CN104988318A - Method and system for treating load type palladium-contained dead catalyst - Google Patents
Method and system for treating load type palladium-contained dead catalyst Download PDFInfo
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- CN104988318A CN104988318A CN201510345394.9A CN201510345394A CN104988318A CN 104988318 A CN104988318 A CN 104988318A CN 201510345394 A CN201510345394 A CN 201510345394A CN 104988318 A CN104988318 A CN 104988318A
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- palladium
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- leaching
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- 238000000034 method Methods 0.000 title claims abstract description 173
- 239000003054 catalyst Substances 0.000 title claims abstract description 112
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 370
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 165
- 239000007788 liquid Substances 0.000 claims abstract description 94
- 239000011347 resin Substances 0.000 claims abstract description 43
- 229920005989 resin Polymers 0.000 claims abstract description 43
- 230000008569 process Effects 0.000 claims description 127
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 88
- 238000002386 leaching Methods 0.000 claims description 66
- 238000005406 washing Methods 0.000 claims description 41
- 238000001354 calcination Methods 0.000 claims description 39
- 238000011068 loading method Methods 0.000 claims description 34
- 229910052751 metal Inorganic materials 0.000 claims description 25
- 239000002184 metal Substances 0.000 claims description 25
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims description 20
- 239000003456 ion exchange resin Substances 0.000 claims description 20
- 229920003303 ion-exchange polymer Polymers 0.000 claims description 20
- 238000003795 desorption Methods 0.000 claims description 18
- 239000011259 mixed solution Substances 0.000 claims description 14
- 238000010521 absorption reaction Methods 0.000 claims description 13
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 12
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 claims description 12
- -1 oxymuriate Chemical compound 0.000 claims description 11
- 239000000460 chlorine Substances 0.000 claims description 8
- 238000007670 refining Methods 0.000 claims description 7
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 6
- 229910052801 chlorine Inorganic materials 0.000 claims description 6
- 229910017604 nitric acid Inorganic materials 0.000 claims description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 5
- 239000003929 acidic solution Substances 0.000 claims description 5
- 150000001450 anions Chemical class 0.000 claims description 5
- 239000003637 basic solution Substances 0.000 claims description 5
- 150000001768 cations Chemical class 0.000 claims description 5
- 238000011084 recovery Methods 0.000 abstract description 37
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 20
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 230000009467 reduction Effects 0.000 abstract description 3
- 230000002829 reductive effect Effects 0.000 abstract description 2
- 229910052594 sapphire Inorganic materials 0.000 abstract 2
- 239000000243 solution Substances 0.000 description 15
- 239000000463 material Substances 0.000 description 12
- 239000010970 precious metal Substances 0.000 description 12
- 230000000694 effects Effects 0.000 description 11
- 239000007800 oxidant agent Substances 0.000 description 10
- 230000001590 oxidative effect Effects 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 239000002253 acid Substances 0.000 description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- 229910052799 carbon Inorganic materials 0.000 description 7
- 238000004090 dissolution Methods 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 7
- 238000001179 sorption measurement Methods 0.000 description 7
- KMWBBMXGHHLDKL-UHFFFAOYSA-N [AlH3].[Si] Chemical compound [AlH3].[Si] KMWBBMXGHHLDKL-UHFFFAOYSA-N 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 230000008859 change Effects 0.000 description 5
- 239000002699 waste material Substances 0.000 description 5
- 241000196324 Embryophyta Species 0.000 description 4
- 229910004298 SiO 2 Inorganic materials 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- 229910021529 ammonia Inorganic materials 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 125000003963 dichloro group Chemical group Cl* 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- BZSXEZOLBIJVQK-UHFFFAOYSA-N 2-methylsulfonylbenzoic acid Chemical compound CS(=O)(=O)C1=CC=CC=C1C(O)=O BZSXEZOLBIJVQK-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000010953 base metal Substances 0.000 description 3
- 239000000428 dust Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- 101150003085 Pdcl gene Proteins 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- QZPSXPBJTPJTSZ-UHFFFAOYSA-N aqua regia Chemical compound Cl.O[N+]([O-])=O QZPSXPBJTPJTSZ-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- NICDRCVJGXLKSF-UHFFFAOYSA-N nitric acid;trihydrochloride Chemical compound Cl.Cl.Cl.O[N+]([O-])=O NICDRCVJGXLKSF-UHFFFAOYSA-N 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 1
- 235000015320 potassium carbonate Nutrition 0.000 description 1
- 235000011118 potassium hydroxide Nutrition 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- PFUVRDFDKPNGAV-UHFFFAOYSA-N sodium peroxide Chemical compound [Na+].[Na+].[O-][O-] PFUVRDFDKPNGAV-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
Classifications
-
- 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
Abstract
The invention discloses a method and system for treating a load type palladium-contained dead catalyst. A carrier of the load type dead catalyst is alpha-Al2O3 or SiO2-alpha-Al2O3. The method includes the steps that 1, the palladium-contained dead catalyst is calcinated; 2, the calcinated dead catalyst is leached, and the carrier and palladium-contained leachate are obtained; 3, exchange treatment is conducted on the palladium-contained leachate, exchanged liquid and resin for adsorbing palladium are obtained, and most of the exchanged liquid is returned to be leached; 4, the resin for adsorbing palladium is desorbed; 5, desorbed liquid is refined, and palladium products are obtained. By the adoption of the method, the reagent use amount can be greatly reduced, reduction of the production process is achieved, and the recovery rate of palladium reaches up to 99% or above.
Description
Technical field
The invention belongs to chemical technology field, specifically, the present invention relates to a kind of method and system processing loading type and contain Used palladium catalyst.
Background technology
Precious metal is scarce resource, and its spent catalyst made plays a part can not be substituted in petrochemical industry.Spent catalyst is after life-time service, due to carbon containing matter deposition or the poisoning of various detrimental impurity, make it gradually lose activity, in the carrier waste catalyst recovery process of scrapping, must manage to make a small amount of precious metal and carrier substance and various magazins' layout.The precious metal spent catalyst of current industrial application, mainly using aluminum oxide or silicon oxide as carrier.Along with industrial expansion, the shortage of resource, in spent catalyst, precious metal is as the secondary resource of preciousness, has very large recovery value.
Reclaim the method for spent noble metals bearing catalysts at present both at home and abroad, mostly only reclaim precious metal wherein, and wherein carrier is utilized.
