CN102173447B - Method for directly synthesizing metal (tungsten or molybdenum) carbonyl complex from tungsten oxide or molybdenum oxide - Google Patents
Method for directly synthesizing metal (tungsten or molybdenum) carbonyl complex from tungsten oxide or molybdenum oxide Download PDFInfo
- Publication number
- CN102173447B CN102173447B CN2010106129963A CN201010612996A CN102173447B CN 102173447 B CN102173447 B CN 102173447B CN 2010106129963 A CN2010106129963 A CN 2010106129963A CN 201010612996 A CN201010612996 A CN 201010612996A CN 102173447 B CN102173447 B CN 102173447B
- Authority
- CN
- China
- Prior art keywords
- tungsten
- molybdenum
- reaction
- reaction kettle
- oxide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Images
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a method for directly synthesizing a metal (tungsten or molybdenum) carbonyl complex from tungsten oxide or molybdenum oxide, belonging to the technical field of powder metallurgy. The method comprises the following steps: putting tungsten or molybdenum oxide, carbon tetrachloride, a nonpolar organic solvent and an independently packaged reducer into a sealed reaction kettle provided with a stirrer; replacing air in the reaction system by repeatedly charging carbon monoxide into the reaction kettle and discharging the carbon monoxide from the reaction kettle, heating the reaction kettle to 200-250 DEG C, and keeping the temperature for 4-8 hours; after the reaction system is cooled to 30-50 DEG C, introducing carbon monoxide to 5-20 MPa, keeping the pressure, starting the stirrer of the reaction kettle, breaking the container packaging the reducer, wherein the stirring is carried out at the rotation speed of 100-200 rpm for 1-12 hours; and after the reaction finishes and the solution is cooled to room temperature, taking out the reaction solution, distilling and heating for sublimation to obtain the clear crystal of tungsten hexacarbonyl or molybdenum hexacarbonyl. The invention has the advantages of simple technique, high safety in production, low cost and high synthesis efficiency, and has wide application prospects in the market.
Description
Technical field
The invention belongs to field of powder metallurgy, particularly a kind of method by Tungsten oxide 99.999 or directly synthetic tungsten of molybdenum or molybdenum metallic carbonyls complex compound.
Background technology
Tungsten, molybdenum all belong to rare metal, in national economy and military industry field extensive application, have become a kind of indispensable strategic resource at present.Tungsten, molybdenum are except being applied to the ferrous metallurgy field, and its compound also is widely used in many fields such as electric light source, machinery, chemical industry.For example, in iron and steel, its decomposition temperature be can reduce behind interpolation tungsten or the molybdenum, the heat-treatment temperature range and the degree of depth enlarged; The HMP of tungsten, molybdenum and HS at high temperature and good conductivity make it be widely used in the electric light source industry; Often tungsten disulfide, molybdenumdisulphide are loaded to the position easy to wear of mechanical component as lubricant in the mechanical industry, strengthen that it is wear-resistant, the anti-attrition performance.In order to bring into play China's tungsten, molybdenum resources advantage and to promote the Sustainable development that China's refractory metal is industrial; Tungsten, molybdenum industry need develop to deep processing and the direction of increasing technology content; And the technology content of tungsten, molybdenum chemical is higher, of many uses, added value is high; Be one of important directions of tungsten resource deep processing, have vast potential for future development, wherein tungsten carbonyl (molybdenum) complex compound is one type of important tungsten (molybdenum) organometallic compound.
Tungsten carbonyl (molybdenum) complex compound is the coordination compound that is formed by magnesium-yttrium-transition metal tungsten (molybdenum) and carbon monoxide part, is generally sexadentate, aspect organic synthesis, is widely used.As under illumination condition, hexacarbonylmolybdenum can be used for the ring-opening polymerization of catalysis cyclenes; Tungsten carbonyl or molybdenum carbonyl complex compound can generate various organic molybdenums with the corresponding insertion reaction of generation such as alkene, fast hydrocarbon, diazomethane, eyeball; Utilize the ligand of tungsten carbonyl or molybdenum carbonyl complex compound to carry out intermolecular displacement or permutoid reaction, can make simple substituted organic molybdenum, also can prepare comparatively complicated binuclear complex.Through the thermal dissociation reaction of tungsten carbonyl (molybdenum) complex compound, also can prepare tungsten (molybdenum) metal powder material, mould material or the one of which series compound material of variform, structure.
