TWI542701B - Method for soaking metal in waste catalyst by acid liquid - Google Patents
Method for soaking metal in waste catalyst by acid liquid Download PDFInfo
- Publication number
- TWI542701B TWI542701B TW101127619A TW101127619A TWI542701B TW I542701 B TWI542701 B TW I542701B TW 101127619 A TW101127619 A TW 101127619A TW 101127619 A TW101127619 A TW 101127619A TW I542701 B TWI542701 B TW I542701B
- Authority
- TW
- Taiwan
- Prior art keywords
- acid
- solution
- leaching
- residue
- waste catalyst
- Prior art date
Links
- 239000002253 acid Substances 0.000 title claims description 97
- 239000003054 catalyst Substances 0.000 title claims description 87
- 229910052751 metal Inorganic materials 0.000 title claims description 78
- 239000002184 metal Substances 0.000 title claims description 78
- 239000007788 liquid Substances 0.000 title claims description 76
- 239000002699 waste material Substances 0.000 title claims description 73
- 238000000034 method Methods 0.000 title claims description 42
- 238000002791 soaking Methods 0.000 title description 2
- 239000000243 solution Substances 0.000 claims description 81
- 238000002386 leaching Methods 0.000 claims description 78
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 62
- 238000000605 extraction Methods 0.000 claims description 58
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 51
- 239000000295 fuel oil Substances 0.000 claims description 47
- 229910052750 molybdenum Inorganic materials 0.000 claims description 47
- 239000011733 molybdenum Substances 0.000 claims description 47
- 239000000203 mixture Substances 0.000 claims description 37
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 36
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 33
- 229910052782 aluminium Inorganic materials 0.000 claims description 31
- 229910052759 nickel Inorganic materials 0.000 claims description 31
- 229910052720 vanadium Inorganic materials 0.000 claims description 30
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 29
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 24
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 20
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 20
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 20
- 229910017604 nitric acid Inorganic materials 0.000 claims description 20
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 20
- 230000001590 oxidative effect Effects 0.000 claims description 15
- 239000003513 alkali Substances 0.000 claims description 13
- 238000007670 refining Methods 0.000 claims description 13
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 12
- 239000011593 sulfur Substances 0.000 claims description 12
- 229910052717 sulfur Inorganic materials 0.000 claims description 12
- 238000000151 deposition Methods 0.000 claims description 11
- 238000007254 oxidation reaction Methods 0.000 claims description 11
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 10
- 239000012670 alkaline solution Substances 0.000 claims description 10
- 238000005238 degreasing Methods 0.000 claims description 10
- 239000000284 extract Substances 0.000 claims description 10
- XTAZYLNFDRKIHJ-UHFFFAOYSA-N n,n-dioctyloctan-1-amine Chemical compound CCCCCCCCN(CCCCCCCC)CCCCCCCC XTAZYLNFDRKIHJ-UHFFFAOYSA-N 0.000 claims description 10
- 230000003647 oxidation Effects 0.000 claims description 10
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 10
- 239000011780 sodium chloride Substances 0.000 claims description 10
- 239000003929 acidic solution Substances 0.000 claims description 9
- 239000002893 slag Substances 0.000 claims description 7
- XTEGARKTQYYJKE-UHFFFAOYSA-N chloric acid Chemical compound OCl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-N 0.000 claims description 6
- 229940005991 chloric acid Drugs 0.000 claims description 6
- 239000003921 oil Substances 0.000 claims description 6
- 238000000926 separation method Methods 0.000 claims description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 5
- IOVCWXUNBOPUCH-UHFFFAOYSA-N Nitrous acid Chemical compound ON=O IOVCWXUNBOPUCH-UHFFFAOYSA-N 0.000 claims description 5
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 5
- QBWCMBCROVPCKQ-UHFFFAOYSA-N chlorous acid Chemical compound OCl=O QBWCMBCROVPCKQ-UHFFFAOYSA-N 0.000 claims description 5
- 229940077239 chlorous acid Drugs 0.000 claims description 5
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 claims description 4
- 239000002244 precipitate Substances 0.000 claims description 4
- 239000010812 mixed waste Substances 0.000 claims description 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims 1
- 239000010931 gold Substances 0.000 claims 1
- 229910052737 gold Inorganic materials 0.000 claims 1
- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical compound [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 claims 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 28
- 229940074355 nitric acid Drugs 0.000 description 18
- 238000011084 recovery Methods 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000005265 energy consumption Methods 0.000 description 4
- 230000005484 gravity Effects 0.000 description 4
- 238000003912 environmental pollution Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 238000003915 air pollution Methods 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000012958 reprocessing Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 238000005987 sulfurization reaction Methods 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
-
- 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
Landscapes
- Manufacture And Refinement Of Metals (AREA)
- Processing Of Solid Wastes (AREA)
Description
本發明係關於一種自廢觸媒中回收金屬之方法,特別是一種以酸浸出經加氫脫硫製程所產出之廢觸媒中所含金屬,並將其中重油重新回收再利用之方法。 The invention relates to a method for recovering metal from a waste catalyst, in particular to a method for acid leaching the metal contained in the waste catalyst produced by the hydrodesulfurization process and recycling the heavy oil therein.
