CN107954464A - A kind of method that cupric oxide is recycled from waste methanol catalyst - Google Patents
A kind of method that cupric oxide is recycled from waste methanol catalyst Download PDFInfo
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- CN107954464A CN107954464A CN201711307061.2A CN201711307061A CN107954464A CN 107954464 A CN107954464 A CN 107954464A CN 201711307061 A CN201711307061 A CN 201711307061A CN 107954464 A CN107954464 A CN 107954464A
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- C01G3/00—Compounds of copper
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Abstract
The present invention relates to a kind of method that cupric oxide is recycled from waste methanol catalyst, including:(1) waste methanol catalyst powder is prepared；(2) low temperature plasma pretreatment is carried out to waste methanol catalyst powder；(3) pretreated waste methanol catalyst powder is added in alkali soluble kettle, appropriate caustic-soda aqueous solution is then added into alkali soluble kettle, closed alkali soluble kettle, opens stirring, be warming up to 40~180 DEG C, and reaction product is obtained when reaction 1~5 is small under pressure itself；(4) reaction product is separated by filtration, wash it is dry after obtain cupric oxide.A kind of method that cupric oxide is recycled from waste methanol catalyst disclosed by the invention has the following effects that：1st, technical process is simple；2nd, cost is low；3rd, the rate of recovery of cupric oxide can reach more than 98%, and the quality of cupric oxide meets《GB/T26046‑2010》The standard of middle primes.
Description
Technical field
The invention belongs to hazardous solid waste recycling disposal field, and in particular to one kind recycles oxygen from waste methanol catalyst
Change the method for copper.
Background technology
Methanol is a kind of important industrial chemicals, and is a kind of vehicle fuel.In basic organic chemical raw material, methanol is used
Amount is only second to ethene, propylene and benzene, occupies the 4th.Methanol synthesis catalyst is mainly Cu-series catalyst, and ten thousand are up to per annual consumption
Tonne.Fresh copper system catalyst for methanol each component is all in oxidation state (copper and aluminium in such as component are cupric oxide and aluminium oxide),
But need to handle by reduction activation before putting into operation, cupric oxide therein is reduced into the (oxidation of metallic copper active component
Aluminium is not easy to be reduced, and is still oxidation state).The service life of usual catalyst for methanol only has 2~3 years, is used under extreme case
Less than 1 year, this tied the sulphur (the mainly presence in the form of hydrogen sulfide and organic sulfur) in unstrpped gas mainly due to metallic copper
Conjunction ability is very strong：The K of copper sulfideSPFor 8.5 × 10-45, this causes catalyst for methanol that sulfur poisoning occurs and inactivates.It is domestic annual
Produce nearly ten thousand tons of waste methanol catalyst.
The component of typical waste methanol catalyst is as shown in table 1, and waste methanol catalyst mainly contains elemental copper and aluminium oxide, this
Containing Sulfur copper and coking material (carbon) etc. are gone back outside, and copper sulfide and coking material (carbon) are the products of catalyst poisoning association.
