CN105314689B - The method that rhodium controlling the water circulation closes radium chloride is reclaimed from carbongl group synthesis reaction spent rhodium catalyst - Google Patents
The method that rhodium controlling the water circulation closes radium chloride is reclaimed from carbongl group synthesis reaction spent rhodium catalyst Download PDFInfo
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Abstract
The invention discloses the method that rhodium controlling the water circulation closes radium chloride is reclaimed in a kind of spent rhodium catalyst from carbongl group synthesis reaction.The method includes：Dimethylformamide is added in spent rhodium catalyst solution; stirring and evenly mixing; under nitrogen protection; substep heats up and heats; the condensed device of steam is collected; tail gas is processed with Water spray absorption tower; gained residual liquid adds ethanol dilution to filter; filtering residue priority washing with alcohol obtains active rhodium simple substance; active rhodium simple substance enriching hydrochloric acid, dioxygen water dissolution obtain rhodium chloride solution; by ion exchange resin except the foreign ion such as de-iron, nickel, calcium, smart rhodium chloride acid solution is obtained, smart rhodium chloride acid solution concentrated drying to obtain high-purity rhodium chloride again.The method of the invention efficiency high, simple to operate, rhodium loss is little, and rhodium yield is more than 99%.
Description
Technical field：
The present invention relates to noble metal recovery technology field, more particularly to one kind is returned from carbongl group synthesis reaction spent rhodium catalyst
Receive the method that rhodium prepares chloride hydrate rhodium.
Background technology：
Oxo process is extremely important reaction in chemical industry, including alkene carbonyl synthesizing aldehyde, methanol carbonyl are combined to
, into acetic anhydride etc., rhodium phosphine complex catalyst is the most frequently used catalyst of carbongl group synthesis reaction for acetic acid, methyl acetate carbonyl compound.In work
In industry production operation, rhodium phosphine complex catalyst is often due to miscellaneous in the various high boiling point by-products produced and raw material that produces in course of reaction
The presence of matter and inactivate.It is due to rhodium resource scarcity, expensive, if wanting to make rhodium catalysis system economically tenable, just see
The rhodium in dead catalyst can economical, be efficiently reclaimed, as chloride hydrate rhodium is the base for preparing the rhodium compounds such as rhodium catalyst
Plinth raw material, therefore, the rhodium in carbongl group synthesis reaction spent rhodium catalyst is reclaimed in the form of chloride hydrate rhodium have great importance.
The spent rhodium catalyst discharged from carbonyl synthesis reactor, is a kind of sufficiently complex organic liquor of thick composition
Body.By taking propenecarbonyl synthesis butyl octanol unit as an example, spent rhodium catalyst main component includes rhodium, light component, heavy constituent, triphenyl
Phosphine and its oxidation product, weight component are mainly the trimer and high polymer of butyraldehyde respectively, it is difficult to expressed with molecular formula, and rhodium is main
In the form of rhodium base complex, rhodium content generally in hundreds to thousands ppm, has the industry dress of activation of catalyst regenerating unit
Put, in catalyst waste solution, rhodium content is higher, generally thousand of ppm.
In recovery dead catalyst, one of rhodium thinking is to realize having in dead catalyst by methods such as extraction, adsorption method of separations
Machine component is separated with rhodium complex so as to reclaim rhodium, due to Noble Metal Rhodium it is stronger with the chemical binding force of organic phosphine compound,
And catalyst residual liquid is more sticky, therefore this kind of method rhodium response rate is relatively low, the extraction that such as the clear 56-2994 of Japan Patent is introduced
The response rate of rhodium complex 90% or so, the adsorption method of separation rhodium yield about 91% that the clear 49-121793 of Japan Patent is introduced, this
Outward, in addition it is also necessary to the useless chemicals of proper treatment and waste water.
Reclaim rhodium thinking in dead catalyst two are that dead catalyst residual liquid is carried out being flared off organic component to reclaim rhodium,
The advantage of the method is efficiency high, but as part rhodium in combustion can spill or vaporize, can lose part with stove burning
Rhodium, and part rhodium can be dissolved in combustion fluid, also so that recovery percent is low, the submerged combustion that such as Deutsche Bundespatent 2438847 is introduced
The method rhodium response rate about 94%.In order to reduce the rhodium entrainment loss that burning brings, Chinese patent ZL01136796.2 is to dead catalyst
The carbonate of alkali metal or alkaline-earth metal is added to carry out burning and reclaim rhodium in residual liquid, rhodium powder recovery per pass is up to more than 96%；
Patent ZL93117639.5 adds a kind of periodic table of elements Ia or the alkali compoundss of IIa races to be burnt in dead catalyst residual liquid
Burn and reclaim rhodium, rhodium recovery percent 93%-99%, but this kind of method, due to the compound that adds in burning process forming salt,
Phosphate is combined to form including with the P elements in spent rhodium catalyst, subsequent processes are extremely complex.Chinese patent
The method that ZL99106262.0 and Chinese patent CN1403604A burns waste catalyst recovery rhodium by precise procedures intensification, rhodium are returned
Up to more than 99%, the method needs strict control to yield to heating rate, and the burning time is longer, and industry is amplified not very
Favorably.This kind of method is usually that rhodium is reclaimed in the form of rhodium simple substance in addition, due to the restriction of recovering condition, in the rhodium simple substance of recovery
Containing a large amount of inertia rhodiums, the rhodium with reactivity to be converted into so as to prepare chloride hydrate rhodium, in addition it is also necessary to through complicated rhodium
Dissolution process.
