CN1775695A - Nickel carbonyl synthesizing method - Google Patents
Nickel carbonyl synthesizing method Download PDFInfo
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- CN1775695A CN1775695A CN 200510134248 CN200510134248A CN1775695A CN 1775695 A CN1775695 A CN 1775695A CN 200510134248 CN200510134248 CN 200510134248 CN 200510134248 A CN200510134248 A CN 200510134248A CN 1775695 A CN1775695 A CN 1775695A
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Abstract
The invention belongs to the field of powder metallurgy, especially relating to a method for synthesizing nickel carbonyl, including the following steps of: (1) preparing active carbonyl synthesizing raw material: firstly heating the alloy to melt at 1600 deg.C-1650 deg.C, then rapidly condensing the melt by 0.3-0.5 MPa high pressure water spray, where the water temperature is controlled at 10 deg.C-15 deg.C and the spraying speed is 4-5 kg/min, and the size of the obtained alloy particles is 0.5 mm-5 mm, and the proportion of the particles of 0.5 mm-2 mm is not less than 85% and that of the particles of 2mm-5mm is not greater than 15%; (2) synthesizing nickel carbonyl: placing the prepared alloy particles in a high pressure kettle of 10 liter, and the carbonyl synthesizing conditions: the CO content fed in the high pressure kettle >=92%; CO circulating speed in the carbonyl synthesizing system is 8-12 times/h, and the pressure is 5-12 MPa, the temperature is 100 deg.C-150 deg.C, and the synthesizing time is 24-32 hours. The invention has the advantages of simple technique, low equipment manufacturing cost, high carbonyl synthesis ratio as compared with the existing technique.
Description
Technical field
The invention belongs to field of powder metallurgy, particularly a kind of synthetic method of nickle carbonoxide.
Background technology
At present, report according to International Nickel company of Canada Ltd., Cu-Ni alloy with certain sulphur content, after the water atomization granulation, can obtain highly active oxo process raw material, the composition of raw material is Ni65-70%, Cu15%, Fe1%, S4-5%, granulometric range 1～5mm, the synthesis condition of nickle carbonoxide are that the content of CO is 90～95%, pressure 7.0MPa, temperature is 180 ℃, through 42 hours building-up reactions, the extraction rate reached to 95% of nickel, above-mentioned bibliographical information is at Journal of Metals July1969.41-45.This technology is being followed Cu in the alloy: S=4: 1 part by weight, its reason is to emphasize Cu in the alloy: S=4: the Cu-Ni alloy just has by the activity of carbonylation under 1 situation, though the alloy of this composition can be by oxo process, carbonylation synthesizes needed pressure height; Carbongl group synthesis reaction speed is slower, generally needs 36～48 hours; The oxo process rate generally≤95%.Particularly Cu: S was less than 4: 1 o'clock, and a large amount of sulphur can cause Ni in the alloy
3S
2The increase of compound is because Ni
3S
2Can not react with CO, the nickel in the sulfide can't be by carbonylation, so synthetic ratio generally all can reduce, the oxo process rate can further descend.And the carbonylation container is a kind of new and high technology that can guarantee rotary seal for rotating synthesis reactor in this report, has only Canada Company to make, and involves great expense.
Summary of the invention
The object of the present invention is to provide the nickle carbonoxide synthetic method that a kind of technology is simple, equipment manufacturing cost is low, the oxo process rate is high.
According to above-mentioned purpose, technical scheme of the present invention is:
The Cu that the present invention breaks traditions: S=4: 1 ratio, reduce sulphur content in the alloy, increase the component of nickel in the sosoloid; Adopt the cryogenic high pressure water atomization, make S uniform distribution in the alloy solid solution body, improve the activity of Cu-Ni alloy, be implemented in the fixing vertical reactor, with low temperature, in be pressed into reaction, the oxo process rate can reach 99%.