The each component content of 1 waste methanol catalyst of table
| Component | Elemental copper | Aluminium oxide | Copper sulfide | Coking material | Other |
| % | 55~60 | 8~10 | 3 | 0.5 | 30~40 |
Waste methanol catalyst is mainly recycled using Wet technique both at home and abroad at present.It is normal using more hydrometallurgic recovery technology
It is referred to as " acid extracting " and " ammonia leaching process ".Chinese patent CN 102125851B report to waste methanol catalyst carry out 800~
1000 DEG C of high temperature oxidation process, it is then using sulfuric acid (or nitric acid) that the molten generation of cupric oxide acid in waste copper catalyst is corresponding
Ion enters solution, and the aluminium oxide after high-temperature stable is then less with acid reaction, it is achieved thereby that the separation of copper and aluminium oxide.It is right
In the acid solution of copper ions, then reducing agent is added thereto copper ion is reduced into metallic copper primary product.Metallic copper primary product
Through follow-up impurity removal procedure, metallic copper industrial goods are can obtain.Key reaction process is as follows：
(1) reaction that high temperature oxidation process is related to：
2Cu+O2→2CuO
2CuS+3O2→2CuO+2SO2
C+O2→CO2
β-Al2O3→α-Al2O3(texture portion conversion)
(2) reaction that the molten recycling copper of acid is related to：
CuO+2H+→Cu2++H2O
α-Al2O3+H+→ do not react
Cu2++ reducing agent → Cu
From the above reaction, it is seen that high temperature oxidation process mainly removes the sulphur of waste methanol catalyst, coke, will be single
Matter copper is converted into oxidation state, and the β type crystal structures of aluminium oxide are partially converted into α types, and conversion completely then needs to reach 1400 DEG C
High temperature above；α-Al2O3For inert substance, do not react with soda acid.It can be seen from the above that high temperature oxidation process is extremely important
The step of, otherwise follow-up sour molten efficiency is then very low.
Chinese patent application CN 102766759A report another hydrometallurgic recovery technology, first still to the methanol that gives up
Catalyst carries out high temperature oxidation process, and ammonium salt (NH is then added into waste methanol catalyst4Cl) solution, ammonium salt can be with other groups
Distribute raw complex reaction and dissolve, but cannot be reacted with cupric oxide, then cupric oxide is retained in catalyst slag.To catalyst slag
Middle addition sulfuric acid, makes cupric oxide change into water miscible copper sulphate, it is achieved thereby that the recycling of copper.Here high temperature oxidation process institute
The reaction being related to is same as above, and the reaction that the dipped journey of ammonia is related to is：
CuO+4NH4Cl→Cu(NH3)4Cl2+2HCl+H2O (hardly reacts)
Cupric oxide separates involved reaction with catalyst slag：
CuO+H2SO→CuSO4+H2O
Obviously more than no matter " acid extracting " or " ammonia leaching process ", all there are following drawback：
1st, it is required for carrying out high temperature oxidation process, can so consumes substantial amounts of fuel and be used to heat up；
2nd, technical process is more complicated, to obtain copper, it is necessary to including at least high temperature oxidation process, sour molten (or ammonia leaching), reduction
Three key steps such as (or sulphation)；Strong acid is used during further, since, causes equipment, pipeline corrosion serious.
3rd, high temperature oxidation process can only be partly by the β-Al in waste methanol catalyst2O3It is converted into inert α-Al2O3, by
It is incomplete in crystal structure conversion, still there are a considerable number of aluminium oxide and the sulfuric acid anti-when sulfuric acid is added in waste methanol catalyst
Aluminum sulfate should be generated and enter liquid phase, cause subsequent process to remove aluminium, such recovery process becomes more complicated, while
The rate of recovery of copper is reduced, the rate of recovery using the general copper of the above method only has 93%~95% or so.
To solve above technical problem, the present invention provides a kind of method that cupric oxide is recycled from waste methanol catalyst.
The content of the invention
Goal of the invention：For existing hydrometallurgic recovery technology, there are process route is complicated, copper recovery is relatively low and operating cost
The problem of again high, the invention discloses a kind of method that cupric oxide is recycled in inexpensive, high-recovery slave waste methanol catalyst.
Technical solution：Waste methanol catalyst is pre-processed first by low temperature plasma, to remove sulphur therein
And carbon, while elemental copper is oxidized to corresponding cupric oxide, then reuse lye and alkali soluble processing carried out to waste methanol catalyst,
Material all in addition to cupric oxide in catalyst is all dissolved in lye, is by separation of solid and liquid, washing, filter cake finally
Technical grade aoxidizes copper products.
