CN103146926A - Pre-treating method for recycling rhodium in tar - Google Patents
Pre-treating method for recycling rhodium in tar Download PDFInfo
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- CN103146926A CN103146926A CN2013101059099A CN201310105909A CN103146926A CN 103146926 A CN103146926 A CN 103146926A CN 2013101059099 A CN2013101059099 A CN 2013101059099A CN 201310105909 A CN201310105909 A CN 201310105909A CN 103146926 A CN103146926 A CN 103146926A
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- rhodium
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- wood dust
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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Abstract
The invention discloses a pre-treating method for recycling rhodium in tar. The method comprises the following steps: mixing a rhodium catalyst containing tar viscous fluid with wood dust, and stirring to obtain a mixed material, wherein the wood dust is combustible; and transferring the mixed material to a pyrolysis container, heating to perform ashing to obtain rhodium-containing ash, analyzing the content of rhodium. According to above form, the combustible wood dust is added in rhodium catalyst containing tar viscous fluid to eliminate the bubble produced in the pyrolysis process and prevent the viscous fluid from overflowing a pyrolysis tray, and the metal rhodium is effectively retained in the tray in the pyrolysis ashing process; and meanwhile, the wood dust is ashed in high temperature heating, and the trouble of post treatment is saved, so that the recovery rate of the rhodium is more than 98%, and the industrial production cost is greatly reduced.
Description
Technical field
The present invention relates to a kind of recovery method of rhodium, particularly relate to a kind of pretreatment process that reclaims rhodium in tar.
Background technology
Carbongl group synthesis reaction is the important homogeneous complex catalysis reaction of a class, and various transition-metal-carbonyl complex compounds all have katalysis to hydroformylation reaction, but only have the carbonylcomplex of cobalt and rhodium to can be used in suitability for industrialized production.The catalytic activity of rhodium carbonyl catalyst in olefin carbonylation is active higher by 10 than cobalt carbonyl catalyst
2~ 10
4Doubly, and reaction conditions is gentle, and the positive isomery ratio of product meets the industrialization demand.As the rhodium of VIII family precious metal, because of its costliness and catalytic activity high, need to it be carried out high efficiente callback and recycling in suitability for industrialized production, could embody the economic worth of rhodium catalyst.Rhodium catalyst recovery method commonly used generally is divided into the several different methods such as solvent extration, ion exchange method, the precipitator method, extraction-chromatography, ion-exchange-chromatography, carbon fiber electrodeposition method, pressurized hydrogen reduction method and combustion method at present.
It is under the condition that the rhodium homogeneous catalyst exists that oxo process prepares aceticanhydride, and ritalin mixes afterwards solution and carbon monoxide to carry out carbonylation reaction and prepare aceticanhydride and acetic acid with methyl iodide.In this process, because carbonylation reaction is to carry out under high temperature and high pressure, equipment is after operation for some time, the coking of reactor mother liquor generates multiple unsaturated compound and then generation macromolecular compound tar, these tar can wrap up homogeneous rhodium catalyst also and the iodate rhodium polymerization that in reaction system, iodide form, produce the tar viscous fluid of rhodium-containing catalyst, the rhodium that contains 0.05-0.2% in general viscous fluid, thereby cause rhodium homogeneous catalyst inactivation, therefore need to reclaim rhodium catalyst, make it recycle to reduce production costs.Reclaim Noble Metal Rhodium by methods such as extraction or burnings, all need the tar viscous fluid is carried out pre-treatment, the tar viscous fluid of rhodium-containing catalyst can be heated to 200-400 ℃ in pyrolysis oven and carry out pre-treatment, but easily produce bubble, cause viscous fluid to overflow the pyrolysis pallet, also rhodium being taken out of pallet can't collect, and causes the organic efficiency of rhodium to reduce.Can add broken ceramics during pre-treatment in the tar viscous fluid, can eliminate the bubble of generation in podzolic process in heating, but broken ceramics can be deposited in recovery system, also need to filter, the step such as cleaning, bring certain loss can for the recovery of rhodium.
Summary of the invention
The technical problem that the present invention mainly solves is to provide a kind of, and the method has improved the rate of recovery of rhodium, has reduced production cost.