Chinese patent ZL200710177195.7 is described in the spent rhodium catalyst that a kind of liquid phase method is produced from oxo process
The method for reclaiming high-purity rhodium chloride.The method is residual to spent rhodium catalyst initially with the mixed solution of mineral acid and oxidant
Liquid carries out obtaining rhodium-containing digestion solution after High-temperature Digestion carbonization oxidation removes organic component in gaseous form, and rhodium-containing digestion solution uses alkali again
Neutralization prepares aqua oxidation rhodium precipitation, then obtains impure rhodium chloride solution, Jing amberlites with dissolving with hydrochloric acid precipitation
Fat is except foreign ions such as de-iron, nickel, calcium, and Jing recrystallizing and refinings obtain high purity hydrous radium chloride, and the rhodium response rate is more than 97%.
The advantage of the method is that rhodium is reclaimed with radium chloride form, and rhodium high income is disadvantageous in that relatively inefficient.
The content of the invention：
The deficiency that the present invention is present for above-mentioned prior art, there is provided one kind is from carbongl group synthesis reaction spent rhodium catalyst
The method that rhodium prepares chloride hydrate rhodium is reclaimed, the less efficient not enough and existing burning method of full liquid phase resolution method is overcome or rhodium is damaged
Lose it is big, or post processing complexity etc. shortcoming, its efficiency high, rhodium loss be little, and post processing is simple, and rhodium is returned in the form of chloride hydrate rhodium
Receive.
The method that rhodium controlling the water circulation closes radium chloride is reclaimed in a kind of spent rhodium catalyst from carbongl group synthesis reaction of the present invention, the method sets
Counting thinking is：Dimethylformamide is added in spent rhodium catalyst solution first, heating evaporation separates out rhodium under nitrogen protection, then
Chloride hydrate rhodium is prepared through post processings such as filtration, washing, dissolving, ion exchanges.The key of the method is to add dimethyl methyl
Amide, which act as：Dimethylformamide discharges carbon monoxide under the conditions of uniform temperature, and the carbon monoxide of release is by useless rhodium
In catalyst, rhodium complex is reduced to the precipitation of simple substance rhodium, as reduction is carried out in gentle liquid phase, reduces the rhodium simple substance of gained
It is active high, facilitate follow-up rhodium dissolving to prepare radium chloride.
The invention provides the method that rhodium prepares chloride hydrate rhodium in a kind of spent rhodium catalyst from carbongl group synthesis reaction, is reclaimed,
It is characterized in that dimethylformamide is added in spent rhodium catalyst solution, stirring and evenly mixing under nitrogen protection, takes substep to rise
Temperature heating, the condensed device of steam are collected, and tail gas is processed with Water spray absorption tower, and gained residual liquid adds ethanol dilution to filter, filtering residue
Priority washing with alcohol obtains active rhodium simple substance, and enriching hydrochloric acid, dioxygen water dissolution obtain rhodium chloride solution to active rhodium simple substance successively,
By ion exchange resin except foreign ions such as de-iron, nickel, calcium, smart rhodium chloride acid solution is obtained, smart rhodium chloride acid solution is concentrated again
Drying to obtain high-purity rhodium chloride；
Wherein described spent rhodium catalyst includes from carbongl group synthesis reaction device rhodium-containing dead catalyst or the initial concentration discharged
Concentration rhodium-containing dead catalyst afterwards, rhodium content 0.05wt%～0.3wt%, and the rhodium-containing dead catalyst gained after distillation
Rhodium slag, rhodium content are 0.3wt%～10wt%；
50～100 times for spent rhodium catalyst rhodium quality of the quality for adding dimethylformamide；
The heating takes substep to heat up：Heat source temperature is controlled first for 90 DEG C, evaporates light component；Apparatus for evaporation condensation without
When drop flows out, heat source temperature is controlled for 150 DEG C～160 DEG C；Apparatus for evaporation condensation again dripless flow out when, control thermal source temperature
Spend for 180 DEG C～200 DEG C, constant temperature 1～2 hour；
10～30 times (mL/gs) of the volume for adding concentrated hydrochloric acid (mass concentration 36%～38%) for filtering residue quality；
0.5～1.0 times for hydrochloric acid volume of the volume for adding hydrogen peroxide (mass concentration 30%).