A kind of method that cupric oxide is recycled from waste methanol catalyst, includes the following steps:
(1) waste methanol catalyst crushed, cross 200~1000 mesh sieve nets, obtain waste methanol catalyst powder；
(2) pre-process
The obtained waste methanol catalyst powder of step (1) is put into reaction of low temperature plasma device, opens low temperature
The air glow discharge generating means of plasma reactor, makes waste methanol catalyst carry out room temperature oxygen in low temperature plasma
Change, the color without sulfur dioxide and waste methanol catalyst is by red in the tail gas to be checked for measuring the discharge of reaction of low temperature plasma device
When being converted into crineous, pretreatment terminates；
(3) pretreated waste methanol catalyst powder is added in alkali soluble kettle, is then added into alkali soluble kettle appropriate
Caustic-soda aqueous solution, closed alkali soluble kettle, opens stirring, is warming up to 40~180 DEG C, is obtained when reaction 1~5 is small under pressure itself anti-
Answer product；
(4) reaction product that step (3) obtains is separated by filtration, it is small in 100~120 DEG C of dryings 8~10 after Washing of Filter Cake
When, that is, obtain cupric oxide.
Further, the cupric oxide that step (4) obtains is at least the industrial goods stair oxidation copper of 99wt% for purity.
Further, the caustic-soda aqueous solution described in step (3) refers to the caustic soda water that molar concentration is 0.5~1.0mol/L
Solution.
Further, the addition of the caustic-soda aqueous solution in step (3) is the 50%~80% of alkali soluble kettle dischargeable capacity.
Further, the filter cake in step (4) is washed through deionized water.
Further, low temperature plasma is the 4th state of material after solid-state, liquid, gaseous state, when applied voltage reaches
To air firing voltage when, air molecule is breakdown, produce including electronics, various ions, atom and free radical including mixing
It is fit.
The technical principle of foundation of the present invention is as follows：
In low temperature plasma, the oxygen molecule in air is dissociated into free with highly reactive electronics and oxygen
Base etc., elemental copper, copper sulfide and coke in waste methanol catalyst obtain electronics and are activated, and in oxidation, these are lived oxygen radical
The material of change, then there occurs desulfurization, decarburization and oxidation reaction：
Plasma exciatiaon：
O2→2O·
It is plasma-activated：
CuS→Cu·+S·
Cu→Cu·
C→C·
Free-radical oxidation：
Cu·+O·→CuO
S·+2O·→SO2
C·+2O·→CO2
Catalyst after being pretreated is reacted by alkali soluble again, and following reaction occurs：
Al2O3+2NaOH→2NaAlO2+H2O
CuO+NaOH → do not react
Aluminium oxide is amphoteric oxide, can be reacted with alkali, and cupric oxide cannot be reacted with alkali.It should be noted that due to
For aluminium oxide not through high-temperature process, crystal structure remains as β types, does not produce inert α types, high with alkali reactivity.In this way,
After aluminium is removed by alkali soluble, for filter cake after deionized water is washed, re-dry is to obtain the oxidation that purity is more than 99%
Copper Processing Industry primes.
Beneficial effect：A kind of method for recycling cupric oxide from waste methanol catalyst disclosed by the invention has following effect
Fruit：
1st, technical process is simple；
2nd, cost is low；
3rd, the rate of recovery of cupric oxide can reach more than 98%, and the quality of cupric oxide meets《GB/T 26046-2010》In one
The standard of level product.
Embodiment：
The embodiment of the present invention is described in detail below.
Specific embodiment 1
A kind of method that cupric oxide is recycled from waste methanol catalyst, includes the following steps:
(1) waste methanol catalyst crushed, cross 200 mesh sieve nets, obtain waste methanol catalyst powder；
(2) pre-process
The obtained waste methanol catalyst powder of step (1) is put into reaction of low temperature plasma device, opens low temperature
The air glow discharge generating means of plasma reactor, makes waste methanol catalyst carry out room temperature oxygen in low temperature plasma
Change, the color without sulfur dioxide and waste methanol catalyst is by red in the tail gas to be checked for measuring the discharge of reaction of low temperature plasma device
When being converted into crineous, pretreatment terminates；
(3) pretreated waste methanol catalyst powder is added in alkali soluble kettle, is then added into alkali soluble kettle appropriate
Caustic-soda aqueous solution, closed alkali soluble kettle, opens stirring, is warming up to 40 DEG C, and reaction product is obtained when reaction 5 is small under pressure itself；
(4) reaction product that step (3) obtains is separated by filtration, after Washing of Filter Cake, when 100 DEG C of dryings 10 are small, to obtain the final product
To cupric oxide.