According to above-mentioned purpose and technical scheme, principle of work of the present invention is:
1) the water at low temperature atomizing makes sulphur be uniform connection net distribution
Make the uniform distribution of sulphur in the Cu-Ni alloying pellet by quenching, form the network structure that is communicated with simultaneously, for oxo process provides two-way channel.Provide the infiltration lane of CO gas to alloying pellet inside on the one hand, carbongl group synthesis reaction is carried out on the surface that arrives nickel rapidly; Also be the desorption of synthetic product on the other hand, provide unobstructed passage to the diffusion of particle space outerpace.Add Cu-Ni alloy solid solution body and cut into numerous small sosoloid by cancellated sulphur line, increased the contact area of CO and nickel greatly, the nickle carbonoxide building-up reactions is on the upgrade everywhere in granule interior.The network channel of sulphur line must be the passage that extends in all direction, even uniform distribution, but be not the resultant velocity that the passage that is communicated with also can influence nickle carbonoxide, control shrend condensing rate is the key of decision sulphur distribution in alloy; And condensing rate will be considered the particle size of alloy.
In addition, reduce sulphur content in the alloy, improve the component of nickel in the sosoloid, just have more nickel naturally, and then improve synthetic ratio by carbonylation.So when the content weight ratio of sulphur in the alloy raw material far below Cu: S=4: during 1 value, Cu: S=8 for example: 1 or 10: 1, even this alloy raw material is when lower pressure 5～8MPa, carbongl group synthesis reaction not only can obtain higher synthesising reacting speed, also can reach the synthetic ratio greater than 98% simultaneously.
2) speed of circulation of CO in the control synthesis system
The desorption rate of synthetic product is the key of control nickle carbonoxide synthesising reacting speed.For this reason, the system of carbongl group synthesis reaction will control the speed of circulation scope of CO gas at 8～12 times/hour; Content＜5% (percent by volume) of nickle carbonoxide gas in the mixed gas in the reactor, in the nickle carbonoxide synthetic reaction process, control nickle carbonoxide synthesising reacting speed can influence the nickle carbonoxide molecule and enter speed the gas phase from the surface desorption of nickel, when particularly carrying out the nickle carbonoxide building-up reactions in Cu-Ni alloying pellet inside, the nickle carbonoxide product diffusion that generates is not gone out, make nickel surface form one " vapour phase nickle carbonoxide saturation zone ", vapour phase nickle carbonoxide saturation zone " stoped the CO molecule to arrive the surface of fresh nickel; make the CO molecule to carry out physical adsorption and chemisorption; cause carbongl group synthesis reaction speed to reduce, even building-up reactions to stop fully on the surface of nickel.Control CO gas circulation speed and the content of nickle carbonoxide in mixed gas, its purpose are just in the prevention of the surface of nickel " vapour phase nickle carbonoxide saturation zone " formation.The uniform distribution of sulphur in the Cu-Ni alloying pellet and the connected network structure of formation, for product provides countless passages to the diffusion of particle space outerpace, make nickel face nickle carbonoxide surface concn reduce, can not form one " vapour phase nickle carbonoxide saturation zone ", there is more CO to enter the unsalted surface of nickel, quickens the nickle carbonoxide building-up reactions.
According to above-mentioned purpose and principle of work, concrete technical scheme of the present invention is:
This method is raw materials used to be the cupronickel of sulfur-bearing, and its chemical composition (weight %) is: Ni60～80%, and Cu 8～18%, and Fe 3～5%, and Co 0.5～2%, and S 1.5～3.5%, wherein Cu: S＞4: 1; This method comprises following concrete steps:
(1) preparation has active oxo process raw material: at first above-mentioned component alloy is heated to 1600 ℃～1650 ℃ of molten states, then this melt is passed through the hydraulic atomized rapid condensation of 0.3～0.5MPa, water temperature is controlled at 10～15 ℃, atomization speed is 4～5kg/ branch, the alloying pellet particle size range that obtains is 0.5～5mm, and wherein particle diameter is at particle 〉=85% of 0.5～2mm; Particle diameter is at particle≤15% of 2～5mm;
(2) nickle carbonoxide is synthetic: it is that the oxo process condition is: CO content 〉=92% that feeds autoclave in 10 liters the autoclave that the alloying pellet of above-mentioned preparation is placed on volume; The speed of circulation of CO gas is at 8～12 times/hour, pressure 5～12MPa; Temperature: 100～150 ℃; Generated time: 24～32 hours.