According to the method for the invention, wherein adding the quality of dimethylformamide to be preferably spent rhodium catalyst rhodium quality
60～80 times.
The inventive method has the advantage that and effect：
(1) the method for the invention is not only suitable for the carbongl group synthesis reaction device for processing rhodium content in hundreds to thousands ppm
The concentration rhodium-containing dead catalyst of the rhodium-containing dead catalyst and initial concentration of discharge, be also applied for process rhodium content be 0.3%～
15% rhodium-containing dead catalyst distillation rhodium slag.
(2) the method for the invention extracts rhodium in gentle liquid phase, the inertia that burning method can be avoided to occur because of rhodium burning
Rhodium, facilitates follow-up rhodium dissolving to prepare radium chloride；
(3) the method for the invention extracts rhodium in gentle liquid phase, can also avoid burning because of the appearance of the reasons such as splash
Rhodium loses, rhodium high income, more than 99%.
(4) the method for the invention is with respect to liquid phase resolution method, it is to avoid remove Organic substance, efficiency using a large amount of strong acid dissolutions
Height, safety are simple to operate.
Specific embodiment：
The present invention further illustrates methods described by following embodiments, but does not constitute the limit to the scope of the present invention
System.
Embodiment 1
Take in 500g rhodium-containing dead catalyst (rhodium content 1750ppm) addition bis- mouthfuls of flasks of 1L, add 80g dimethyl formyls
Amine, is placed in the oil bath pan with magnetic agitation, flatly connection condensing units and exhaust gas processing device, another mouthful of connection nitrogen, opens
Stirring and evenly mixing, is slowly passed through nitrogen, and substep heats up：Oil bath temperature is controlled first for 90 DEG C, evaporates light component；Apparatus for evaporation condensation
When dripless flows out, oil bath temperature is controlled for 152 DEG C；Apparatus for evaporation condensation again dripless flow out when, controlling oil bath temperature is
180 DEG C, constant temperature 1.5 hours obtains residual liquid 116.5g.
120mL ethanol dilutions are added in residual liquid, are filtered with sand core funnel, with 60mL washing with alcohol filtering residue three times, dried up,
37% hydrochloric acid 10mL, 30% hydrogen peroxide 5mL dissolving filtering residue is sequentially added in sand core funnel filtering residue, rhodium chloride solution is collected, it is dilute
After releasing adjustment PH, smart rhodium chloride acid solution is obtained Jing after cation exchange resin remove impurity, smart rhodium chloride acid solution is concentrated again to be drying to obtain
To high-purity rhodium chloride.Analysis testing result shows that rhodium chloride impurity element total amount is 0.047%, meets YS/T593-
2006 primes quality index, are computed rhodium yield for 99.3%.
Rhodium yield is calculated using following formula：
Rhodium yield=(rhodium weight/mass percentage composition in radium chloride quality × radium chloride)/(rhodium-containing dead catalyst quality × give up and urge
Agent rhodium weight/mass percentage composition) × 100%
It is analyzed with ICP after in rhodium-containing dead catalyst, rhodium content is cleared up, rhodium content gravimetric analysis in rhodium chloride.
Each impurity content ICP is analyzed detection.
Embodiment 2
Raw material, material quantity, device and step are with embodiment 1, different addition 60g dimethylformamides；Substep heats up：It is first
Oil bath temperature is first controlled for 90 DEG C, light component is evaporated；When apparatus for evaporation condensation dripless flows out, oil bath temperature is controlled for 155 DEG C；
Apparatus for evaporation condensation again dripless flow out when, control oil bath temperature be 185 DEG C, constant temperature 2.0 hours.Obtain residual liquid 102.8g.
Analysis testing result shows that rhodium chloride impurity element total amount is 0.046%, meets YS/T593-2006 primes
Quality index, is computed rhodium yield 99.5%.
Embodiment 3
Take in 50g rhodium-containings dead catalyst distillation rhodium slag (rhodium content 4.7%) addition bis- mouthfuls of flasks of 500mL, add 120g bis-
Methylformamide, is placed in the oil bath pan with magnetic agitation, flatly connection condensing units and exhaust gas processing device, another mouthful of connection
Nitrogen, opens stirring and evenly mixing, is slowly passed through nitrogen, and substep heats up：Oil bath temperature is controlled first for 90 DEG C, evaporates light component；Evaporation
When condensing units dripless flows out, oil bath temperature is controlled for 158 DEG C；Apparatus for evaporation condensation again dripless flow out when, control oil
Bath temperature is 185 DEG C, constant temperature 2 hours.Obtain residual liquid 43.5g.