Normal new reductive reactive metal tungsten of employing of the method for present synthesizing wolfram carbonyl (molybdenum) complex compound or molybdenum and carbon monoxide carry out the high pressure carbonylation reaction and produce; Temperature of reaction is more than 250 ℃; More than the reaction pressure 15MPa, the time surpasses 12 hours, and synthetic yield generally is lower than 35%.Improved method for the oxide compound that adopts tungsten (molybdenum) or halogenide behind hydrogen reducing more than 800 ℃, directly feeding the high pressure carbon monoxide carries out carbonylation reaction, synthetic yield increases.Generally speaking, the oxide compound of tungsten (molybdenum) does not possess carbonylation activity, can not generate tungsten carbonyl (molybdenum) complex compound with reaction of carbon monoxide.Existing method all things considered severe reaction conditions, process is complicated, and combined coefficient is low, and cost is higher.
Summary of the invention
The objective of the invention is to improve the deficiency in existing tungsten carbonyl (molybdenum) the complex compound synthetic technology, provide that a kind of technology is simple, the compound method of tungsten carbonyl (molybdenum) complex compound of high efficiency, low cost.
According to above-mentioned purpose, technical scheme of the present invention is:
(1) reductive agent with oxide compound, tetracol phenixin, non-polar organic solvent and the individual packages of tungsten (molybdenum) places the reaction kettle that has whisking appliance of sealing;
(2) through in reaction kettle, charging and discharging carbon monoxide repeatedly the air displacement in the reaction system is removed, and then reaction kettle is warming up to 200-250 ℃, is incubated 4-8 hour;
(3) after the question response system is cooled to 30-50 ℃, feed carbon monoxide to 5-20MPa and pressurize, open stirring apparatus for reaction kettle then, break the container for reducing agent of encapsulation, agitator speed is 100-200 rev/min, sustained reaction 1-12 hour;
(4) reaction finishes and treats that solution is chilled to after the room temperature reaction soln is taken out, and promptly obtains the clear crystal of tungsten hexacarbonyl or hexacarbonylmolybdenum through distillation and heating sublimation.
In the technique scheme, the oxide compound of tungsten (molybdenum) is tungstic oxide or molybdic oxide; The reductive agent material is the mixture of active metal powder and metallic carbonyls complex compound (mass ratio of the two is 1: 2), and active metal powder can be aluminium powder, zinc powder or iron powder, and the metallic carbonyls complex compound that the CO part is provided can be nickel tetracarbonyl or pentacarbonyl iron; Non-polar organic solvent is anhydrous diethyl ether or anhydrous propanone.2-5%, 8-12%, 9-15%, 70-80% that the mass percent of oxide compound, tetracol phenixin, reductive agent and the non-polar organic solvent of tungsten (molybdenum) is.Used carbon monoxide purity requirement is not less than 92% in the reaction process.
The chemical reaction process of such scheme can be expressed as:
Outstanding advantage of the present invention is: it is raw material that (1) this method adopts Tungsten oxide 99.999, molybdenum, wide material sources, cheap; (2) synthesis condition is gentle, and is lower to the requirement of equipment configuration, helps reducing cost; (3) can overcome the deliquescent problem of tungsten (molybdenum) muriate, reach higher combined coefficient; (4) production technique simple, be convenient to operation, can carry out scale operation; (5) compound method suitability of the present invention is wide, can be used for the carbonylation reaction of many magnesium-yttrium-transition metals.
Description of drawings
Fig. 1 is the X-ray diffractogram spectrum analysis of synthetic tungsten hexacarbonyl complex compound of the present invention.
Fig. 2 is the X-ray diffractogram spectrum analysis of synthetic hexacarbonylmolybdenum complex compound of the present invention.
Embodiment
Below in conjunction with specific embodiment, further set forth the present invention, but embodiment does not limit the present invention, and do not address part and be applicable to prior art in the invention.
The difference of and reaction conditions raw materials used according to the present invention has prepared 3 batches of molybdenum carbonyls, 3 batches of tungsten carbonyls, table 1 by the present invention the process step and the processing parameter of employing compound method, sequence number is an embodiment of the invention sequence number in the table 1.