The present invention compared with prior art has the advantage that technology is simple, equipment manufacturing cost is low, the oxo process rate is high.Be specially the present invention and reduced the oxo process temperature, make the sealing of suite of equipment solve easily, equipment manufacturing cost is low; Carbongl group synthesis reaction speed improves, and low synthetic ratio can arrive 99% in present 24 hours.
Description of drawings
The metallographic structure figure that accompanying drawing 1 is evenly distributed in alloy for sulphur.
Accompanying drawing 2 is the metallographic structure figure that shows the distribution of sulphur in alloy by electronic probe.
As can be seen from Figure:, make the network channel that sulphur is evenly distributed in the Cu-Ni alloy and formation is communicated with alloy to be divided into countless individual small sosoloid by water scold rapid condensation.
Embodiment
The raw materials used chemical composition according to the present invention adopts synthetic method of the present invention, has synthesized 6 batches of nickle carbonoxides.Wherein table 1 is the raw materials used chemical composition table of the present invention, and table 2 is the processing step of synthetic method of the present invention and processing parameter, synthetic counting rate meter.
Table 1 is the raw materials used chemical composition table (weight %) of the present invention
| Sequence number | Chemical component weight % | ||||
| Ni | Cu | Fe | Co | S | |
| 1 # | 64.14 | 16.86 | 4.40 | 1.00 | 2.50 |
| 2 # | 79.58 | 10.23 | 4.80 | 1.37 | 1.85 |
| 3# | 67.24 | 17.32 | 3.50 | 1.32 | 3.15 |
| 4# | 67.24 | 17.32 | 3.50 | 1.32 | 3.15 |
| 5# | 76.9 | 8.03 | 4.20 | 1.00 | 3.12 |
| 6# | 76.9 | 8.03 | 4.20 | 1.00 | 3.12 |
Table 2 is the processing step of synthetic method of the present invention and process parameter table, synthetic counting rate meter
| Sequence number | Preparation has active oxo process raw material | Nickle carbonoxide is synthetic | The synthetic ratio % of nickel | ||||||
| Atomizing pressure MPa | Atomizing water temperature ℃ | Atomization speed kg/min | Granularity mm | CO ％ | Pressure MPa | Temperature ℃ | Generated time h | ||
| 1 | 0.3-0.5 | 10-15 | 4-5 | 0.5-2.0 | 92 | 6-8 | 100-150 | 24 | 99.5 |
| 2 | 0.3-0.5 | 10-15 | 4-5 | 0.5-2.0 | 92 | 6-8 | 100-120 | 24 | 99.5 |
| 3 | 0.3-0.5 | 10-15 | 4-5 | 1.0-3.0 | 92 | 6-10 | 100-150 | 24 | 97.6 |
| 4 | 0.3-0.5 | 10-15 | 4-5 | 1.0-3.0 | 92 | 6-12 | 100-150 | 24 | 98.5 |
| 5 | 0.3-0.5 | 10-15 | 4-5 | 3.0-5.0 | 92 | 8-12 | 100-150 | 32 | 98.5 |
| 6 | 0.3-0.5 | 10-15 | 4-5 | 3.0-5.0 | 92 | 6-12 | 100-150 | 32 | 97.8 |
Adopt the raw materials used and synthetic method of the present invention, sulphur is even connection net distribution in alloy, so under lower pressure, it is very fast that the nickle carbonoxide building-up reactions is carried out.The nickle carbonoxide synthetic ratio arrives 99.5% in 24 hours.