Further, the cupric oxide that step (4) obtains is at least the industrial goods stair oxidation copper of 99wt% for purity.
Further, the caustic-soda aqueous solution described in step (3) refers to the caustic-soda aqueous solution that molar concentration is 0.5mol/L.
Further, the addition of the caustic-soda aqueous solution in step (3) is the 50% of alkali soluble kettle dischargeable capacity.
Further, the filter cake in step (4) is washed through deionized water.
Further, low temperature plasma is the 4th state of material after solid-state, liquid, gaseous state, when applied voltage reaches
To air firing voltage when, air molecule is breakdown, produce including electronics, various ions, atom and free radical including mixing
It is fit.
Specific embodiment 2
A kind of method that cupric oxide is recycled from waste methanol catalyst, includes the following steps:
(1) waste methanol catalyst crushed, cross 1000 mesh sieve nets, obtain waste methanol catalyst powder；
(2) pre-process
The obtained waste methanol catalyst powder of step (1) is put into reaction of low temperature plasma device, opens low temperature
The air glow discharge generating means of plasma reactor, makes waste methanol catalyst carry out room temperature oxygen in low temperature plasma
Change, the color without sulfur dioxide and waste methanol catalyst is by red in the tail gas to be checked for measuring the discharge of reaction of low temperature plasma device
When being converted into crineous, pretreatment terminates；
(3) pretreated waste methanol catalyst powder is added in alkali soluble kettle, is then added into alkali soluble kettle appropriate
Caustic-soda aqueous solution, closed alkali soluble kettle, opens stirring, is warming up to 180 DEG C, and reaction product is obtained when reaction 1 is small under pressure itself；
(4) reaction product that step (3) obtains is separated by filtration, after Washing of Filter Cake, when 120 DEG C of dryings 8 are small, that is, obtained
Cupric oxide.
Further, the cupric oxide that step (4) obtains is at least the industrial goods stair oxidation copper of 99wt% for purity.
Further, the caustic-soda aqueous solution described in step (3) refers to the caustic-soda aqueous solution that molar concentration is 1.0mol/L.
Further, the addition of the caustic-soda aqueous solution in step (3) is the 80% of alkali soluble kettle dischargeable capacity.
Further, the filter cake in step (4) is washed through deionized water.
Further, low temperature plasma is the 4th state of material after solid-state, liquid, gaseous state, when applied voltage reaches
To air firing voltage when, air molecule is breakdown, produce including electronics, various ions, atom and free radical including mixing
It is fit.
Specific embodiment 3
A kind of method that cupric oxide is recycled from waste methanol catalyst, includes the following steps:
(1) waste methanol catalyst crushed, cross 400 mesh sieve nets, obtain waste methanol catalyst powder；
(2) pre-process
The obtained waste methanol catalyst powder of step (1) is put into reaction of low temperature plasma device, opens low temperature
The air glow discharge generating means of plasma reactor, makes waste methanol catalyst carry out room temperature oxygen in low temperature plasma
Change, the color without sulfur dioxide and waste methanol catalyst is by red in the tail gas to be checked for measuring the discharge of reaction of low temperature plasma device
When being converted into crineous, pretreatment terminates；
(3) pretreated waste methanol catalyst powder is added in alkali soluble kettle, is then added into alkali soluble kettle appropriate
Caustic-soda aqueous solution, closed alkali soluble kettle, opens stirring, is warming up to 120 DEG C, and reaction production is obtained when reaction 1~5 is small under pressure itself
Thing；
(4) reaction product that step (3) obtains is separated by filtration, after Washing of Filter Cake, when 110 DEG C of dryings 9 are small, that is, obtained
Cupric oxide.