Embodiment 1
The iron powder (60g) that at first in reaction kettle, adds 60g tungstic oxide, 100ml tetracol phenixin, 2030ml anhydrous propanone, 180g individual packages with pentacarbonyl iron (120g) with 1: 2 quality than blended reductive agent (mass percent is followed successively by 3%, 8%, 80%, 9%); In reaction kettle, charge and discharge 2MPa carbon monoxide 3 times the air displacement in the reaction system is removed, reaction kettle is warming up to 200 ℃ then, is incubated 4 hours; After the question response system is cooled to 30 ℃, feed carbon monoxide to 8MPa and pressurize, open stirring apparatus for reaction kettle then, break the container for reducing agent of encapsulation, agitator speed is 100 rev/mins, sustained reaction 1 hour; Reaction finishes and treats that solution is chilled to after the room temperature reaction soln is taken out, and promptly obtains the clear crystal 10.9g of tungsten hexacarbonyl through distillation and heating sublimation, and product yield is about 12%.
Embodiment 2
The zinc powder (60g) that at first in reaction kettle, adds 60g tungstic oxide, 85ml tetracol phenixin, 1580ml anhydrous diethyl ether, 180g individual packages with nickel tetracarbonyl (120g) with 1: 2 quality than blended reductive agent (mass percent is followed successively by 4%, 9%, 75%, 12%); In reaction kettle, charge and discharge 2MPa carbon monoxide 3 times the air displacement in the reaction system is removed, reaction kettle is warming up to 220 ℃ then, is incubated 6 hours; After the question response system is cooled to 40 ℃, feed carbon monoxide to 10MPa and pressurize, open stirring apparatus for reaction kettle then, break the container for reducing agent of encapsulation, agitator speed is 150 rev/mins, sustained reaction 6 hours; Reaction finishes and treats that solution is chilled to after the room temperature reaction soln is taken out, and promptly obtains the clear crystal 24.6g of tungsten hexacarbonyl through distillation and heating sublimation, and product yield is about 27%.
Embodiment 3
The aluminium powder (80g) that at first in reaction kettle, adds 80g tungstic oxide, 100ml tetracol phenixin, 1570ml anhydrous diethyl ether, 240g individual packages with pentacarbonyl iron (160g) with 1: 2 quality than blended reductive agent (mass percent is followed successively by 5%, 10%, 70%, 15%); In reaction kettle, charge and discharge 2MPa carbon monoxide 3 times the air displacement in the reaction system is removed, reaction kettle is warming up to 250 ℃ then, is incubated 8 hours; After the question response system is cooled to 50 ℃, feed carbon monoxide to 20MPa and pressurize, open stirring apparatus for reaction kettle then, break the container for reducing agent of encapsulation, agitator speed is 200 rev/mins, sustained reaction 12 hours; Reaction finishes and treats that solution is chilled to after the room temperature reaction soln is taken out, and promptly obtains the clear crystal 55.8g of tungsten hexacarbonyl through distillation and heating sublimation, and product yield is about 46%.
Embodiment 4
The iron powder (75g) that at first in reaction kettle, adds 50g molybdic oxide, 140ml tetracol phenixin, 2540ml anhydrous propanone, 225g individual packages with pentacarbonyl iron (150g) with 1: 2 quality than blended reductive agent (mass percent is followed successively by 2%, 9%, 80%, 9%); In reaction kettle, charge and discharge 2MPa carbon monoxide 3 times the air displacement in the reaction system is removed, reaction kettle is warming up to 200 ℃ then, is incubated 4 hours; After the question response system is cooled to 30 ℃, feed carbon monoxide to 5MPa and pressurize, open stirring apparatus for reaction kettle then, break the container for reducing agent of encapsulation, agitator speed is 100 rev/mins, sustained reaction 1 hour; Reaction finishes and treats that solution is chilled to after the room temperature reaction soln is taken out, and promptly obtains the clear crystal 16.5g of hexacarbonylmolybdenum through distillation and heating sublimation, and product yield is about 18%.
Embodiment 5
The aluminium powder (80g) that at first in reaction kettle, adds 60g molybdic oxide, 150ml tetracol phenixin, 2050ml anhydrous diethyl ether, 240g individual packages with nickel tetracarbonyl (160g) with 1: 2 quality than blended reductive agent (mass percent is followed successively by 3%, 12%, 73%, 12%); In reaction kettle, charge and discharge 2MPa carbon monoxide 3 times the air displacement in the reaction system is removed, reaction kettle is warming up to 220 ℃ then, is incubated 6 hours; After the question response system is cooled to 40 ℃, feed carbon monoxide to 12MPa and pressurize, open stirring apparatus for reaction kettle then, break the container for reducing agent of encapsulation, agitator speed is 150 rev/mins, sustained reaction 6 hours; Reaction finishes and treats that solution is chilled to after the room temperature reaction soln is taken out, and promptly obtains the clear crystal 36.2g of hexacarbonylmolybdenum through distillation and heating sublimation, and product yield is about 33%.