For solving the problems of the technologies described above, the technical scheme that the present invention adopts is: a kind of pretreatment process that reclaims rhodium in tar is provided, comprises that step is:
The tar viscous fluid that (1) will contain rhodium catalyst mixes with wood chip and stirs, and obtains mixture, and wherein wood chip can burn;
(2) mixture is transferred in pyrolysis container, ashing is carried out in heating, the content that obtains containing the ash of rhodium and analyze rhodium.
In a preferred embodiment of the present invention, containing the tar viscous fluid of rhodium catalyst and the mass ratio of described wood chip described in step (1) is 1:1-10.
In a preferred embodiment of the present invention, containing the tar viscous fluid of rhodium catalyst and the mass ratio of described wood chip described in step (1) is 1:1.
In a preferred embodiment of the present invention, described in step (2), pyrolysis container is pallet.
In a preferred embodiment of the present invention, described in step (2), Heating temperature is 500-700 ℃, and the ashing time is 3-5 hour.
The invention has the beneficial effects as follows: the pretreatment process of rhodium in recovery tar of the present invention, flammable wood chip is joined in the tar viscous fluid that contains rhodium catalyst, can eliminate the bubble that produces in pyrolytic process, prevent that viscous fluid from overflowing the pyrolysis pallet, in in the process of pyrolysis ashing, metal rhodium being retained in pallet efficiently, simultaneously wood chip ashing when heat has reduced the trouble of subsequent disposal, thereby the organic efficiency that makes rhodium reaches more than 98%, greatly reduces industrial cost.
Embodiment
The below is described in detail preferred embodiment of the present invention, thereby so that advantages and features of the invention can be easier to be it will be appreciated by those skilled in the art that, protection scope of the present invention is made more explicit defining.
Embodiment one:
The tar viscous fluid that (1) will contain rhodium catalyst mixes for 1:1 in mass ratio and stirs with wood chip, obtains mixture;
(2) mixture is transferred in pallet, pallet is put on tray supporter, with forklift, tray supporter is sent in the pyrolysis body of heater, close upper furnace door, parameters makes the interior temperature of stove rise to 600 ℃, and ashing was taken out tray supporter after 3 hours;
(3) ash of the rhodium-containing in pallet carefully is moved into composite samples in agitation vat and analyze the content of rhodium, the massfraction that obtains rhodium is 5-20%, and the rhodium quality of recovery is greater than 98% of raw material rhodium quality.
Embodiment two:
The tar viscous fluid that (1) will contain rhodium catalyst mixes for 5:1 in mass ratio and stirs with wood chip, obtains mixture;
(2) mixture is transferred in pallet, pallet is put on tray supporter, with forklift, tray supporter is sent in the pyrolysis body of heater, close upper furnace door, parameters makes the interior temperature of stove rise to 600 ℃, and ashing was taken out tray supporter after 4 hours;
(3) ash of the rhodium-containing in pallet carefully is moved into composite samples in agitation vat and analyze the content of rhodium, the massfraction that obtains rhodium is 5-20%, and the rhodium quality of recovery is greater than 98% of raw material rhodium quality.
Embodiment three:
The tar viscous fluid that (1) will contain rhodium catalyst mixes for 10:1 in mass ratio and stirs with wood chip, obtains mixture;
(2) mixture is transferred in pallet, pallet is put on tray supporter, with forklift, tray supporter is sent in the pyrolysis body of heater, close upper furnace door, parameters makes the interior temperature of stove rise to 600 ℃, and ashing was taken out tray supporter after 5 hours;
(3) ash of the rhodium-containing in pallet carefully is moved into composite samples in agitation vat and analyze the content of rhodium, the massfraction that obtains rhodium is 5-20%, and the rhodium quality of recovery is greater than 98% of raw material rhodium quality.
The pretreatment process of rhodium in the recovery tar that the present invention discloses, flammable wood chip is joined in the tar viscous fluid that contains rhodium catalyst, can eliminate the bubble that produces in pyrolytic process, prevent that viscous fluid from overflowing the pyrolysis pallet, in in the process of pyrolysis ashing, metal rhodium being retained in pallet efficiently, simultaneously wood chip ashing when heat has reduced the trouble of subsequent disposal, thereby the organic efficiency that makes rhodium reaches more than 98%, greatly reduces industrial cost.
The above is only embodiments of the invention; not thereby limit the scope of the claims of the present invention; every equivalent structure or equivalent flow process conversion that utilizes specification sheets of the present invention to do, or directly or indirectly be used in other relevant technical fields, all in like manner be included in scope of patent protection of the present invention.