Further, the cupric oxide that step (4) obtains is at least the industrial goods stair oxidation copper of 99wt% for purity.
Further, the caustic-soda aqueous solution described in step (3) refers to the caustic-soda aqueous solution that molar concentration is 0.8mol/L.
Further, the addition of the caustic-soda aqueous solution in step (3) is the 65% of alkali soluble kettle dischargeable capacity.
Further, the filter cake in step (4) is washed through deionized water.
Further, low temperature plasma is the 4th state of material after solid-state, liquid, gaseous state, when applied voltage reaches
To air firing voltage when, air molecule is breakdown, produce including electronics, various ions, atom and free radical including mixing
It is fit.
Embodiments of the present invention are elaborated above.But present invention is not limited to the embodiments described above,
In the knowledge that technical field those of ordinary skill possesses, it can also be done on the premise of present inventive concept is not departed from
Go out various change.
Claims (4)
- A kind of 1. method that cupric oxide is recycled from waste methanol catalyst, it is characterised in that include the following steps:(1) waste methanol catalyst crushed, cross 200~1000 mesh sieve nets, obtain waste methanol catalyst powder；(2) pre-processThe obtained waste methanol catalyst powder of step (1) is put into reaction of low temperature plasma device, open low temperature etc. from The air glow discharge generating means of daughter reactor, makes waste methanol catalyst carry out normal temperature oxidation in low temperature plasma, The color without sulfur dioxide and waste methanol catalyst is turned by red in the tail gas to be checked for measuring the discharge of reaction of low temperature plasma device When turning to crineous, pretreatment terminates；(3) pretreated waste methanol catalyst powder is added in alkali soluble kettle, appropriate caustic soda is then added into alkali soluble kettle Aqueous solution, closed alkali soluble kettle, opens stirring, is warming up to 40~180 DEG C, and reaction production is obtained when reaction 1~5 is small under pressure itself Thing；(4) reaction product that step (3) obtains is separated by filtration, after Washing of Filter Cake, when 100~120 DEG C of dryings 8~10 are small, Obtain cupric oxide.
- A kind of 2. method that cupric oxide is recycled from waste methanol catalyst according to claim 1, it is characterised in that step (4) cupric oxide obtained is at least the industrial goods stair oxidation copper of 99wt% for purity.
- A kind of 3. method that cupric oxide is recycled from waste methanol catalyst according to claim 1, it is characterised in that step (3) caustic-soda aqueous solution described in refers to the caustic-soda aqueous solution that molar concentration is 0.5~1.0mol/L.
- A kind of 4. method that cupric oxide is recycled from waste methanol catalyst according to claim 1, it is characterised in that step (4) filter cake in is washed through deionized water.
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| CN103495426A (en) * | 2013-09-22 | 2014-01-08 | 大连瑞克科技有限公司 | Method for recycling waste copper-based methanol waste catalyst |
| CN104475009A (en) * | 2014-12-09 | 2015-04-01 | 北京三聚环保新材料股份有限公司 | Method for preparing mercury removing agent from waste methanol catalyst |
| CN106238040A (en) * | 2016-07-29 | 2016-12-21 | 西安科技大学 | The preparation method of modified fly ash loading Mn Ce bimetallic denitration catalyst |
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2017
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| CN101205079A (en) * | 2007-09-25 | 2008-06-25 | 李文志 | Treatment of electronic intelligent label chemical etching waste liquor with another waste and abstraction technology |
| CN103495426A (en) * | 2013-09-22 | 2014-01-08 | 大连瑞克科技有限公司 | Method for recycling waste copper-based methanol waste catalyst |
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| CN104475009A (en) * | 2014-12-09 | 2015-04-01 | 北京三聚环保新材料股份有限公司 | Method for preparing mercury removing agent from waste methanol catalyst |
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