Patent CN 19979961A discloses a kind of method reclaiming platinum metals from precious metal automobile waste catalyzer or aluminum oxide spent catalyst, add the reductive agent of moisture content in spent catalyst while, spent catalyst is crushed to average particle size particle size and is less than 20 μm, pulverize and carry out with reduction process simultaneously, precious metal in aqua regia dissolution spent catalyst, carrier is insoluble, adds ammonium chloride precipitate precious metals after leach liquor is concentrated.But the method chloroazotic acid consumption is large, precious metal is residual many, and the concentrated amount of solution is large, and the rate of recovery is low.
Patent CN 1788095A discloses a kind of method reclaiming platinum metals from the rich solution containing platinum metals and base metal or leach liquor, first carry out non-selective precipitation, form expensive, base metal throw out, and then Selectively leaching is carried out to precipitation, what its Selectively leaching adopted is that caustic alkali leaches, and base metal is dissolved, precious metal is insoluble, or high and low metal all dissolves, then resins exchange or calcine again, from insolubles, pressurized acid leaching reclaims precious metal.But the method long flow path, equipment requirements is high.
Patent CN 103045872A discloses and a kind ofly reclaims the novel process that silicon carries palladium, adopt and useless silicon carried Used palladium catalyst and caustic soda, Pian Zhuan caustic potash flakes or the strong alkaline substance such as sodium carbonate, salt of wormwood and sodium peroxide melting under middle temperature, the method of water logging is then adopted to make silicon carrier wherein all proceed to liquid phase, filtration makes solid-liquor separation collection solid carry out refining, carries out neutralizing treatment make it to become white carbon black to silicon solution.Although this technique is simple, pollution-free, there is the shortcoming that a small amount of palladium enters infusion, filtration difficulty, and to α-Al
2o
3or α-Al
2o
3/ SiO
2the spent catalyst of carrier is inapplicable.
Therefore, existing process loading type is further improved containing the technology of Used palladium catalyst.
Summary of the invention
The present invention is intended to solve one of technical problem in correlation technique at least to a certain extent.For this reason, one object of the present invention is to propose a kind of method and system processing loading type and contain Used palladium catalyst, the method can greatly reduce reagent dosage, reclaim the palladium element in spent catalyst and carrier simultaneously, thus realize the comprehensive utilization of loading type containing Used palladium catalyst, and the rate of recovery of palladium element is up to more than 99%.
In one aspect of the invention, the present invention proposes a kind of method processing loading type and contain Used palladium catalyst, the carrier of described loading type spent catalyst is α-Al
2o
3or SiO
2-α-Al
2o
3, described method comprises:
(1) calcination process is carried out described containing Used palladium catalyst;
(2) spent catalyst through calcination process that step (1) obtains is carried out leaching process, to obtain carrier and to contain palladium leach liquor;
(3) adopt ion exchange resin to described containing palladium leach liquor carry out exchanges process, to obtain the resin exchanging rear liquid and adsorbing metal palladium, and a part for liquid after described exchange is returned step (2) carry out described leaching process;
(4) resin of stripping liquid to described adsorbing metal palladium is adopted to carry out desorb process, so that liquid after obtaining desorb;
(5) liquid after described desorb is carried out refinement treatment, to obtain palladium product.
The method of Used palladium catalyst is contained by carrying out Selectively leaching to Palladium from Wasted Catalyst element according to the process loading type of the embodiment of the present invention, make the rate of recovery of final palladium element up to more than 99%, and ensure that carrier is not destroyed, thus can as aluminium silicon resource material use, realize the maximum using of resource, after the exchange simultaneously obtained by exchange process, liquid returns and carries out leaching process, the service efficiency of leach liquor can be significantly improved, and significantly can reduce the usage quantity of leach liquor, thus reduce the processing cost of spent catalyst, achieve the minimizing of production process, resource utilization.
In addition, following additional technical characteristic can also be had according to the process loading type of the embodiment of the present invention containing the method for Used palladium catalyst:
In some embodiments of the invention, described process loading type comprises further containing the method for Used palladium catalyst: the described carrier that step (2) obtains is carried out carrying out washing treatment by (6), and liquid after the washing obtained is returned step (3) and carry out described exchanges and process.Thus, the rate of recovery of palladium element can be significantly improved.
In some embodiments of the invention, described calcination process carries out 2 ~ 4 hours under 500 ~ 700 degrees Celsius.Thus, carbon deposit and organic removal efficiency on spent catalyst can be significantly improved.
In some embodiments of the invention, described leaching process adopts the following step to carry out: (2-1) is by the described spent catalyst through calcination process and mixed in hydrochloric acid; (2-2) mixed solution that step (2-1) obtains is contacted with oxygenant, to obtain described carrier and described containing palladium leach liquor.
In some embodiments of the invention, in step (2-1), the described spent catalyst through calcination process is that (1:3) ~ (1:6) mixes with described hydrochloric acid according to mass ratio, the concentration of described hydrochloric acid is 2 ~ 5mol/L, in step (2-2), described mixed solution and described oxygenant are that (100:1) ~ (100:2) contacts according to mass ratio, and described oxygenant is be selected from least one in chlorine, oxymuriate, hypochlorite, hydrogen peroxide and nitric acid.Thus, the leaching efficiency of palladium element can be significantly improved, thus improve the rate of recovery of palladium element further.
In some embodiments of the invention, in step (3), described ion exchange resin is be selected from least one in the absorption resin anion(R.A) of palladium, resin cation (R.C.) and resin.Thus, the adsorption efficiency of palladium element can be significantly improved.
In some embodiments of the invention, in step (4), the mass concentration of described stripping liquid is 4 ~ 20%.Thus, the desorption efficiency of palladium element can be significantly improved.
In some embodiments of the invention, described stripping liquid is at least one in basic solution, acidic solution, saline solution.Thus, the desorption efficiency of palladium element can be improved further.
In another aspect of the present invention, the present invention proposes a kind of system processing loading type and contain Used palladium catalyst, comprising:
Calciner, described calciner is suitable for carrying out calcination process by described containing Used palladium catalyst;
Leaching device, described leaching device is connected with described calciner, and is suitable for the spent catalyst through calcination process obtained being carried out leaching process, to obtain carrier and to contain palladium leach liquor;
Switch, described switch is connected with described leaching device, and be suitable for adopting ion exchange resin to carry out exchange process to described containing palladium leach liquor, to obtain the resin exchanging rear liquid and adsorbing metal palladium, and a part for liquid after described exchange is returned described leaching device;
Desorption apparatus, described desorption apparatus is connected with described switch, and is suitable for adopting the resin of stripping liquid to described adsorbing metal palladium to carry out desorb process, so that liquid after obtaining desorb; And
Refining plant, described refining plant is connected with described desorption apparatus, and is suitable for liquid after described desorb being carried out refinement treatment, to obtain palladium product.