Claims (1)
1, a kind of synthetic method of nickle carbonoxide is characterized in that this method is raw materials used and is the cupronickel of sulfur-bearing that its chemical composition (weight %) is: Ni 60～80%, Cu 8～18%, and Fe 3～5%, and Co 0.5～2%, S 1.5～3.5%, wherein Cu: S＞4: 1; This method comprises following concrete steps:
(1) preparation has active oxo process raw material
At first above-mentioned alloy component is heated to 1600 ℃～1650 ℃ of molten states, then this melt is passed through 0.3～0.5Mpa high-pressure atomization rapid condensation, water temperature is controlled at 10～15 ℃, atomization speed is 4～5kg/ minute, the alloying pellet particle size range that obtains is 0.5～5mm, and wherein particle diameter is at particle 〉=85% of 0.5～2mm; Particle diameter is at particle≤15% of 2～5mm;
(2) nickle carbonoxide is synthetic
It is that the oxo process condition is: feed CO content 〉=92% in the autoclave in 10 liters the autoclave that the alloying pellet of above-mentioned preparation is placed on volume; CO gas speed of circulation 8～12 times/hour in the system of oxo process, pressure 5～12MPa; Temperature: 100～150 ℃; Generated time: 24～32 hours.
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| CNB2005101342488A CN100357188C (en) | 2005-12-15 | 2005-12-15 | Nickel carbonyl synthesizing method |
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| CNB2005101342488A CN100357188C (en) | 2005-12-15 | 2005-12-15 | Nickel carbonyl synthesizing method |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102070180A (en) * | 2010-12-07 | 2011-05-25 | 吉林吉恩镍业股份有限公司 | Method for synthesizing hexacarbonyl tungsten or molybdenum complex |
| CN102719801A (en) * | 2012-06-05 | 2012-10-10 | 金川集团股份有限公司 | Method for preparing nickel foil |
| CN103241782A (en) * | 2013-04-24 | 2013-08-14 | 东华工程科技股份有限公司 | Method for synthesizing nickel carbonyl under medium pressure in rotating kettle |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4097272A (en) * | 1977-09-08 | 1978-06-27 | Kennecott Copper Corporation | Winning nickel and cobalt with mercaptide extractants and carbon monoxide strip |
| US6153167A (en) * | 1998-05-12 | 2000-11-28 | American Air Liquide | Generation of metal-carbonyl standards for the calibration of spectroscopic systems |
| JP2001266870A (en) * | 1999-09-27 | 2001-09-28 | Sony Corp | Negative electrode material for secondary battery, its manufacturing method and secondary battery using the same |
| CN1184146C (en) * | 2002-08-01 | 2005-01-12 | 中国科学院兰州化学物理研究所 | Oxo-process of preparing nickel carbonyl from coarse ore nickel |
| US7198770B2 (en) * | 2002-12-04 | 2007-04-03 | Chemical Vapour Metal Refining, Inc. | Process for producing nickel carbonyl, nickel powder and use thereof |
| CN1305774C (en) * | 2003-09-29 | 2007-03-21 | 中国科学院兰州化学物理研究所 | Method for synthesizing nickel tetracarbonyl |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102070180A (en) * | 2010-12-07 | 2011-05-25 | 吉林吉恩镍业股份有限公司 | Method for synthesizing hexacarbonyl tungsten or molybdenum complex |
| CN102719801A (en) * | 2012-06-05 | 2012-10-10 | 金川集团股份有限公司 | Method for preparing nickel foil |
| CN103241782A (en) * | 2013-04-24 | 2013-08-14 | 东华工程科技股份有限公司 | Method for synthesizing nickel carbonyl under medium pressure in rotating kettle |
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Owner name: GAUNA BEIJING INSTITUTE OF TECHNOLOGY CO. Free format text: FORMER OWNER: IRON AND STEEL RESEARCH GEUERAL INST. Effective date: 20080523 |
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Effective date of registration: 20080523 Address after: Beijing City, Haidian District Daliushu Village No. 19 Patentee after: BEIJING CISRI-GAONA MATERILALS & TECHNOLOGY Co., LTD. Address before: No. 76, South College Road, Beijing, Haidian District Patentee before: Central Iron & Steel Research Institute |
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Granted publication date: 20071226 Termination date: 20201215 |