Embodiment 6
The zinc powder (100g) that at first in reaction kettle, adds 60g molybdic oxide, 125ml tetracol phenixin, 2020ml anhydrous diethyl ether, 300g individual packages with pentacarbonyl iron (200g) with 1: 2 quality than blended reductive agent (mass percent is followed successively by 3%, 10%, 72%, 15%); In reaction kettle, charge and discharge 2MPa carbon monoxide 3 times the air displacement in the reaction system is removed, reaction kettle is warming up to 250 ℃ then, is incubated 8 hours; After the question response system is cooled to 50 ℃, feed carbon monoxide to 20MPa and pressurize, open stirring apparatus for reaction kettle then, break the container for reducing agent of encapsulation, agitator speed is 200 rev/mins, sustained reaction 12 hours; Reaction finishes and treats that solution is chilled to after the room temperature reaction soln is taken out, and promptly obtains the clear crystal 57.1g of hexacarbonylmolybdenum through distillation and heating sublimation, and product yield is about 52%.
Claims (5)
1. method by directly synthetic tungsten of Tungsten oxide 99.999 or molybdenum or molybdenum metallic carbonyls complex compound is characterized in that process step is:
(1) reductive agent with oxide compound, tetracol phenixin, non-polar organic solvent and the individual packages of tungsten or molybdenum places the reaction kettle that has whisking appliance of sealing;
(2) through in reaction kettle, charging and discharging carbon monoxide repeatedly the air displacement in the reaction system is removed, and then reaction kettle is warming up to 200-250 ℃, is incubated 4-8 hour;
(3) after the question response system is cooled to 30-50 ℃, feed carbon monoxide to 5-20MPa and pressurize, open stirring apparatus for reaction kettle then, break the container for reducing agent of encapsulation, agitator speed is 100-200 rev/min, sustained reaction 1-12 hour;
(4) reaction finishes, and treats after solution is chilled to room temperature reaction soln to be taken out, and through distillation and heating sublimation, obtains the clear crystal of tungsten hexacarbonyl or hexacarbonylmolybdenum;
The material of described reductive agent is active metal powder and the mixture that the metallic carbonyls complex compound of CO part can be provided, and the mass ratio of the two is 1: 2; Active metal powder is aluminium powder, zinc powder or iron powder, and the metallic carbonyls complex compound that the CO part is provided is nickel tetracarbonyl or pentacarbonyl iron.
2. method according to claim 1 is characterized in that, the mass percent of the tungsten of participation carbonylation reaction or oxide compound, tetracol phenixin, reductive agent and the non-polar organic solvent of molybdenum is: 2-5%, 8-12%, 9-15%, 70-80%.
3. method according to claim 1 and 2 is characterized in that, the oxide compound of said tungsten or molybdenum is tungstic oxide or molybdic oxide.
4. method according to claim 1 and 2 is characterized in that, described non-polar organic solvent is anhydrous diethyl ether or anhydrous propanone.