The system of Used palladium catalyst is contained by carrying out Selectively leaching to Palladium from Wasted Catalyst element according to embodiment of the present invention process loading type, make the rate of recovery of final palladium element up to more than 99%, and ensure that carrier is not destroyed, thus can as aluminium silicon resource material use, realize the maximum using of resource, after the exchange simultaneously obtained by exchange process, liquid repeatedly returns and carries out leaching process, the service efficiency of leach liquor can be significantly improved, and significantly can reduce the usage quantity of leach liquor, thus reduce the processing cost of spent catalyst, realize production process minimizing, the object of resource utilization.
In addition, process loading type according to the above embodiment of the present invention can also have following additional technical characteristic containing the system of Used palladium catalyst:
In some embodiments of the invention, described loading type comprises further containing the system of Used palladium catalyst:
Washing device, described washing device is connected with described leaching device and switch respectively, and is suitable for described carrier to carry out carrying out washing treatment, and liquid after the washing obtained is returned described switch.Thus, the rate of recovery of palladium element can be significantly improved.
In some embodiments of the invention, described calcination process carries out 2 ~ 4 hours under 500 ~ 700 degrees Celsius.Thus, carbon deposit and organic removal efficiency on spent catalyst can be significantly improved.
In some embodiments of the invention, described leaching process adopts the following step to carry out: by the described spent catalyst through calcination process and mixed in hydrochloric acid; The mixed solution obtained is contacted with oxygenant, to obtain described carrier and described containing palladium leach liquor.
In some embodiments of the invention, the described spent catalyst through calcination process and described hydrochloric acid are (1:3) ~ (1:6) according to mass ratio, the concentration carrying out contacting described hydrochloric acid is 2 ~ 5mol/L, described mixed solution and described oxygenant are that (100:1) ~ (100:2) mixes according to mass ratio, and described oxygenant is be selected from least one in chlorine, oxymuriate, hypochlorite, hydrogen peroxide and nitric acid.Thus, the leaching efficiency of palladium element can be significantly improved, thus improve the rate of recovery of palladium element further.
In some embodiments of the invention, described ion exchange resin is be selected from least one in the absorption resin anion(R.A) of palladium, resin cation (R.C.), resin.Thus, the adsorption efficiency of palladium element can be significantly improved.
In some embodiments of the invention, the mass concentration of described stripping liquid is 4 ~ 20%.Thus, the desorption efficiency of palladium element can be significantly improved.
In some embodiments of the invention, described stripping liquid is at least one in basic solution, acidic solution, saline solution.
Additional aspect of the present invention and advantage will part provide in the following description, and part will become obvious from the following description, or be recognized by practice of the present invention.
Accompanying drawing explanation
Fig. 1 processes the method flow schematic diagram of loading type containing Used palladium catalyst according to an embodiment of the invention;
Fig. 2 is the method flow schematic diagram containing Used palladium catalyst according to the process loading type of another embodiment of the present invention;
Fig. 3 processes the system architecture schematic diagram of loading type containing Used palladium catalyst according to an embodiment of the invention;
Fig. 4 is the system architecture schematic diagram containing Used palladium catalyst according to the process loading type of another embodiment of the present invention.
Embodiment
Be described below in detail embodiments of the invention, the example of described embodiment is shown in the drawings, and wherein same or similar label represents same or similar element or has element that is identical or similar functions from start to finish.Be exemplary below by the embodiment be described with reference to the drawings, be intended to for explaining the present invention, and can not limitation of the present invention be interpreted as.
In describing the invention, it will be appreciated that, term " " center ", " longitudinal direction ", " transverse direction ", " length ", " width ", " thickness ", " on ", D score, " front ", " afterwards ", " left side ", " right side ", " vertically ", " level ", " top ", " end ", " interior ", " outward ", " clockwise ", " counterclockwise ", " axis ", " radial direction ", orientation or the position relationship of the instruction such as " circumference " are based on orientation shown in the drawings or position relationship, only the present invention for convenience of description and simplified characterization, instead of indicate or imply that the device of indication or element must have specific orientation, with specific azimuth configuration and operation, therefore limitation of the present invention can not be interpreted as.
In the present invention, unless otherwise clearly defined and limited, the term such as term " installation ", " being connected ", " connection ", " fixing " should be interpreted broadly, and such as, can be fixedly connected with, also can be removably connect, or integral; Can be mechanical connection, also can be electrical connection; Can be directly be connected, also indirectly can be connected by intermediary, can be the connection of two element internals or the interaction relationship of two elements, unless otherwise clear and definite restriction.For the ordinary skill in the art, above-mentioned term concrete meaning in the present invention can be understood as the case may be.
In the present invention, unless otherwise clearly defined and limited, fisrt feature second feature " on " or D score can be that the first and second features directly contact, or the first and second features are by intermediary indirect contact.And, fisrt feature second feature " on ", " top " and " above " but fisrt feature directly over second feature or oblique upper, or only represent that fisrt feature level height is higher than second feature.Fisrt feature second feature " under ", " below " and " below " can be fisrt feature immediately below second feature or tiltedly below, or only represent that fisrt feature level height is less than second feature.
In one aspect of the invention, the present invention proposes a kind of method processing loading type and contain Used palladium catalyst.According to embodiments of the invention, the carrier of loading type spent catalyst can be α-Al
2o
3or SiO
2-α-Al
2o
3, it should be noted that SiO
2-α-Al
2o
3can be understood as containing SiO
2with α-Al
2o
3mixture.Below with reference to Fig. 1-2, the method for the process loading type of the embodiment of the present invention containing Used palladium catalyst is described in detail.According to a particular embodiment of the invention, the method comprises:
S100: calcination process will be carried out containing Used palladium catalyst
According to embodiments of the invention, calcination process will be carried out containing Used palladium catalyst, thus the carbon deposit can effectively removed in spent catalyst and organism.
According to embodiments of the invention, the condition of calcination process is also not particularly limited, and according to a particular embodiment of the invention, calcination process can carry out 2 ~ 4 hours under 500 ~ 700 degrees Celsius.Contriver finds, can significantly improve the roasting efficiency of spent catalyst, thus significantly improve carbon deposit and organic removal efficiency on spent catalyst under this condition.
S200: the spent catalyst through calcination process is carried out leaching process
According to embodiments of the invention, the spent catalyst through calcination process obtained above is carried out leaching process, thus carrier can be obtained and contain palladium leach liquor.Contriver finds, by carrying out Selectively leaching to Palladium from Wasted Catalyst element, making the rate of recovery of final palladium element up to more than 99%, and ensureing that carrier is not destroyed, thus as aluminium silicon resource material use, can realize the maximum using of resource.
According to embodiments of the invention, leach process and adopt the following step to carry out: by through the spent catalyst of calcination process and mixed in hydrochloric acid, then the mixed solution obtained is contacted with oxygenant.According to a particular embodiment of the invention, oxygenant can for being selected from least one in chlorine, oxymuriate, hypochlorite, hydrogen peroxide and nitric acid.Concrete, due to α-Al in carrier
2o
3do not belong to activated alumina, very stable, strong alkali-acid resistance, and SiO
2also be insoluble to acid, therefore carrier is insoluble when spent catalyst contacts with hydrochloric acid, and in the hydrochloric acid soln of palladium under certain temperature condition, when there being oxygenant to exist, can being oxidized to the muriate of palladium and dissolving in the solution, its reaction equation is: Pd+ClO
3 -+ 6H
++ 11Cl
-=3PdCl
4 2-+ 3H
2o or 3Pd+2NO
3 -+ 8H
++ 12Cl
-=3PdCl
4 2-+ 4H
2o+2NO ↑ or Pd+Cl
2+ 2H
++ 2Cl
-=PdCl
4 2-+ 2H
+or 2Pd+4HCl+2H
2o
2=2H
2pdCl
4+ O
2+ 2H
2o.Thus by above-mentioned leaching method, can realize leaching palladium, not destroy used catalyst support again simultaneously, thus be conducive to recovery and the recycling of carrier.
According to embodiments of the invention, be not particularly limited through the spent catalyst of calcination process and mixed in hydrochloric acid ratio, according to a particular embodiment of the invention, be that (1:3) ~ (1:6) mix with hydrochloric acid according to mass ratio through the spent catalyst of calcination process.After applicant proposes above-mentioned leaching method, continue to be studied the optimum mixture ratio example of catalyzer and hydrochloric acid, and find: when mass ratio is higher than above-mentioned scope, feed liquid is feeding-up, be unfavorable for that reaction is carried out smoothly, and when mass ratio is lower than above-mentioned scope, salt acid consumption is caused to increase, increase subsequent disposal burden and cost, and tail washings amount increases, the rate of recovery reduces, and contriver finds to select aforementioned proportion scope that palladium leaching yield can be made higher through repeatedly studying thus, tail washings amount is less, and the rate of recovery is higher and reagent consumes less.
According to embodiments of the invention, the concentration of hydrochloric acid is also not particularly limited, and according to a particular embodiment of the invention, the concentration of hydrochloric acid can be 2 ~ 5mol/L.After applicant proposes above-mentioned leaching method, continue to be studied the optimum mixture ratio example of catalyzer and hydrochloric acid, and find: when concentration of hydrochloric acid higher than this scope constantly, be unfavorable on the one hand the exchange adsorption palladium of resin, increase reagent consumption on the other hand; And when concentration of hydrochloric acid is lower than this scope, the dissolution rate of palladium declines, contriver is through repeatedly studying the concentration of hydrochloric acid finding to select this concentration range thus, can when ensureing that palladium dissolution rate is higher, and reagent consumption is less, resin absorption better effects if.
According to embodiments of the invention, the blending ratio of mixed solution and oxygenant is also not particularly limited, and according to a particular embodiment of the invention, mixed solution can be that (100:1) ~ (100:2) mixes according to mass ratio with oxygenant.After applicant proposes above-mentioned leaching method, continue to be studied the optimum mixture ratio example of catalyzer and hydrochloric acid, and find: when mass ratio is higher than this scope, oxidant content is not enough, can not palladium be dissolved completely in solution, and when mass ratio is lower than this scope, oxidant consumption amount increases, effective rate of utilization reduces, and solute effect there is no considerable change, contriver finds to select this proportional range through repeatedly studying thus, and palladium solubility rate is higher, and reagent consumes less.
According to embodiments of the invention, the mass concentration of oxygenant is also not particularly limited, and according to a particular embodiment of the invention, the mass concentration of oxygenant can be 5 ~ 15%.After applicant proposes above-mentioned leaching method, continue to be studied the optimum mixture ratio example of catalyzer and hydrochloric acid, and find: when oxidant concentration is higher than this scope, reaction is violent instantaneously, unnecessary oxygenant has little time reaction, reduce the reactivity of oxygenant, add reagent consumption, and when oxidant concentration is lower than this scope, react too slow, oxidant content is not enough, palladium can not be made fully to dissolve, the dissolution rate of palladium is declined.Contriver is through repeatedly studying the oxygenant finding to select this concentration range thus, can ensure in the consoluet situation of palladium, and reagent consumes less, and utilization ratio is higher.
Concrete, the spent catalyst through calcination process mixes with hydrochloric acid by this step, and is heated to 70 ~ 80 DEG C, then slowly adds oxygenant, reacts 0.5 ~ 2 hour, thus makes most of palladium element be dissolved in leach liquor, obtains carrier and contains palladium leach liquor.
According to embodiments of the invention, leaching process can be carried out the spent catalyst gradation through calcination process, thus the rate of recovery of palladium element can be improved significantly further.
S300: adopt ion exchange resin to carrying out exchange process containing palladium leach liquor, and the part exchanging rear liquid is returned step S200
According to embodiments of the invention, adopt ion exchange resin to carry out exchanges process to described containing palladium leach liquor, thus the resin exchanging rear liquid and adsorbing metal palladium can be obtained, and the major part of liquid after the exchange obtained is returned step S200 and carry out leaching and process.One of ordinary skill in the art will readily recognize that major part refers to thing amount over half herein.
For a long time, reclaim field at spent catalyst precious metal, after the exchange of ion exchange resin adsorption treatment, liquid is all reclaiming wherein discharge or directly as tail liquid emissions after minute amount of noble metal.Contriver finds, after the exchange obtained by exchange process, liquid returns and carries out leaching process, significant adverse impact can't be produced to leaching effect, but what can significantly improve leach liquor recycles efficiency, thus significantly can reduce the usage quantity of leach liquor, and then reduce the processing cost of spent catalyst, realize production process minimizing, the maximization of the utilization of resources.
According to embodiments of the invention, the particular type of ion exchange resin is also not particularly limited, and according to a particular embodiment of the invention, ion exchange resin can for being selected from least one in the resin anion(R.A) of absorption palladium, resin cation (R.C.), resin.Contriver finds, the ion exchange resin of the type can significantly improve the adsorption efficiency of palladium element, thus improves the rate of recovery of palladium element further.
S400: adopt stripping liquid to carry out desorb process to the resin of adsorbing metal palladium
According to embodiments of the invention, stripping liquid is adopted to carry out desorb process to the resin of adsorbing metal palladium, thus liquid after desorb can be obtained.Thus, the rate of recovery of palladium element can be improved further.
According to embodiments of the invention, the concentration of stripping liquid is also not particularly limited, and according to a particular embodiment of the invention, the mass concentration of stripping liquid can be 4 ~ 20%.Contriver finds, if concentration is higher than this scope, increase strippant and rinse water consumption on the one hand, increase the reagent dosage of acidity adjustment in subsequent step on the other hand, and concentration is lower than this scope, then desorption effect declines, contriver is through repeatedly studying discovery thus, when stripping liquid mass concentration is in this scope, desorption effect is better, and reagent consumes less.
According to embodiments of the invention, the particular type of stripping liquid is also not particularly limited, and according to a particular embodiment of the invention, stripping liquid can be at least one in basic solution, acidic solution, saline solution.Contriver finds, the stripping liquid of the type can significantly improve the desorption efficiency of the resin of adsorbing metal palladium, thus improves the rate of recovery of palladium element further.
S500: liquid after desorb is carried out refinement treatment
According to embodiments of the invention, liquid after desorb is carried out refinement treatment, thus palladium product can be obtained.Thus, palladium product purity can be significantly improved.
According to embodiments of the invention, the purity of palladium product is not less than 99.95%, and the rate of recovery is up to more than 99%.
In this step, concrete, after desorb, liquid carries out ammoniated treatment (such as: add ammoniacal liquor) after adjustment acidity, make palladium change into dichloro four ammonia palladium solution, then filter, filtrate is used hcl acidifying again, obtain dichloro diamino palladium precipitation, use water slurry after sedimentation and filtration washing, then add ammonia solvent, obtain pure palladium with hydrazine hydrate reduction.
The method of Used palladium catalyst is contained by carrying out Selectively leaching to Palladium from Wasted Catalyst element according to the process loading type of the embodiment of the present invention, make the rate of recovery of final palladium element up to more than 99%, and ensure that carrier is not destroyed, thus can as aluminium silicon resource material use, realize the maximum using of resource, after the exchange simultaneously obtained by exchange process, liquid returns and carries out leaching process, the service efficiency of leach liquor can be significantly improved, and significantly can reduce the usage quantity of leach liquor, thus reduce the processing cost of spent catalyst, realize production process minimizing, maximum resource utilization.
With reference to figure 2, the process loading type of the embodiment of the present invention comprises further containing the method for Used palladium catalyst:
S600: carrier is carried out carrying out washing treatment, and liquid after the washing obtained is returned S300 carry out exchange process
According to embodiments of the invention, the carrier obtained by S200 carries out carrying out washing treatment, and liquid after the washing obtained is returned S300 carry out exchange process.Concrete, the carrier leached after process can wash with water, to reduce the leach liquor that carrier is carried secretly, can reduce palladium loss on the one hand, on the other hand carrier is washed till neutrality not containing residual acid, and in carrier after washing palladium content lower than 6ppm.Thus, the rate of recovery of palladium element can be improved further.
In second of the present invention, the present invention proposes a kind of system processing loading type and contain Used palladium catalyst.According to embodiments of the invention, the carrier of loading type spent catalyst can be α-Al
2o
3or SiO
2-α-Al
2o
3.The system that process loading type below with reference to Fig. 3-4 pairs of embodiment of the present invention contains Used palladium catalyst is described in detail.According to a particular embodiment of the invention, this system comprises:
Calciner 100: according to embodiments of the invention, calciner 100 is suitable for carrying out calcination process by containing Used palladium catalyst, thus the carbon deposit can effectively removed in spent catalyst and organism.
According to embodiments of the invention, the condition of calcination process is also not particularly limited, and according to a particular embodiment of the invention, calcination process can carry out 2 ~ 4 hours under 500 ~ 700 degrees Celsius.Contriver finds, can significantly improve the roasting efficiency of spent catalyst, thus significantly improve carbon deposit and organic removal efficiency on spent catalyst under this condition.
Leaching device 200: according to embodiments of the invention, leaching device 200 is connected with calciner 100, and is suitable for the spent catalyst through calcination process obtained above being carried out leaching process, thus can obtain carrier and contain palladium leach liquor.Contriver finds, by carrying out Selectively leaching to Palladium from Wasted Catalyst element, making the rate of recovery of final palladium element up to more than 99%, and ensureing that carrier is not destroyed, thus as aluminium silicon resource material use, can realize the maximum using of resource.
According to embodiments of the invention, leach process and adopt the following step to carry out: by through the spent catalyst of calcination process and mixed in hydrochloric acid, then the mixed solution obtained is contacted with oxygenant.According to a particular embodiment of the invention, oxygenant can for being selected from least one in chlorine, oxymuriate, hypochlorite, hydrogen peroxide and nitric acid.Concrete, due to α-Al in carrier
2o
3do not belong to activated alumina, very stable, strong alkali-acid resistance, and SiO
2also be insoluble to acid, therefore carrier is insoluble when spent catalyst contacts with hydrochloric acid, and in the hydrochloric acid soln of palladium under certain temperature condition, when there being oxygenant to exist, can being oxidized to the muriate of palladium and dissolving in the solution, its reaction equation is: Pd+ClO
3 -+ 6H
++ 11Cl
-=3PdCl
4 2-+ 3H
2o or 3Pd+2NO
3 -+ 8H
++ 12Cl
-=3PdCl
4 2-+ 4H
2o+2NO ↑ or Pd+Cl
2+ 2H
++ 2Cl
-=PdCl
4 2-+ 2H
+or 2Pd+4HCl+2H
2o
2=2H
2pdCl
4+ O
2+ 2H
2o.Thus by above-mentioned leaching method, can realize leaching palladium, not destroy used catalyst support again simultaneously, thus be conducive to recovery and the recycling of carrier.
According to embodiments of the invention, be not particularly limited through the spent catalyst of calcination process and mixed in hydrochloric acid ratio, according to a particular embodiment of the invention, be that (1:3) ~ (1:6) mix with hydrochloric acid according to mass ratio through the spent catalyst of calcination process.Contriver finds: when mass ratio is higher than above-mentioned scope, feed liquid is feeding-up, be unfavorable for that reaction is carried out smoothly, and when mass ratio is lower than above-mentioned scope, cause salt acid consumption to increase, increase subsequent disposal burden and cost, and tail washings amount increases, the rate of recovery reduces, and contriver finds to select aforementioned proportion scope that palladium leaching yield can be made higher through repeatedly studying thus, tail washings amount is less, and the rate of recovery is higher and reagent consumes less.
According to embodiments of the invention, the concentration of hydrochloric acid is also not particularly limited, and according to a particular embodiment of the invention, the concentration of hydrochloric acid can be 2 ~ 5mol/L.Contriver finds: when concentration of hydrochloric acid higher than this scope constantly, be unfavorable on the one hand the exchange adsorption palladium of resin, increase reagent consumption on the other hand; And when concentration of hydrochloric acid is lower than this scope, the dissolution rate of palladium declines, contriver is through repeatedly studying the concentration of hydrochloric acid finding to select this concentration range thus, can when ensureing that palladium dissolution rate is higher, and reagent consumption is less, resin absorption better effects if.
According to embodiments of the invention, the blending ratio of mixed solution and oxygenant is also not particularly limited, and according to a particular embodiment of the invention, mixed solution can be that (100:1) ~ (100:2) mixes according to mass ratio with oxygenant.Contriver finds, when mass ratio is higher than this scope, oxidant content is not enough, palladium can not be dissolved completely in solution, and when mass ratio is lower than this scope, oxidant consumption amount increases, effective rate of utilization reduces, and solute effect there is no considerable change, and contriver finds to select this proportional range through repeatedly studying thus, palladium solubility rate is higher, and reagent consumes less.
According to embodiments of the invention, the mass concentration of oxygenant is also not particularly limited, and according to a particular embodiment of the invention, the mass concentration of oxygenant can be 5 ~ 15%.Contriver finds: when oxidant concentration is higher than this scope, reaction is violent instantaneously, unnecessary oxygenant has little time reaction, reduce the reactivity of oxygenant, add reagent consumption, and when oxidant concentration is lower than this scope, react too slow, oxidant content is not enough, palladium can not be made fully to dissolve, the dissolution rate of palladium is declined.Contriver is through repeatedly studying the oxygenant finding to select this concentration range thus, can ensure in the consoluet situation of palladium, and reagent consumes less, and utilization ratio is higher.
Concrete, the spent catalyst through calcination process mixes with hydrochloric acid by this step, and is heated to 70 ~ 80 DEG C, then slowly adds oxygenant, reacts 0.5 ~ 2 hour, thus makes most of palladium element be dissolved in leach liquor, obtains carrier and contains palladium leach liquor.
According to embodiments of the invention, leaching process can be carried out the spent catalyst gradation through calcination process, thus the rate of recovery of palladium element can be improved significantly further.
Switch 300: according to embodiments of the invention, switch 300 is connected with leaching device 200, and be suitable for adopting ion exchange resin to carrying out exchange process containing palladium leach liquor, thus the resin exchanging rear liquid and adsorbing metal palladium can be obtained, and the major part of liquid after the exchange obtained is returned leaching device 200 carry out leaching process.Contriver finds, after the exchange obtained by exchange process, liquid returns and carries out leaching process, can't produce significant adverse impact to leaching effect, but can significantly improve leach liquor recycle efficiency, thus significantly can reduce the usage quantity of leach liquor, and then reduce the processing cost of spent catalyst.
According to embodiments of the invention, the particular type of ion exchange resin is also not particularly limited, and according to a particular embodiment of the invention, ion exchange resin can for being selected from least one in the resin anion(R.A) of absorption palladium, resin cation (R.C.), resin.Contriver finds, the ion exchange resin of the type can significantly improve the adsorption efficiency of palladium element, thus improves the rate of recovery of palladium element further.
Desorption apparatus 400: according to embodiments of the invention, desorption apparatus 400 is connected with switch 300, and is suitable for adopting stripping liquid to carry out desorb process to the resin of adsorbing metal palladium, thus liquid after desorb can be obtained.Thus, the rate of recovery of palladium element can be improved further.
According to embodiments of the invention, the concentration of stripping liquid is also not particularly limited, and according to a particular embodiment of the invention, the mass concentration of stripping liquid can be 4 ~ 20%.Contriver finds, if concentration is higher than this scope, increase strippant and rinse water consumption on the one hand, increase the reagent dosage of acidity adjustment in subsequent step on the other hand, and concentration is lower than this scope, then desorption effect declines, contriver is through repeatedly studying discovery thus, when stripping liquid mass concentration is in this scope, desorption effect is better, and reagent consumes less.
According to embodiments of the invention, the particular type of stripping liquid is also not particularly limited, and according to a particular embodiment of the invention, stripping liquid can be at least one in basic solution, acidic solution, saline solution.Contriver finds, the stripping liquid of the type can significantly improve the desorption efficiency of the resin of adsorbing metal palladium, thus improves the rate of recovery of palladium element further.
Refining plant 500: according to embodiments of the invention, refining plant 500 is connected with desorption apparatus 400, and is suitable for liquid after desorb to carry out refinement treatment, thus can obtain palladium product.Thus, palladium product purity can be significantly improved.
According to embodiments of the invention, the purity of palladium product is not less than 99.95%, and the rate of recovery is up to more than 99%.
In this step, concrete, after desorb, liquid carries out ammoniated treatment (such as: add ammoniacal liquor) after adjustment acidity, make palladium change into dichloro four ammonia palladium solution, then filter, filtrate is used hcl acidifying again, obtain dichloro diamino palladium precipitation, use water slurry after sedimentation and filtration washing, then add ammonia solvent, obtain pure palladium with hydrazine hydrate reduction.
The system of Used palladium catalyst is contained by carrying out Selectively leaching to Palladium from Wasted Catalyst element according to the process loading type of the embodiment of the present invention, make the rate of recovery of final palladium element up to more than 99%, and ensure that carrier is not destroyed, thus can as aluminium silicon resource material use, realize the maximum using of resource, liquid after the exchange of exchange process is returned simultaneously and carry out leaching process, the service efficiency of leach liquor can be significantly improved, and significantly can reduce the usage quantity of leach liquor, thus reduce the processing cost of spent catalyst, realize production process minimizing, maximum resource utilization.
With reference to figure 4, the process loading type of the embodiment of the present invention comprises further containing the system of Used palladium catalyst:
Washing device 600: according to embodiments of the invention, washing device 600 is connected with leaching device 200 and switch 300, and is suitable for carrier to carry out carrying out washing treatment, and liquid after the washing obtained is returned switch 300.Concrete, the carrier leached after process can wash with water, to reduce the leach liquor that carrier is carried secretly, can reduce palladium loss on the one hand, on the other hand carrier is washed till neutrality not containing residual acid, and in carrier after washing palladium content lower than 6ppm.Thus, the rate of recovery of palladium element can be improved further.
Below with reference to specific embodiment, ordinary method and method of the present invention are contrasted, and present invention is described, it should be noted that, these embodiments are only descriptive, and do not limit the present invention in any way.
Comparative example (ordinary method)
By waste loading type, containing Used palladium catalyst, (carrier is SiO
2-α-Al
2o
3) have gather dust and tail gas absorption condition under in 600 DEG C of roastings 3 hours, then the spent catalyst 1500 grams (containing palladium 0.27wt%) after roasting is got, be divided into 3 parts, 500 grams every part, be numbered 1# respectively, 2#, 3#, under the condition with negative pressure and tail gas absorption, the hydrochloric acid soln 2L of 4.0mol/L is added toward 1#, be heated to 75 DEG C, and slowly drip the sodium chlorate solution 5 ~ 15mL of 10wt%, react 1 hour, major part palladium proceeds to solution, obtain containing palladium leach liquor, repeat aforesaid operations, respectively to 1#, 2#, 3# carries out three times and leaches, suitable quantity of water is supplemented to process ratio in process, total after 1# ~ 3# material is all leached through three times is 18L containing palladium leach liquor, total hydrochloric acid consumption is 6L, leaching is processed the carrier obtained and carries out carrying out washing treatment, obtain carrier and the rear liquid of washing, ion exchange resin is adopted to carry out exchange process to what obtain containing liquid after palladium leach liquor and washing, obtain the resin exchanging rear liquid and adsorbing metal palladium, wherein: after exchanging, in liquid, palladium content is 0.018ppm, in carrier after washing, palladium content is lower than 6ppm, then adopt the stripping liquid of 4 ~ 20wt% to carry out desorb process to the resin of adsorbing metal palladium, obtain liquid after desorb, liquid after desorb is carried out refinement treatment, obtain purity higher than 99.95% palladium sponge 4.016g, the rate of recovery of palladium is 99.16%.
Embodiment 1
By waste loading type, containing Used palladium catalyst, (carrier is SiO
2-α-Al
2o
3) have gather dust and tail gas absorption condition under in 600 DEG C of roastings 3 hours, then the spent catalyst 1500 grams (containing palladium 0.27wt%) after roasting is got, be divided into 3 parts, 500 grams every part, be numbered 1# respectively, 2#, 3#, under the condition with negative pressure and tail gas absorption, the hydrochloric acid soln 2L of 4.0mol/L is added toward 1#, be heated to 75 DEG C, and slowly drip the sodium chlorate solution 5 ~ 15mL of 10wt%, react 1 hour, major part palladium proceeds to solution, obtain containing palladium leach liquor, ion exchange resin is adopted to carry out exchange process to what obtain containing palladium leach liquor, obtain the resin exchanging rear liquid and adsorbing metal palladium, and liquid after exchange is returned 1# and carry out secondary and leach process, repeat aforesaid operations, successively to 1#, 2#, 3# carries out three times respectively and leaches process, suitable quantity of water is supplemented to process ratio in process.After 1# ~ 3# material all leaches through three times, leach liquor total amount is 2L, the total consumption of hydrochloric acid is 0.67L, leaching is processed the carrier obtained and carries out carrying out washing treatment, and liquid after the washing obtained is returned carry out exchange process, wherein, in carrier after washing, palladium content is lower than 6ppm, and exchanging palladium content in tail washings is 0.019ppm; Then adopt the stripping liquid of 4 ~ 20wt% to carry out desorb process to the resin of adsorbing metal palladium, obtain liquid after desorb, liquid after desorb is carried out refinement treatment, obtain purity higher than 99.95% palladium sponge 4.017g, the rate of recovery of palladium is 99.18%.
Embodiment 2
By waste loading type, containing Used palladium catalyst, (carrier is SiO
2-α-Al
2o
3) have gather dust and tail gas absorption condition under in 600 DEG C of roastings 3 hours, then the spent catalyst 18000 grams (containing palladium 0.27wt%) after roasting is got, be divided into 36 parts, 500 grams every part, divide three group #, totally 12 groups, namely 1-1 is numbered, 1-2, 1-3, 2-1, 2-2, 2-3, the like, under the condition with negative pressure and tail gas absorption, the hydrochloric acid soln 2L of 4.0mol/L is added in 1-1, be heated to 75 DEG C, and slowly drip the sodium chlorate solution 5 ~ 15mL of 10wt%, react 1 hour, major part palladium proceeds to solution, obtain containing palladium leach liquor, repeat aforesaid operations, again two-stage leaching is carried out to 1-1, suitable quantity of water is supplemented to process ratio in process, the rest may be inferred, total after 12 groups of materials are all leached through three times is 6L containing palladium leach liquor, total hydrochloric acid consumption is 3.6L, leaching is processed the carrier obtained and carries out carrying out washing treatment, liquid after the washing obtained, ion exchange resin is adopted to carry out exchange process to what obtain containing liquid after palladium leach liquor and washing, obtain the resin exchanging rear liquid and adsorbing metal palladium, and the major part of liquid after exchanging is returned carry out leachings and process, wherein, in carrier after washing, palladium content is lower than 6ppm, exchanging palladium content in tail washings is 0.019ppm, then adopt the stripping liquid of 4 ~ 20wt% to carry out desorb process to the resin of adsorbing metal palladium, obtain liquid after desorb, liquid after desorb is carried out refinement treatment, obtain purity higher than 99.95% palladium sponge 48.22g, the rate of recovery of palladium is 99.22%.
