 crust, preferred 5-25 crust, preferred especially 12-18 crust.
25. claim 1-24 method one of at least is used to purify the waste water that is loaded with sulfide, preferably from the purposes of the waste water of preparation barium sulfate or papermaking.
26. claim 1-24 method one of at least is used to obtain the purposes of vitriol, described vitriol can be used in the production method, is preferred for producing barium sulfate.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE102006024917.8 | 2006-05-24 | ||
| DE102006024917 | 2006-05-24 | ||
| PCT/EP2007/055035 WO2007135184A2 (en) | 2006-05-24 | 2007-05-24 | Method for the catalytic oxidation of sulfide to sulfate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101495404A true CN101495404A (en) | 2009-07-29 |
| CN101495404B CN101495404B (en) | 2013-05-29 |
Family
ID=38537640
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200780027892.2A Expired - Fee Related CN101495404B (en) | 2006-05-24 | 2007-05-24 | Method for the catalytic oxidation of sulfide to sulfate |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP2029479A2 (en) |
| CN (1) | CN101495404B (en) |
| BR (1) | BRPI0712503A2 (en) |
| WO (1) | WO2007135184A2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101798068A (en) * | 2010-03-29 | 2010-08-11 | 罗德春 | Sulfide or thiosulfate catalytic air complete oxidation at normal temperature and pressure |
| CN111099712A (en) * | 2020-01-15 | 2020-05-05 | 山东汇海医药化工有限公司 | Method for treating sodium sulfide wastewater generated in DCC synthesis process by using oxygen |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4024229A (en) * | 1970-11-06 | 1977-05-17 | The Mead Corporation | Production of polysulfide with PTFE coated catalyst |
| JPS62247812A (en) * | 1986-04-18 | 1987-10-28 | Chiyoda Chem Eng & Constr Co Ltd | Pressure-type upward flow deep bed filtration method and filter used in said method |
| US4839154A (en) * | 1986-12-29 | 1989-06-13 | Conoco Inc. | Process for converting sulfide ion to innocuous, solubile sulfur species |
| DE3718277A1 (en) * | 1987-05-30 | 1988-12-15 | Metallgesellschaft Ag | METHOD FOR PRODUCING BARIUM SULFATE WITH CHEMOREACTIVE SURFACE |
| US5207927A (en) * | 1992-03-18 | 1993-05-04 | Uop | Treatment of an aqueous stream containing water-soluble inorganic sulfide compounds |
-
2007
- 2007-05-24 BR BRPI0712503-8A patent/BRPI0712503A2/en not_active IP Right Cessation
- 2007-05-24 CN CN200780027892.2A patent/CN101495404B/en not_active Expired - Fee Related
- 2007-05-24 EP EP07729466A patent/EP2029479A2/en not_active Withdrawn
- 2007-05-24 WO PCT/EP2007/055035 patent/WO2007135184A2/en active Application Filing
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101798068A (en) * | 2010-03-29 | 2010-08-11 | 罗德春 | Sulfide or thiosulfate catalytic air complete oxidation at normal temperature and pressure |
| CN101798068B (en) * | 2010-03-29 | 2011-10-26 | 罗德春 | Sulfide or thiosulfate catalytic air complete oxidation at normal temperature and pressure |
| CN111099712A (en) * | 2020-01-15 | 2020-05-05 | 山东汇海医药化工有限公司 | Method for treating sodium sulfide wastewater generated in DCC synthesis process by using oxygen |
| WO2021143250A1 (en) * | 2020-01-15 | 2021-07-22 | 山东汇海医药化工有限公司 | Method for using oxygen to treat alkali sulfide wastewater produced during process of dcc synthesis |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101495404B (en) | 2013-05-29 |
| WO2007135184A3 (en) | 2008-04-17 |
| EP2029479A2 (en) | 2009-03-04 |
| WO2007135184A2 (en) | 2007-11-29 |
| BRPI0712503A2 (en) | 2012-08-28 |
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