CN101495404B - Method for the catalytic oxidation of sulfide to sulfate - Google Patents
Method for the catalytic oxidation of sulfide to sulfate Download PDFInfo
- Publication number
- CN101495404B CN101495404B CN200780027892.2A CN200780027892A CN101495404B CN 101495404 B CN101495404 B CN 101495404B CN 200780027892 A CN200780027892 A CN 200780027892A CN 101495404 B CN101495404 B CN 101495404B
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- Prior art keywords
- sulfide
- vitriol
- oxygen
- reactor
- catalyzer
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- Expired - Fee Related
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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
- C01B17/48—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 large industries, produce the Na of aqueous solution form
2S is for example at preparation barium sulfate (BaSO
4) in namely 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 thus problem.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 for sulfide oxidation known in the state of the art.
Disclose using under the non-impregnated C catalyst condition such 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 the method also needs expensive catalyzer except 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 being oxidation of the sulfide into 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 solid 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 the H of dissolving
2The little dissociation degree of S (only 10
-13Mol/L) sulfide as dissolving exists.Differently therewith be the Na that when industry prepares barium sulfate, in the aqueous solution, forms
2S exists with the concentration of 3mol/L at the most before oxidation, and this salt dissociates fully.The unexposed sulfide that its medium sulphide content is existed with the salt anionic form of dissolving in the aqueous solution of US-A-6017501 is oxidized to the method for vitriol.
The 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 (reactor volume is 15ml) of being made by tetrafluoroethylene 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 inadequate, in addition because because loss the method for 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 that will be in the aqueous solution exists with the anionic form of salt by the method eshaustibility may be simple and cost is favourable mode is oxidized to vitriol.Other purpose is that the method is the loss that continuous 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 for catalytic oxidation of sulfide being become vitriol of the present invention, the aqueous solution of sulfide is at phase reactor particularly in the fixed bed spray-type reactor, use C catalyst particularly untreated porous carbon materials for example can be after for the first time by this reactor 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 the pure oxygen of gaseous state 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 the reactor when this reactor can be designed to less than use 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 thus its activity.
The preferred fixed bed spray-type of the present invention reactor is 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 thing (Substrat) concentration gradient that is applied can reach almost completely Substance Transformation.In addition, this type of reactor only has little running cost.
But the shortcoming of this type of reactor is poor heat transfer characteristic, must take technology measure with the optimum temperature profile in the realization response device to this.Should be excessively not low such as the 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, such as the catalyzer of SIBUNIT-series, particularly preferably SIBUNIT-3.This catalyzer has high activity to be oxidized to vitriol from sulfide in highly selective, have simultaneously long work-ing life.The structure and characteristics of this catalyzer is described among the patent application DE-A-3912886, and its whole disclosures are integral parts of this specification sheets, and is recorded in " Proceedings of 12
ThInternational Congresson Catalysis, Spain (the 2000)/people such as Bal ' zhinmaev " in.
Details are as follows for theme of the present invention:
-for the method that catalytic oxidation of sulfide is become 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 reaction is in containing the phase reactor of 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;
-being used for catalytic oxidation of sulfide is become the method for vitriol, its medium sulphide content 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 the salt anionic form of dissolving;
-be used for catalytic oxidation of sulfide is become the method for vitriol, wherein this vitriol exists with the salt anionic form of dissolving;
-be used for catalytic oxidation of sulfide is become the method for vitriol, wherein the 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% in selectivity wherein, in the preferred 99.5-99.99% situation, the transformation efficiency that sulfide changes into vitriol is 99-99.999%, preferred 99.5-99.99%;
-being used for catalytic oxidation of sulfide is become the method for vitriol, its medium sulphide content is alkali metalsulphide, preferred sodium sulphite and/or potassium sulphide;
-being used for catalytic oxidation of sulfide is become the method for vitriol, its medium sulphide content is alkaline earth sulfide, preferred magnesium sulfide and/or sulfurated lime;
-being used for catalytic oxidation of sulfide is become the method for vitriol, its medium sulphide content is ammonium sulfide;
-being used for catalytic oxidation of sulfide is become the method for vitriol, its medium sulphide content 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, particularly preferably 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 the mixture of other gaseous state composition 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 super-stoichiometry with respect to sulfide;
-for the method that catalytic oxidation of sulfide is become vitriol, wherein stoichiometric factor n (O
2)/n (S
2-) be 1-10, preferred 1.5-8, particularly preferably 2-6, very particularly preferably 3-5;
-being used for catalytic oxidation of sulfide is become the method for vitriol, the oxygen that does not wherein consume is sent back in the method again;
-be used for catalytic oxidation of sulfide is become the method for vitriol, be 1 by the vitriol of discharging in the method and the ratio that turns back to the vitriol in the reactor wherein: 2-1: 20, preferred 1: 5-1: 15, particularly preferably 1: 7-1: 12;
-be used for catalytic oxidation of sulfide is become the method for vitriol, wherein be used for guaranteeing high liquid load and be used for making along the minimized sulfate liquor that turns back to reactor of the thermal insulation warming of catalyst filling through heat exchanger cooling, and mix with sulfide solution;
-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 ℃, particularly preferably 115-145 ℃;
-be used for catalytic oxidation of sulfide is become the method for vitriol, wherein reactor inlet temperature is 90-150 ℃, preferred 100-140 ℃, particularly preferably 110-130 ℃;
-be used for catalytic oxidation of sulfide is become the method for vitriol, wherein the reactor outlet temperature is 110-170 ℃, preferred 120-160 ℃, particularly preferably 130-150 ℃;
-be used for catalytic oxidation of sulfide is become the method for vitriol, wherein the pressure of oxidizing reaction is the 1-50 bar, preferred 5-25 bar, particularly preferably 12-18 bar;
-be used for becoming the method for vitriol to be used for purifying 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 for obtaining 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 the schematic diagram be used to the device of implementing the method for catalytic oxidation of sulfide being become 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 catalyst surface close contact, at catalyst surface actual oxidizing reaction occurs.