Conclusion: embodiment 1 and 2 compares with comparative example, the material of process same amount, the middle liquid measure of embodiment 1 and 2 obviously reduces, and reagent dosage also greatly reduces, and does not affect the rate of recovery of palladium after reagent minimizing.
In the description of this specification sheets, specific features, structure, material or feature that the description of reference term " embodiment ", " some embodiments ", " example ", " concrete example " or " some examples " etc. means to describe in conjunction with this embodiment or example are contained at least one embodiment of the present invention or example.In this manual, to the schematic representation of above-mentioned term not must for be identical embodiment or example.And the specific features of description, structure, material or feature can combine in one or more embodiment in office or example in an appropriate manner.In addition, when not conflicting, the feature of the different embodiment described in this specification sheets or example and different embodiment or example can carry out combining and combining by those skilled in the art.
Although illustrate and describe embodiments of the invention above, be understandable that, above-described embodiment is exemplary, can not be interpreted as limitation of the present invention, and those of ordinary skill in the art can change above-described embodiment within the scope of the invention, revises, replace and modification.
Claims (12)
1. process the method for loading type containing Used palladium catalyst, the carrier of described loading type spent catalyst is α-Al
2o
3or SiO
2-α-Al
2o
3, it is characterized in that, described method comprises:
(1) calcination process is carried out described containing Used palladium catalyst;
(2) spent catalyst through calcination process that step (1) obtains is carried out leaching process, to obtain carrier and to contain palladium leach liquor;
(3) adopt ion exchange resin to described containing palladium leach liquor carry out exchanges process, to obtain the resin exchanging rear liquid and adsorbing metal palladium, and the major part of liquid after described exchange is returned step (2) carry out described leaching process;
(4) resin of stripping liquid to described adsorbing metal palladium is adopted to carry out desorb process, so that liquid after obtaining desorb; And
(5) liquid after described desorb is carried out refinement treatment, to obtain palladium product.
2. method according to claim 1, is characterized in that, comprises further:
(6) the described carrier that step (2) obtains is carried out carrying out washing treatment, and liquid after the washing obtained is returned step (3) carry out described exchange process.
3. method according to claim 1, is characterized in that, described calcination process carries out 2 ~ 4 hours under 500 ~ 700 degrees Celsius.
4. method according to claim 1, is characterized in that, described leaching process adopts the following step to carry out:
(2-1) by the described spent catalyst through calcination process and mixed in hydrochloric acid;
(2-2) mixed solution that step (2-1) obtains is contacted with oxygenant, to obtain described carrier and described containing palladium leach liquor.
5. method according to claim 1, is characterized in that,
In described step (2-1), the described spent catalyst through calcination process is that (1:3) ~ (1:6) mixes with described hydrochloric acid according to mass ratio, and the concentration of described hydrochloric acid is 2 ~ 5mol/L,
In described step (2-2), described mixed solution and described oxygenant are that (100:1) ~ (100:2) contacts according to mass ratio, and described oxygenant is be selected from least one in chlorine, oxymuriate, hypochlorite, hydrogen peroxide and nitric acid.
6. method according to claim 1, is characterized in that, in step (3), described ion exchange resin is be selected from least one in the absorption resin anion(R.A) of palladium, resin cation (R.C.) and resin.
7. method according to claim 1, is characterized in that, in step (4), the mass concentration of described stripping liquid is 4 ~ 20%.
8. method according to claim 7, is characterized in that, described stripping liquid is at least one in basic solution, acidic solution, saline solution.
9. process the system of loading type containing Used palladium catalyst, it is characterized in that, comprising:
Calciner, described calciner is suitable for carrying out calcination process by described containing Used palladium catalyst;
Leaching device, described leaching device is connected with described calciner, and is suitable for the spent catalyst through calcination process obtained being carried out leaching process, to obtain carrier and to contain palladium leach liquor;
Switch, described switch is connected with described leaching device, and be suitable for adopting ion exchange resin to carry out exchange process to described containing palladium leach liquor, to obtain the resin exchanging rear liquid and adsorbing metal palladium, and the major part of liquid after described exchange is returned described leaching device;
Desorption apparatus, described desorption apparatus is connected with described switch, and is suitable for adopting the resin of stripping liquid to described adsorbing metal palladium to carry out desorb process, so that liquid after obtaining desorb; And
Refining plant, described refining plant is connected with described desorption apparatus, and is suitable for liquid after described desorb being carried out refinement treatment, to obtain palladium product.
10. system according to claim 9, is characterized in that, comprises further:
Washing device, described washing device is connected with described leaching device and switch respectively, and is suitable for described carrier to carry out carrying out washing treatment, and liquid after the washing obtained is returned described switch.
11. systems according to claim 9, is characterized in that, described leaching process adopts the following step to carry out:
By the described spent catalyst through calcination process and mixed in hydrochloric acid;
The mixed solution obtained is contacted with oxygenant, to obtain described carrier and described containing palladium leach liquor.
12. systems according to claim 9, is characterized in that,
The described spent catalyst through calcination process and described hydrochloric acid are (1:3) ~ (1:6) according to mass ratio, and the concentration carrying out contacting described hydrochloric acid is 2 ~ 5mol/L,
Described mixed solution and described oxygenant are that (100:1) ~ (100:2) mixes according to mass ratio, and described oxygenant is be selected from least one in chlorine, oxymuriate, hypochlorite, hydrogen peroxide and nitric acid.
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| CN108950232A (en) * | 2018-06-26 | 2018-12-07 | 北京科技大学 | A method of the green reclaim palladium of waste material containing palladium |
| CN108889342A (en) * | 2018-07-06 | 2018-11-27 | 福州大学 | A kind of regeneration and recycling and reusing method for nitrile rubber heterogeneous hydrogenation catalyst |
| CN108889342B (en) * | 2018-07-06 | 2021-04-27 | 福州大学 | Regeneration and recycling method for heterogeneous hydrogenation catalyst of nitrile rubber |
| CN111500872A (en) * | 2019-01-30 | 2020-08-07 | 鹏鼎控股(深圳)股份有限公司 | Recovery treatment method of low-concentration palladium-containing waste liquid |
| CN110358922A (en) * | 2019-08-20 | 2019-10-22 | 泉州丰鹏环保科技有限公司 | A kind of recovery method containing Used palladium catalyst |
| CN111455182A (en) * | 2020-04-24 | 2020-07-28 | 金川集团股份有限公司 | Method for separating and extracting silver, palladium and ruthenium from waste catalyst |
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Application publication date: 20151021 |