5. method according to claim 1 is characterized in that, the used carbon monoxide purity of reaction system is greater than 92%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010106129963A CN102173447B (en) | 2010-12-20 | 2010-12-20 | Method for directly synthesizing metal (tungsten or molybdenum) carbonyl complex from tungsten oxide or molybdenum oxide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010106129963A CN102173447B (en) | 2010-12-20 | 2010-12-20 | Method for directly synthesizing metal (tungsten or molybdenum) carbonyl complex from tungsten oxide or molybdenum oxide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102173447A CN102173447A (en) | 2011-09-07 |
| CN102173447B true CN102173447B (en) | 2012-11-14 |
Family
ID=44516753
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2010106129963A Expired - Fee Related CN102173447B (en) | 2010-12-20 | 2010-12-20 | Method for directly synthesizing metal (tungsten or molybdenum) carbonyl complex from tungsten oxide or molybdenum oxide |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102173447B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103086434A (en) * | 2011-11-03 | 2013-05-08 | 中国科学院兰州化学物理研究所 | Synthesis method of carbonyl molybdenum |
| CN106006743B (en) * | 2016-05-31 | 2017-07-18 | 上海应用技术学院 | A kind of orthorhombic phase black WO3Preparation method |
| CN114433233B (en) * | 2020-10-16 | 2023-07-04 | 中国石油化工股份有限公司 | Hydrodenitrogenation catalyst, and preparation method and application thereof |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7270848B2 (en) * | 2004-11-23 | 2007-09-18 | Tokyo Electron Limited | Method for increasing deposition rates of metal layers from metal-carbonyl precursors |
| CN1332965C (en) * | 2005-11-29 | 2007-08-22 | 钢铁研究总院 | Method for synthesizing wolfram carbonyl from wolfram alloy waste |
| CN100384860C (en) * | 2006-07-04 | 2008-04-30 | 首都师范大学 | Process for preparing tungsten complex crystal with multiple channel structure characteristic |
-
2010
- 2010-12-20 CN CN2010106129963A patent/CN102173447B/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN102173447A (en) | 2011-09-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Wang et al. | DNA-directed growth of ultrafine CoAuPd nanoparticles on graphene as efficient catalysts for formic acid dehydrogenation | |
| Creutz et al. | Exploring secondary-sphere interactions in Fe–N x H y complexes relevant to N 2 fixation | |
| CN106040303B (en) | β-di-imidogen bivalent rare earth boron hydrogen complex is in catalysis ketone and the application in borine hydroboration | |
| Chen et al. | Stereospecific polymerization of 1, 3-butadiene catalyzed by cobalt complexes bearing N-containing diphosphine PNP ligands | |
| CN102173447B (en) | Method for directly synthesizing metal (tungsten or molybdenum) carbonyl complex from tungsten oxide or molybdenum oxide | |
| Wang et al. | Hydroboration of nitriles and imines by highly active zinc dihydride catalysts | |
| Yao et al. | Zwitterionic half-sandwich Rh and Ir complexes containing a diphosphine nido-carborane ligand: synthesis, structure transformation and application in H 2 activation | |
| EP3260198A1 (en) | Ammonia synthesis catalyst and method for producing same | |
| WO2016133213A1 (en) | Ammonia synthesis catalyst and method for producing same | |
| KR20130129827A (en) | Process for the production of hydrogen | |
| Demir et al. | Scandium and yttrium metallocene borohydride complexes: comparisons of (BH 4) 1− vs.(BPh 4) 1− coordination and reactivity | |
| CN112404447A (en) | Preparation method and application of metallic nickel | |
| CN104936903A (en) | Production method for dodecacarbonyl triruthenium | |
| CN1332965C (en) | Method for synthesizing wolfram carbonyl from wolfram alloy waste | |
| CN101973537A (en) | Method for preparing transition metal phosphide | |
| Masaro et al. | Bis (N‐Heterocyclic Carbene) Manganese (I) Complexes in Catalytic N‐Formylation/N‐Methylation of Amines Using Carbon Dioxide and Phenylsilane | |
| CN102070180A (en) | Method for synthesizing hexacarbonyl tungsten or molybdenum complex | |
| CN107486208B (en) | Preparation method and application of carbon nanotube-loaded quaternary amorphous nickel-based catalyst | |
| CN103130284B (en) | Method for producing nickel carbonyl powder from nickel hydroxide | |
| Zhu et al. | Direct detection of self-reconstruction-accelerated oxygen evolution activity in MoCoNi hydroxides | |
| Lee et al. | Carbyne complexes of the group 6 metals containing 1, 4, 7-triazacyclononane and its 1, 4, 7-trimethyl derivative | |
| Falkenhagen et al. | Organoelement Complexes of a Dinucleating Double β‐Diiminato Ligand–Precedent Cases from Groups 1, 2, and 13 | |
| Mostajeran et al. | Base-metal nanoparticle-catalyzed hydrogen release from ammine yttrium and lanthanum borohydrides | |
| JP7340256B2 (en) | Synthesis method of ammonia borane | |
| Nako et al. | Yttrium-catalysed dehydrocoupling of alanes with amines |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| ASS | Succession or assignment of patent right |
Owner name: BEIJING CISRI-GAONA MATERILALS + TECHNOLOGY CO., L Free format text: FORMER OWNER: INST OF IRON + STEEL Effective date: 20130910 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20130910 Address after: 100081 Beijing city Haidian District Daliushu Village No. 19 Patentee after: BEIJING CISRI-GAONA MATERILALS & TECHNOLOGY Co., LTD. Address before: 100081 Haidian District Institute of South Road, Beijing, No. 76 Patentee before: Central Iron & Steel Research Institute |
|
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20121114 Termination date: 20201220 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |