CN102925699B - Method for recovering rhodium from dead catalysts containing rhodium of hydroformylation reaction through treatment of hydrogen peroxide - Google Patents
Method for recovering rhodium from dead catalysts containing rhodium of hydroformylation reaction through treatment of hydrogen peroxide Download PDFInfo
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Abstract
The invention discloses a method for recovering rhodium from dead catalysts containing rhodium of hydroformylation reaction through treatment of hydrogen peroxide. The method is characterized by firstly treating waste rhodium liquid through hydrogen peroxide, recovering nearly 90% of rhodium in the waste rhodium liquid in deposition mode, concentrating the remaining rhodium liquid containing nearly 10% of rhodium to obtain rhodium slag, burning the rhodium slag in an electric furnace, removing residual carbon deposition in the slag to obtain rhodium metal containing other metal impurities, and preparing the rhodium metal obtained from the two-step treatment into rhodium chloride hydrate which is the raw material of a complex catalyst for preparing rhodium phosphine.
Description
Technical field:
The present invention relates to catalysis technical field; about reclaim the method for rhodium from hydroformylation of olefin rhodium-containing spent catalyst; be exactly the method with hydrogen peroxide treatment hydroformylation reaction rhodium-containing waste catalyst recovery rhodium or rather, can be by the rhodium wherein containing simply, reclaim efficiently.
Background of invention:
Hydroformylation of olefin is in chemical industry, to produce one of aldehyde and the most important reaction of alcohol compound, and rhodium phosphine complex catalyst is the most frequently used catalyzer of hydroformylation of olefin.In industrial production operation, rhodium phosphine complex catalyst is the inactivation due to the existence of the impurity in the various high boiling point by-products produced and raw material producing in reaction process often.Due to rhodium resource scarcity, expensive, if want, make rhodium catalyst system tenable economically, can reclaim economical, efficiently the rhodium in spent catalyst, this industrial be very important.
The spent rhodium catalyst of discharging from hydroformylation of olefin device, is a kind of thick liquid, and complicated component contains butyraldehyde, butyraldehyde polymkeric substance, triphenylphosphine, triphenylphosphine oxide, rhodium phosphine complex catalyst and other material such as high boiling point by-products produced.Rhodium in rhodium-containing spent catalyst is that the form with rhodium phosphine complex exists, and the mass content of rhodium is conventionally at 0.01-0.1%.According to the difference of its recovering state, the state of rhodium phosphine complex is wherein roughly two kinds, and a kind of is active higher rhodium catalyst, and another kind is the rhodium catalyst of complete deactivation.For example, active higher rhodium catalyst can be from rhodium-containing spent catalyst solution separating out through simple processing; The processing of the rhodium catalyst of complete deactivation is relative complex, because level of deactivation is higher, simple processing is difficult to it from rhodium-containing spent catalyst solution, to separate, and the more harsh recovery method of condition such as generally needing to burn, liquid phase is cleared up could be reclaimed rhodium wherein.
Through years of researches, developed the method that a series of rhodiums reclaim, wherein representational method has: extraction process, submerged combustion, adsorption method of separation, ashing combustion method etc.
Wherein, the extraction process that the clear 56-2994 of Japanese Patent introduces, employing first drops into reaction mixture the aqueous solution and carries out oxide treatment and acid treatment, generates the organic two-phase mixture of water-polarity; Then dewater; Again the phosphine of oleophylic or phosphite are dissolved in to non-polar solvent (not dissolving each other with aforementioned organic phase) wiring solution-forming, add organic phase, form two-phase mixture, in nonpolar organic phase, contain rhodium, lipotropy phosphine, in polarity organic phase, contain phosphite degraded product and high boiling point organic compound, finally two-phase is separated.The rhodium complex rate of recovery approximately 90%.
The submerged combustion that German Patent 2438847 is introduced, it is indoor that employing is sent spent catalyst raffinate into submerged combustion together with air, and water absorbs combustion gases, rhodium is stayed in water with suspended state, after filtration, obtain rhodium, this method is high to equipment requirements, the rhodium rate of recovery approximately 94%.
The adsorption method of separation that the clear 49-121793 of Japanese Patent introduces, employing bringing Selection In property sorbent material in spent catalyst adsorbs rhodium phosphine complex catalyst, then with benzene, make solvent, thorough high boiling point by-products produced in eccysis catalyzer, with polar organic solvent stripping rhodium phosphine complex from sorbent material of a small amount of phosphine.The rhodium rate of recovery 91%.
The ashing combustion method that Chinese patent CN01136796.2 introduces, the carbonate of basic metal or alkaline-earth metal of take is additive, at 650～700 ℃, spent catalyst raffinate is burned to ashing, residual residue again with molten state under alkali-metal bisulphate reactant salt, generate the rhodium salt of solubility, then adopt electrolysis tech that rhodium is separated.This method rhodium powder once through yield is more than 96%.
Chinese patent ZL200710177195.7 has introduced a kind of method that liquid phase method reclaims high purity Trichlororhodium from spent rhodium catalyst.The method is first to adopt the method for underpressure distillation to carry out evaporation concentration to rhodium-containing catalyst waste liquid, then by adding the mixing solutions of mineral acid and oxygenant, after being cleared up under hot conditions, removes with the form of gas organic constituent in spent catalyst residue, rhodium is converted into the recovery that soluble rhodium salt is realized rhodium, and the rhodium rate of recovery is greater than 97%.
Because rhodium is expensive, therefore, when being reclaimed, the rhodium in rhodium-containing spent catalyst solution must guarantee that the very high rate of recovery could meet the economy of reclaimer operation.In addition without the rhodium reclaiming, being discharged in environment, is also very large harm to environment.
At present, single recovery method is difficult to realize the recovery of the high yield of rhodium, and for example extraction process and adsorption method of separation only can reclaim the part rhodium in spent rhodium catalyst, generally can only reach the rate of recovery of 90% left and right.And burn, liquid phase is cleared up etc., and although the rhodium recovery method rate of recovery is higher, recovery process condition is comparatively harsh, is difficult to control rhodium loss in actual mechanical process.
With regard to burning, with regard to the rhodium recovery method cleared up and so on of liquid phase, it is generally the rhodium liquid evaporation concentration of first giving up, steam the components such as the aldehydes that wherein contains, aldehyde polymer, the residue of the high rhodium content then evaporation being obtained further processes to reclaim rhodium wherein, the ashing combustion method of introducing as ZL01136796.2, and the disclosed liquid phase of ZL200710177195.7 is cleared up etc.Yet, when adopting above method to process rhodium-containing spent catalyst solution, exist a series of problem.First in useless rhodium liquid still-process, due to the boiling range of component in useless rhodium liquid very wide (from the aldehydes organism of 60 ℃ until boiling point reach 377 ℃ triphenylphosphine with and boiling point on superpolymer), this makes the temperature of evaporative process and vacuum tightness be difficult to control, easily formed and boiled, and made velocity of evaporation too fast and cause rhodium to enter light constituent loss.For rhodium-containing catalyst waste liquid concentrated, develop a series of method, for example in GB2097795, disclosed employing multi-level thin film vaporizer carries out the method for reduction vaporization, the method that the disclosed rectification under vacuum of Chinese patent CN1403604A and reduction vaporization combine, and the disclosed employing short distance evaporation of Chinese patent CN101691385 is carried out concentrated method to rhodium-containing waste liquid.The equipment of the employing of these methods is different, but their object is to improve vaporization efficiency guaranteeing that rhodium loses in little, to reduce the rhodium entrainment loss in rhodium-containing waste liquid concentration process process.But by the disclosed content of these patents, can be found out, even through operation meticulously, the rhodium loss in rhodium-containing waste liquid concentration process is still difficult to avoid.For example, in GB2097795, disclosed employing multi-level thin film vaporizer carries out the method for reduction vaporization, although the velocity of evaporation of rhodium-containing waste liquid is very fast, the rhodium content steaming in light constituent is higher, owing to steaming the rhodium loss that the rhodium carried secretly in component causes, once can reach 5%.When the rectifying column that Chinese patent CN1403604A is furnished with Stainless Steel Helices in employing carries out underpressure distillation to rhodium-containing waste liquid, the rhodium content in the light constituent of collection is 2.4ppm; While adopting subsequently reduction vaporization further to concentrate preliminary concentrated rhodium-containing waste liquid, the rhodium content of the light constituent steaming be 5.3ppm(account for add rhodium total amount 0.206%).Because the rhodium concentration in rhodium-containing waste liquid concentration process is more and more higher, therefore, rhodium is slightly carried secretly, will cause larger rhodium loss.Although the rhodium that can reduce in concentration process with the underpressure distillation of filled column by use loses, this operation but makes the concentration process time elongated; And because the boiling range of component in the useless rhodium liquid of mentioning is before very wide, although can control well rhodium loss when this makes to use the disclosed distillating method of patent in the bench scale stage, but when concentrated scale is amplified to pilot scale or industrial rank, easily formed and boil, velocity of evaporation is too fast and cause rhodium loss.
Next the rhodium residue of the high density after concentrated is exactly to burn or liquid phase is cleared up to further remove difficulty evaporation organic substance wherein, and by organic complex state-transition, is mineralized by rhodium, to carry out ensuing recovery process.
Take burning method as example, and because incineration temperature is very high, and residue rhodium content is very high, and the organic matter carbonizing in rhodium residue is easy to by flue gas, take rhodium wherein out of system while burning, thereby causes rhodium loss.For head it off, reported all multi-methods, such as Chinese patent ZL01136796.2 is disclosed, add when the rhodium-containing burning residual dregs a large amount of additives and the disclosed temperature programming of ZL99106262.0 to burn the methods such as rhodium-containing residue.But add a large amount of additives that rhodium purification processing subsequent step is lengthened, whole rhodium recovery process yield declines.And adding of additive solids salt mixes with the rhodium concentrated residue of pitch shape completely completely owing to being difficult to, make it limited playing a role of reducing that rhodium loses.The method of the disclosed temperature programming of patent ZL99106262.0 is to make the organism of different boiling component in rhodium-containing residue under different temperature sections, carry out decomposition combustion, due to complicated component in rhodium-containing residue, is difficult to segmentation and controls ashing temperature in operation.And owing to adopting temperature programming, heat-up rate is slow, and the time that ashing is burned is partially long; In addition this invention need to strictly be controlled between 200 ℃-300 ℃, otherwise rhodium loss raises, but a lot of organic point of ignition are just in this interval in rhodium-containing residue, when organism will be difficult to control ashing incineration temperature after this temperature section catches fire, be therefore difficult to avoid rhodium loss.
Summary of the invention:
The invention relates to a kind of method that reclaims rhodium from hydroformylation of olefin rhodium-containing spent catalyst; be exactly exactly first with hydrogen peroxide, the rhodium-containing spent catalyst solution without concentrated to be processed; most of rhodium is precipitated out from useless rhodium liquid; then the rhodium-containing solution evaporation after processing is concentrated; residue after concentrated, through burning disposal, reclaims the rhodium not being precipitated out in rhodium-containing solution.
We have known that current published single recovery method is difficult to realize the recovery of the high yield of rhodium, and by method of the present invention, can realize the recovery of the high yield of rhodium in rhodium-containing spent catalyst.First by simple method, useless rhodium liquid is processed, reclaimed most of rhodium wherein (generally can reach in rhodium-containing waste liquid rhodium content 90%), reduce the rhodium concentration in useless rhodium liquid, then with burning method, rhodium-containing waste liquid is further processed.Due to previous recycling by useless rhodium liquid nearly 90% rhodium reclaim, then the rhodium loss of reality will reduce greatly when the waste liquid of low rhodium content is carried out to subsequent disposal.The rhodium recovery process before carrying out just reclaims easy to handle rhodium return, and the rhodium not reclaiming enters subsequent processing and reclaims, and substantially there is no the problem of rhodium loss.Thus, the method reclaiming in conjunction with rhodium through two steps, the rhodium rate of recovery is easy to just can reach more than 99%, is that the single rhodium recovery method of report is before incomparable.
The present invention is just for the rhodium catalyst in two kinds of different states in spent rhodium catalyst, adopt first latter two method to reclaim successively, both utilized the precipitator method to process simple, can reclaim in rhodium-containing waste liquid active higher rhodium catalyst component, utilize again burning method can thoroughly remove organism in rhodium-containing waste liquid to reclaim the rhodium catalyst component of complete deactivation.Evaded simultaneously adsorption precipitation method for rhodium-containing waste liquid carry out rhodium while reclaiming recycled in its entirety rate low, and burning method in evaporation concentration and while burning the material that reclaims high rhodium content rhodium loss be difficult to the problems such as control.
The present invention is the method with hydrogen peroxide treatment hydroformylation reaction rhodium-containing waste catalyst recovery rhodium, it is characterized in that:
First adopt hydrogen peroxide to process useless rhodium liquid, by wherein nearly 90% rhodium with precipitation form reclaimed, the remaining rhodium solution that contains nearly 10% left and right obtains rhodium slag through concentration again, again rhodium slag is burned in electric furnace, carbon distribution remaining in lime-ash is removed to the rhodium metal obtaining containing other metallic impurity, finally two steps are processed to the rhodium metal merging processing obtaining and made the raw material rhodium trichloride hydrate of preparing rhodium phosphine complex catalyst.
Comprise following technological process:
(a) in rhodium-containing waste reaction solution, add hydrogen peroxide, at the temperature of 100 ℃-150 ℃, stop 1-3 hour, most of rhodium in rhodium-containing catalyst solution is precipitated out, and wherein in hydrogen peroxide and rhodium-containing spent catalyst solution, the mol ratio of institute's rhodium-containing is 100-500;
(b) precipitation is filtered out from reaction soln, rhodium-containing filtrate, through underpressure distillation, obtains rhodium-containing residue;
(c) rhodium-containing residue heats in the electric furnace of 500 ℃, keeps 2-4 hour, obtains the lime-ash of rhodium-containing, is then further heated to 800 ℃-1000 ℃, keeps 1-2 hour, carbon distribution remaining in lime-ash is removed to the rhodium metal obtaining containing other metallic impurity.
Two steps are processed after the rhodium metal obtaining merges can carry out following process processing.First logical hydrogen reducing, leads to warm chlorination in chlorine after then mixing with sodium-chlor, then through alkali neutralization, dissolving with hydrochloric acid, obtains the acid of chlorine rhodium after Zeo-karb removal of impurities, can obtain preparing the raw material rhodium trichloride hydrate of rhodium phosphine complex catalyst after evaporation concentration.
Embodiment:
Embodiment 1
Pack 202.3 grams of the rhodium-containing catalyst waste liquids of inactivation in propene hydroformylation reaction full scale plant (rhodium mass content 0.0687%) into 1 liter of round-bottomed flask; add 15.3 grams of superoxols (30%; massfraction), under stirring, be heated to 150 ℃, keep 5 hours.Reacted rear filtration, obtained rhodium-containing black solid, after hydrogen reducing, with sodium pyrosulfate heating and melting in retort furnace, the molten solids that is dissolved in water obtains the aqueous solution of rhodium-containing, and solution is analyzed rhodium content with ICP-OES, and this step rhodium rate of recovery is 88.6%.Filtrate after hydrogen peroxide treatment obtains 24.2 grams of gram rhodium-containing residues through reduction vaporization, in retort furnace, be heated to 500 ℃, keep 4 hours, further be heated to 800 ℃, keep obtaining for 2 hours the ferrous metal powder of rhodium-containing, salt acid elution is removed foreign metal, after hydrogen reducing, use sodium pyrosulfate heating and melting in retort furnace, the molten solids that is dissolved in water obtains the aqueous solution of rhodium-containing, and solution is analyzed rhodium content with ICP-OES, and this step rhodium rate of recovery is 10.6%.Rhodium total yield based on above step is 99.2%.
Embodiment 2
Pack 210.8 grams of the rhodium-containing catalyst waste liquids of inactivation in propene hydroformylation reaction full scale plant (rhodium mass content 0.0687%) into 1 liter of round-bottomed flask; add 47.8 grams of superoxols (30%; massfraction), under stirring, be heated to 120 ℃, keep 4 hours.Reacted rear filtration, obtained rhodium-containing black solid, after hydrogen reducing, with sodium pyrosulfate heating and melting in retort furnace, the molten solids that is dissolved in water obtains the aqueous solution of rhodium-containing, and solution is analyzed rhodium content with ICP-OES, and this step rhodium rate of recovery is 89.3%.Filtrate obtains 18.9 grams of gram rhodium-containing residues through reduction vaporization, is heated to 500 ℃ in retort furnace, keeps 2 hours, is further heated to 1000 ℃, keeps obtaining for 1 hour the ferrous metal powder of rhodium-containing.The rhodium-containing metal-powder obtaining for twice is merged, and salt acid elution is removed foreign metal, and after hydrogen reducing, with sodium pyrosulfate heating and melting in retort furnace, the molten solids that is dissolved in water obtains the aqueous solution of rhodium-containing.Solution is analyzed rhodium content with ICP-OES, and this step rhodium rate of recovery is 10.2%.Rhodium total yield based on above step is 99.5%.
Embodiment 3
Pack 201.6 grams of the rhodium-containing catalyst waste liquids of inactivation in propene hydroformylation reaction full scale plant (rhodium mass content 0.0687%) into 1 liter of round-bottomed flask; add 76.3 grams of superoxols (30%; massfraction), under stirring, be heated to 120 ℃, keep 2 hours.Reacted rear filtration, obtained rhodium-containing black solid, after hydrogen reducing, with sodium pyrosulfate heating and melting in retort furnace, the molten solids that is dissolved in water obtains the aqueous solution of rhodium-containing, and solution is analyzed rhodium content with ICP-OES, and this step rhodium rate of recovery is 90.1%.Filtrate obtains 20.1 grams of gram rhodium-containing residues through reduction vaporization, is heated to 500 ℃ in retort furnace, keeps 4 hours, is further heated to 800 ℃, keeps obtaining for 2 hours the ferrous metal powder of rhodium-containing.The rhodium-containing metal-powder obtaining for twice is merged, and salt acid elution is removed foreign metal, and after hydrogen reducing, with sodium pyrosulfate heating and melting in retort furnace, the molten solids that is dissolved in water obtains the aqueous solution of rhodium-containing.Solution is analyzed rhodium content with ICP-OES, and this step rhodium rate of recovery is 9.6%.Rhodium total yield based on above step is 99.7%.
Embodiment 4
Pack 202.5 grams of the rhodium-containing catalyst waste liquids of inactivation in propene hydroformylation reaction full scale plant (rhodium mass content 0.0687%) into 1 liter of round-bottomed flask; add 30.6 grams of superoxols (30%; massfraction), under stirring, be heated to 100 ℃, keep 5 hours.React rear filtration, obtained rhodium-containing black solid.Filtrate obtains 22.3 grams of gram rhodium-containing residues through reduction vaporization, is heated to 500 ℃ in retort furnace, keeps 4 hours, is further heated to 1000 ℃, keeps obtaining for 1 hour the ferrous metal powder of rhodium-containing.The rhodium-containing metal-powder obtaining for twice is merged, and salt acid elution is removed foreign metal, and after hydrogen reducing, with sodium pyrosulfate heating and melting in retort furnace, the molten solids that is dissolved in water obtains the aqueous solution of rhodium-containing.Solution is analyzed rhodium content with ICP-OES, and the rhodium total yield based on above step is 99.0%.
Embodiment 5
10105 grams of the rhodium-containing catalyst waste liquids of inactivation in propene hydroformylation reaction full scale plant (rhodium mass content 0.0687%) are packed in 20 liters of reactors; add 3000 grams of superoxols (30%; massfraction), under stirring, be heated to 120 ℃, keep 3 hours.React rear filtration, obtained rhodium-containing black solid.Filtrate obtains 1112 grams of gram rhodium-containing residues through reduction vaporization, is heated to 500 ℃ in retort furnace, keeps 3 hours, is further heated to 1000 ℃, keeps obtaining for 1 hour the ferrous metal powder of rhodium-containing.The rhodium-containing metal-powder obtaining for twice is merged, and salt acid elution is removed foreign metal, and after hydrogen reducing, with sodium pyrosulfate heating and melting in retort furnace, the molten solids that is dissolved in water obtains the aqueous solution of rhodium-containing.Solution is analyzed rhodium content with ICP-OES, and the rhodium total yield based on above step is 99.5%.The aqueous solution of rhodium-containing is neutralized to pH=7 through 20% sodium hydroxide, and rhodium is separated out from solution with the form of rhodium gel, filter, and deionized water wash rhodium gel, after appropriate hydrochloric acid dissolving, in water-bath, evaporate to dryness obtains rhodium trichloride hydrate.
The rhodium rate of recovery is calculated in the following ways:
The rhodium rate of recovery=(mass content of the quality * rhodium of the rhodium-containing aqueous solution)/(rhodium-containing waste liquid quality * rhodium concentration) * 100%, rhodium content is analyzed with ICP-OES.
Table 1
| Embodiment | Total yield |
| Embodiment 1 | 99.2% |
| Embodiment 2 | 99.5% |
| Embodiment 3 | 99.7% |
| Embodiment 4 | 99.0% |
| Embodiment 5 | 99.5% |
Claims (1)
1. with hydrogen peroxide treatment hydroformylation reaction rhodium-containing spent catalyst solution, reclaim the method for rhodium, it is characterized in that:
First adopt hydrogen peroxide to process rhodium-containing spent catalyst solution, form by 90% rhodium wherein with precipitation is reclaimed, remaining 10% the rhodium solution of containing obtains rhodium-containing residue through concentration again, again rhodium-containing residue is burned in electric furnace, carbon distribution remaining in lime-ash is removed to the rhodium metal obtaining containing other metallic impurity, finally two steps are processed to the rhodium metal obtaining and merged;
Comprise following technological process:
(a) in rhodium-containing spent catalyst solution, add hydrogen peroxide, at the temperature of 100 ℃-150 ℃, stop 1-3 hour, most of rhodium in rhodium-containing spent catalyst solution is precipitated out, and wherein in hydrogen peroxide and rhodium-containing spent catalyst solution, the mol ratio of institute's rhodium-containing is 100-500;
(b) precipitation is filtered out from reaction soln, rhodium-containing filtrate, through underpressure distillation, obtains rhodium-containing residue;
(c) rhodium-containing residue heats in the electric furnace of 500 ℃, keeps 2-4 hour, obtains the lime-ash of rhodium-containing, is then further heated to 800 ℃-1000 ℃, keeps 1-2 hour, carbon distribution remaining in lime-ash is removed to the rhodium metal obtaining containing other metallic impurity.
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| CN105572104A (en) * | 2015-12-08 | 2016-05-11 | 中国海洋石油总公司 | Method for accurately measuring content of rhodium in rhodium-containing organic solution |
| TW201840362A (en) * | 2016-11-08 | 2018-11-16 | 美商陶氏科技投資有限公司 | Methods to rejuvenate a deactivated hydroformylation catalyst solution |
| TWI758353B (en) * | 2016-11-08 | 2022-03-21 | 美商陶氏科技投資有限公司 | Methods to rejuvenate a deactivated hydroformylation catalyst solution |
| JP7269238B2 (en) | 2017-11-13 | 2023-05-08 | ダウ テクノロジー インベストメンツ リミティド ライアビリティー カンパニー | Process for recovering rhodium from hydroformylation processes |
| CN112791748B (en) * | 2021-01-15 | 2022-09-20 | 万华化学集团股份有限公司 | Method for recovering catalytic metal from hydroformylation reaction liquid |
| CN115838864B (en) * | 2021-09-22 | 2024-09-17 | 中国石油化工股份有限公司 | Method for preparing rhodium salt by recovering rhodium from waste rhodium slag and recovered rhodium salt |
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| CN1273278A (en) * | 1999-05-07 | 2000-11-15 | 中国石油化工集团公司北京化工研究院 | Method for recovering metal rhodium from waste rhodium catalyst raffinate |
| CN102373335A (en) * | 2010-08-27 | 2012-03-14 | 中国石油化工股份有限公司 | Method for recovering rhodium from inactivated rhodium-phosphine complex catalyst |
| CN102557155A (en) * | 2011-10-25 | 2012-07-11 | 中国海洋石油总公司 | Method for recovering rhodium from rhodium-containing waste liquid and preparing rhodium chloride hydrate |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1273278A (en) * | 1999-05-07 | 2000-11-15 | 中国石油化工集团公司北京化工研究院 | Method for recovering metal rhodium from waste rhodium catalyst raffinate |
| CN102373335A (en) * | 2010-08-27 | 2012-03-14 | 中国石油化工股份有限公司 | Method for recovering rhodium from inactivated rhodium-phosphine complex catalyst |
| CN102557155A (en) * | 2011-10-25 | 2012-07-11 | 中国海洋石油总公司 | Method for recovering rhodium from rhodium-containing waste liquid and preparing rhodium chloride hydrate |
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Address after: 100010 Beijing, Chaoyangmen, North Street, No. 25, No. Patentee after: CHINA NATIONAL OFFSHORE OIL Corp. Patentee after: CNOOC TIANJIN CHEMICAL RESEARCH & DESIGN INSTITUTE Co.,Ltd. Patentee after: CNOOC ENERGY TECHNOLOGY & SERVICES Ltd. Address before: 100010 Beijing, Chaoyangmen, North Street, No. 25, No. Patentee before: CHINA NATIONAL OFFSHORE OIL Corp. Patentee before: CNOOC TIANJIN CHEMICAL RESEARCH & DESIGN INSTITUTE Patentee before: CNOOC ENERGY TECHNOLOGY & SERVICES Ltd. |
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Effective date of registration: 20161010 Address after: No. three road 300131 Tianjin city Hongqiao District dingzigu No. 85 Patentee after: CNOOC TIANJIN CHEMICAL RESEARCH & DESIGN INSTITUTE Co.,Ltd. Patentee after: CNOOC ENERGY TECHNOLOGY & SERVICES Ltd. Address before: 100010 Beijing, Chaoyangmen, North Street, No. 25, No. Patentee before: CHINA NATIONAL OFFSHORE OIL Corp. Patentee before: CNOOC TIANJIN CHEMICAL RESEARCH & DESIGN INSTITUTE Co.,Ltd. Patentee before: CNOOC ENERGY TECHNOLOGY & SERVICES Ltd. |