After the liquid stream percolation was crossed catalyzer, this liquid stream left with the reactor outlet 7 of vitriol through the reactor lower end of dissolving.Because being oxidized to vitriol by sulfide 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 material stream 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 for the preparation of barium sulfate.Larger section's part-streams 12 of this sulfate liquor merges with sulfide solution material stream 1, and sends into reactor through entrance again.Thus this undiluted sulfide solution material preheating of flowing through, and also through to a certain degree dilution, so that on the one hand at the reactor inlet place, should when oxidizing reaction, reach the optimum temps (90-170 ℃) for catalyzer, do not surpass this optimum temps at reactor exit on the other hand.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 thus completely OTR.In addition, also can make the pressure-losses in the system remain low.
The below exemplarily provides relevant operating parameter, and the present invention is not subject to this.
Embodiment 1:
Oxygenant: oxygen (100%, industry)
Pressure p=15 bar
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 bar
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 bar
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 bar
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 (13)
1. method that is used for catalytic oxidation of sulfide is become vitriol, its medium sulphide content and vitriol in the aqueous solution all the form with the salt anionic that dissolves exist, and this reaction is carried out by means of gaseous oxidizer in containing the phase reactor of catalyzer;
It is characterized in that,
The method is moved in the successive reaction mode,
Wherein use untreated porous carbon materials as catalyzer; And catalyzer is SIBUNIT-3;
The concentration of described sulfide solution is 0.5-1.5mol/L, and wherein uses oxygen as oxygenant;
Wherein oxygen is used with hyperstoichiometry and stoichiometric factor n (O with respect to sulfide
2)/n (S
2-) be 3-5;
Be 1 by the vitriol of discharging in the method with the ratio that turns back to the vitriol in the reactor wherein: 7-1: 12;
Wherein reactor inlet temperature is that 110-130 ℃ and reactor outlet temperature are 130-150 ℃, and the pressure of oxidizing reaction is the 12-18 bar.
2. according to claim 1 method is characterized in that, oxygen is gaseous state as industrial pure oxygen and adds.
3. according to claim 1 method is characterized in that, oxygen with the mixture of other gaseous state composition in be gaseous state and add.
4. according to claim 2 method is characterized in that oxygen adds with the pressurized air form.
5. according to claim 3 method is characterized in that oxygen adds with the pressurized air form.
6. method one of according to claim 1-5 is characterized in that, the oxygen that consumes is not sent back in the method again.
7. method one of according to claim 1-5 is characterized in that, turns back to sulfate liquor in the reactor heat exchanger of flowing through.
8. according to claim 7 method is characterized in that, the heat energy that produces in heat exchanger is used for other method.
9. method one of according to claim 1-5, wherein, described reaction is carried out by means of gaseous oxidizer in containing the fixed-bed reactor of catalyzer.
10. method one of according to claim 1-5, wherein, described reaction is carried out by means of gaseous oxidizer in containing the fixed bed spray-type reactor of catalyzer.
11. the method for one of claim 1-10 is used for purifying the purposes of the waste water that is loaded with sulfide.
12. method according to claim 11 is used for purifying the purposes from the waste water of preparation barium sulfate or papermaking.
13. a production method of having used vitriol to produce barium sulfate said method comprising the steps of: the method that obtains one of the claim 1-10 of described vitriol.
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 CN101495404A (en) | 2009-07-29 |
| CN101495404B true 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) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN88103235A (en) * | 1987-05-30 | 1988-12-21 | 金属股份有限公司 | Preparation method with barium sulfate of chemically reactive surface |
Family Cites Families (4)
| 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 |
| 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
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN88103235A (en) * | 1987-05-30 | 1988-12-21 | 金属股份有限公司 | Preparation method with barium sulfate of chemically reactive surface |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2007135184A3 (en) | 2008-04-17 |
| CN101495404A (en) | 2009-07-29 |
| EP2029479A2 (en) | 2009-03-04 |
| WO2007135184A2 (en) | 2007-11-29 |
| BRPI0712503A2 (en) | 2012-08-28 |
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