Claims (5)
1. a pretreatment process that reclaims rhodium in tar, is characterized in that, comprises that step is:
The tar viscous fluid that (1) will contain rhodium catalyst mixes with wood chip and stirs, and obtains mixture, and wherein wood chip can burn;
(2) mixture is transferred in pyrolysis container, ashing is carried out in heating, the content that obtains containing the ash of rhodium and analyze rhodium.
2. pretreatment process according to claim 1, is characterized in that, containing the tar viscous fluid of rhodium catalyst and the mass ratio of described wood chip described in step (1) is 1:1-10.
3. pretreatment process according to claim 2, is characterized in that, containing the tar viscous fluid of rhodium catalyst and the mass ratio of described wood chip described in step (1) is 1:1.
4. pretreatment process according to claim 1, is characterized in that, described in step (2), pyrolysis container is pallet.
5. pretreatment process according to claim 1, is characterized in that, described in step (2), Heating temperature is 500-700 ℃, and the ashing time is 3-5 hour.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2013101059099A CN103146926A (en) | 2013-03-29 | 2013-03-29 | Pre-treating method for recycling rhodium in tar |
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| Application Number | Priority Date | Filing Date | Title |
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| CN2013101059099A CN103146926A (en) | 2013-03-29 | 2013-03-29 | Pre-treating method for recycling rhodium in tar |
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| CN103146926A true CN103146926A (en) | 2013-06-12 |
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| CN2013101059099A Pending CN103146926A (en) | 2013-03-29 | 2013-03-29 | Pre-treating method for recycling rhodium in tar |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109554553A (en) * | 2018-12-17 | 2019-04-02 | 浙江省冶金研究院有限公司 | The recovery method of rhodium in a kind of spent rhodium catalyst |
| CN109930006A (en) * | 2019-04-16 | 2019-06-25 | 福建工程学院 | A method of noble metal platinum in recycling TDI tar residue |
| CN111020200A (en) * | 2019-12-17 | 2020-04-17 | 山东博苑医药化学有限公司 | Method for recovering rhodium from rhodium-containing waste liquid |
| CN111566237A (en) * | 2018-01-24 | 2020-08-21 | 贺利氏德国有限两合公司 | Method for recovering noble metal from petrochemical process residues |
| CN111910077A (en) * | 2020-07-08 | 2020-11-10 | 武汉工程大学 | Method for efficiently enriching rhodium from rhodium-containing organic waste liquid |
Citations (2)
| 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 |
| WO2012140128A1 (en) * | 2011-04-13 | 2012-10-18 | Umicore Ag & Co. Kg | Process for providing noble metal-containing mixtures for recovering noble metals |
-
2013
- 2013-03-29 CN CN2013101059099A patent/CN103146926A/en active Pending
Patent Citations (2)
| 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 |
| WO2012140128A1 (en) * | 2011-04-13 | 2012-10-18 | Umicore Ag & Co. Kg | Process for providing noble metal-containing mixtures for recovering noble metals |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111566237A (en) * | 2018-01-24 | 2020-08-21 | 贺利氏德国有限两合公司 | Method for recovering noble metal from petrochemical process residues |
| CN109554553A (en) * | 2018-12-17 | 2019-04-02 | 浙江省冶金研究院有限公司 | The recovery method of rhodium in a kind of spent rhodium catalyst |
| CN109554553B (en) * | 2018-12-17 | 2021-09-03 | 浙江省冶金研究院有限公司 | Method for recovering rhodium in waste rhodium catalyst |
| CN109930006A (en) * | 2019-04-16 | 2019-06-25 | 福建工程学院 | A method of noble metal platinum in recycling TDI tar residue |
| CN109930006B (en) * | 2019-04-16 | 2020-12-25 | 福建工程学院 | Method for recovering noble metal platinum in TDI tar residue |
| CN111020200A (en) * | 2019-12-17 | 2020-04-17 | 山东博苑医药化学有限公司 | Method for recovering rhodium from rhodium-containing waste liquid |
| CN111910077A (en) * | 2020-07-08 | 2020-11-10 | 武汉工程大学 | Method for efficiently enriching rhodium from rhodium-containing organic waste liquid |
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Application publication date: 20130612 |