50mL ethanol dilutions are added in residual liquid, are filtered with sand core funnel, with 90mL washing with alcohol filtering residue three times, dried up,
37% hydrochloric acid 50mL, 30% hydrogen peroxide 30mL dissolving filtering residue is sequentially added in sand core funnel filtering residue, rhodium chloride solution is collected, it is dilute
After releasing adjustment PH, smart rhodium chloride acid solution is obtained Jing after cation exchange resin remove impurity, smart rhodium chloride acid solution is concentrated again to be drying to obtain
To high-purity rhodium chloride.Analysis testing result shows that rhodium chloride impurity element total amount is 0.047%, meets YS/T593-
2006 primes quality index, are computed rhodium yield for 99.1%.
Embodiment 4
Raw material, material quantity, device and step are with embodiment 1, different addition 160g dimethylformamides；Substep heats up：
Oil bath temperature is controlled first for 90 DEG C, evaporates light component；When apparatus for evaporation condensation dripless flows out, oil bath temperature is controlled for 155
℃；Apparatus for evaporation condensation again dripless flow out when, control oil bath temperature be 185 DEG C, constant temperature 1.5 hours.Obtain residual liquid
47.2g。
Analysis testing result shows that rhodium chloride impurity element total amount is 0.046%, meets YS/T593-2006 primes
Quality index, is computed rhodium yield 99.6%.
Claims (2)
1. the method that rhodium controlling the water circulation closes radium chloride is reclaimed in a kind of spent rhodium catalyst from carbongl group synthesis reaction, it is characterised in that to useless
Dimethylformamide, stirring and evenly mixing is added under nitrogen protection, to take substep to heat up and heat in rhodium catalyst solution, steam Jing
Condensing units are collected, and tail gas is processed with Water spray absorption tower, and gained residual liquid adds ethanol dilution to filter, filtering residue washing with alcohol three times
Active rhodium simple substance is obtained, enriching hydrochloric acid, dioxygen water dissolution obtain rhodium chloride solution to active rhodium simple substance successively, by amberlite
Fat removes de-iron, nickel, calcium impurities ion, obtains smart rhodium chloride acid solution, and smart rhodium chloride acid solution is concentrated again to be dried to obtain high-purity three
Radium chloride；
After wherein described spent rhodium catalyst includes from carbongl group synthesis reaction device the rhodium-containing dead catalyst discharged or initial concentration
Concentration rhodium-containing dead catalyst, rhodium content be 0.05wt%～0.3wt%, and rhodium-containing dead catalyst after distillation gained rhodium
Slag, rhodium content are 0.3wt%～10wt%；
50～100 times for spent rhodium catalyst rhodium quality of the quality of the dimethylformamide；
Described heating takes substep to heat up：Heat source temperature is controlled first for 90 DEG C, evaporates light component；Apparatus for evaporation condensation aneroid
When drip goes out, heat source temperature is controlled for 150 DEG C～160 DEG C；Apparatus for evaporation condensation again dripless flow out when, control heat source temperature
For 180 DEG C～200 DEG C, constant temperature 1～2 hour；
The mass concentration of the concentrated hydrochloric acid is 36%～38%, and the volume of addition is 10～30 times of filtering residue quality, and unit is mL/
g；
The mass concentration of the hydrogen peroxide is 30%, and the volume of addition is 0.5～1.0 times of concentrated hydrochloric acid volume.
2. in accordance with the method for claim 1, it is characterised in that：The quality for adding dimethylformamide is spent rhodium catalyst rhodium
60～80 times of quality.
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| CN105944768B (en) * | 2016-05-10 | 2018-06-29 | 能特科技有限公司 | A kind of method that rhodium catalyst is recycled in the waste water phase from rhodium-containing |
| CN106315697B (en) * | 2016-08-30 | 2018-08-10 | 昆明铂磊科技有限公司 | The method of rhodium chloride continuous crystallisation |
| CN107879382B (en) * | 2017-12-08 | 2019-04-16 | 中海油天津化工研究设计院有限公司 | A method of radium chloride is prepared from recycling rhodium in useless rhodium slag is burned |
| CN112481494A (en) * | 2019-09-12 | 2021-03-12 | 中国石油化工股份有限公司 | Method for recovering rhodium from residual liquid of waste rhodium catalyst in oxo synthesis reaction |
| CN111020210A (en) * | 2019-12-19 | 2020-04-17 | 浙江省冶金研究院有限公司 | Method for recovering rhodium from waste homogeneous rhodium catalyst |
| CN114427027A (en) * | 2020-09-30 | 2022-05-03 | 中国石油化工股份有限公司 | Method for preparing rhodium trichloride by recovering rhodium from waste rhodium residues and obtained rhodium trichloride |
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