於石油煉製產業中,用以對石油作加氫脫硫工序之觸媒多是以三氧化二鋁為載體,再將具有活性之釩、鉬或鎳等金屬或其氧化物固著該載體表面。但當觸媒於催化過程吸附大量的鐵、磷等元素後,即會導致觸媒失效而形成所謂RDS或HDS廢觸媒,此種RDS或HDS廢觸媒若未經過有效處理則可能造成嚴重的環境毒害。 In the petroleum refining industry, the catalyst for the hydrodesulfurization process of petroleum is mostly based on alumina, and then the active metal such as vanadium, molybdenum or nickel or its oxide is fixed to the carrier. surface. However, when the catalyst adsorbs a large amount of iron, phosphorus and other elements in the catalytic process, it will cause the catalyst to fail and form a so-called RDS or HDS waste catalyst. Such RDS or HDS waste catalyst may cause serious damage if it is not effectively treated. Environmental poisoning.
事實上,用以處理重油所產生的RDS廢觸媒中富含有釩、鉬、鎳、鋁及重油,用以處理柴油所產生的HDS廢觸媒中富含有鉬、鎳、鋁及重油。因此,該些廢觸媒對於多數業者而言,仍然存在有再處理之價值。 In fact, the RDS waste catalyst used to treat heavy oil is rich in vanadium, molybdenum, nickel, aluminum and heavy oil. The HDS waste catalyst produced by treating diesel oil is rich in molybdenum, nickel, aluminum and heavy oil. . Therefore, these waste catalysts still have the value of reprocessing for most operators.
現階段多是以鈉化焙燒法來作廢觸媒之有效處理,除了能藉此將廢觸媒所含重油予以燃燒去除外,還能將其中所含之釩、鉬、鎳等金屬加以回收。 At present, most of the sodium-based roasting method is used as an effective treatment for the waste catalyst. In addition to the heavy oil contained in the waste catalyst, the vanadium, molybdenum, nickel and other metals contained therein can be recovered.
然而,焙燒過程的耗時及高溫,不僅耗費能源而造成處理成本之負擔,更無法對各種金屬作全面性回收,其整體回收效率確實有待進一步改善。次之,若是用以處理含大量重油之RDS廢觸媒,則勢必容易因高溫燃燒重油,而導致溶於重油內之硫或其化合物隨之飄散於空氣中。如此 一來,非但無法在耗時、耗能的焙燒過程,將有價重油重新回收再利用,更隨之產生嚴重的空污問題。 However, the time-consuming and high-temperature of the roasting process not only consumes energy and causes a burden of processing costs, but also makes it impossible to comprehensively recover various metals, and the overall recovery efficiency does need to be further improved. Secondly, if it is used to treat RDS waste catalysts containing a large amount of heavy oil, it is easy to burn heavy oil at high temperature, and the sulfur or its compound dissolved in the heavy oil will be dispersed in the air. in this way As a result, not only can the heavy oil in the time-consuming and energy-consuming roasting process be recycled and reused, but it also has serious air pollution problems.
有鑑於此,確實有必要發展一種新穎之廢觸媒有效處理方法,以用於經加氫脫硫製程所產出之RDS或HDS廢觸媒,進而解決如上所述之各種問題。 In view of this, it is indeed necessary to develop a novel effective treatment method for waste catalyst for use in the RDS or HDS waste catalyst produced by the hydrodesulfurization process, thereby solving various problems as described above.
本發明主要目的乃改善上述缺點,以提供一種以酸浸出廢觸媒中所含金屬之方法,其係能夠全面回收其中所含金屬,且同時將富含之重油直接回收再利用,以減少耗能並降低環境污染之疑慮。 The main object of the present invention is to improve the above disadvantages to provide a method for leaching the metal contained in the waste catalyst by acid, which is capable of comprehensively recovering the metal contained therein, and simultaneously recovering and reusing the rich heavy oil directly to reduce the consumption. Can reduce and reduce environmental pollution concerns.
本發明之次一目的係提供一種以酸浸出廢觸媒中所含金屬之方法,係能夠直接傾出氧化態之金屬,以降低後續處理之困難度且提升金屬之傾出率。 A second object of the present invention is to provide a method for leaching a metal contained in a spent catalyst by acid, which is capable of directly decanting the metal in an oxidized state to reduce the difficulty of subsequent treatment and to enhance the metal pouring rate.
為達到前述發明目的,本發明以酸浸出廢觸媒中所含金屬之方法,係用以處理經加氫脫硫製程所產生的一廢觸媒,其包含:一浸出步驟,將該廢觸媒混料浸泡於一高氧化性之酸液中,使得該混料中之硫與該酸液反應,以產出包含有重油、傾出液及殘渣體的一混合液,且該傾出液及殘渣體富含有氧化態金屬,其中,該廢觸媒混料係為RDS廢觸媒或該RDS廢觸媒混合HDS廢觸媒,且該RDS廢觸媒或該混合後之廢觸媒中富含有釩、鉬、鎳、鋁及重油,該高氧化性之酸液為硝酸、次氯酸、氯酸、亞氯酸、高氯酸、亞硝酸或濃硫酸,於該浸出步驟中另添加一輔助酸,且該輔助酸為鹽酸或硫酸;一除油步驟,自該混合液中移 除該殘渣體後,靜待該傾出液與重油產生分層,以透過油液分離將該重油予以濾除,而得該傾出液;及一精製步驟,將該殘渣體內之金屬浸出,取得一殘渣浸出液,以分別由該傾出液及殘渣浸出液中萃取並沉出二者所含金屬,該精製步驟另包含有一第一提取步驟及一第二提取步驟,該第一提取步驟係自該傾出液中萃取並沉出大量的釩、鎳及少量鋁、鉬,且該第二提取步驟係將該殘渣體浸漬於一鹼液中,以生成該殘渣浸出液,再由該殘渣浸出液中萃取並沉出鉬及生成大量鋁渣,該第一提取步驟及該第二提取步驟係先以一萃取劑對該傾出液進行共萃取,以獲得一共萃液,再利用一鹼性溶液或一酸性溶液對該共萃液進行反萃,而取得一反萃液後,再以該反萃液沉出該傾出液中所含金屬。 In order to achieve the foregoing object, the present invention uses a method for acid leaching a metal contained in a spent catalyst to treat a waste catalyst produced by a hydrodesulfurization process, comprising: a leaching step, the waste contact The medium mixture is immersed in a highly oxidizing acid liquid, so that the sulfur in the mixture reacts with the acid liquid to produce a mixed liquid containing the heavy oil, the decanting liquid and the residue body, and the decanting liquid And the residue body is rich in oxidized metal, wherein the waste catalyst mixture is an RDS waste catalyst or the RDS waste catalyst mixed HDS waste catalyst, and the RDS waste catalyst or the mixed waste catalyst Rich in vanadium, molybdenum, nickel, aluminum and heavy oil, the highly oxidizing acid is nitric acid, hypochlorous acid, chloric acid, chlorous acid, perchloric acid, nitrous acid or concentrated sulfuric acid, in the leaching step Further adding an auxiliary acid, and the auxiliary acid is hydrochloric acid or sulfuric acid; and a degreasing step, moving from the mixed liquid After the residue is removed, the decanted liquid and the heavy oil are layered to filter the heavy oil by oil separation to obtain the decanted liquid; and a refining step is performed to leaching the metal in the residue. Obtaining a residue leaching solution for extracting and depositing the metal contained in the leaching solution and the residue leaching solution respectively, the refining step further comprising a first extraction step and a second extraction step, wherein the first extraction step is Extracting and depositing a large amount of vanadium, nickel and a small amount of aluminum and molybdenum in the decanting liquid, and the second extraction step immersing the residue body in an alkali solution to generate the residue leachate, and then from the residue leach solution Extracting and depositing molybdenum and generating a large amount of aluminum slag, the first extraction step and the second extraction step are first co-extracting the decanted liquid with an extractant to obtain a total extraction solution, and then using an alkaline solution or The acid solution is back-extracted to obtain a stripping solution, and then the stripping solution is used to precipitate the metal contained in the extract.
其中,該輔助酸添加於該酸液中的重量百分比濃度係為1~50%。 The concentration of the auxiliary acid added to the acid solution is 1 to 50% by weight.
其中,該酸液與混料之相對重量比值(酸液/混料)為1至4。再且,該高氧化性酸液之濃度為5~40%。 Wherein, the relative weight ratio (acid solution/mixture) of the acid liquid to the mixed material is 1 to 4. Further, the concentration of the highly oxidizing acid liquid is 5 to 40%.
其中,該第二提取步驟係直接以一鹼液浸泡該殘渣體,使得該殘渣體內所含之鉬傾出於該殘渣浸出液中,且依該第一提取步驟萃取該殘渣浸出液以沉岀其所含金屬。 Wherein, the second extraction step directly soaks the residue body in an alkali solution, so that the molybdenum contained in the residue body is poured into the residue leaching solution, and the residue leaching solution is extracted according to the first extraction step to sink the residue. Contains metal.
其中,該鹼液可以為碳酸鈉、氫氧化鈉或氯化鈉等溶液。該萃取劑可以選自由N-235、Alamine336、Aliquit306、P204、P507、N236及TOA所組成之群組。另外,該萃取用之鹼性溶液係為氨水、氫氧化鈉、氯化鈉或碳酸鈉,且該萃取用之酸性溶液係為硫酸、鹽酸、磷酸或過氯酸。 The lye may be a solution of sodium carbonate, sodium hydroxide or sodium chloride. The extractant may be selected from the group consisting of N-235, Alamine 336, Aliquit 306, P204, P507, N236, and TOA. Further, the alkaline solution for extraction is ammonia water, sodium hydroxide, sodium chloride or sodium carbonate, and the acidic solution for extraction is sulfuric acid, hydrochloric acid, phosphoric acid or perchloric acid.
又,本發明以酸浸出廢觸媒中所含金屬之方法,係用以處理經加氫脫硫製程所產生的一廢觸媒,其包含:一浸出步驟,將該廢觸媒混料浸泡於一高氧化性之酸液中,使得該混料中之硫與該酸液反應,以產出包含有重油、傾出液及殘渣體的一混合液,且該傾出液及殘渣體內富含有氧化態金屬,其中,該廢觸媒混料係為HDS廢觸媒,且該HDS廢觸媒中富含有鉬、鎳、鋁及重油,該高氧化性之酸液為硝酸、次氯酸、氯酸、亞氯酸、高氯酸、亞硝酸或濃硫酸,於該浸出步驟中另添加一輔助酸,且該輔助酸係為鹽酸或硫酸;一除油步驟,自該混合液中移除該殘渣體後,靜待該傾出液與重油產生分層,以透過油液分離將該重油予以濾除,而得該傾出液;及一精製步驟,將該殘渣體內之金屬浸出,取得一殘渣浸出液,以分別由該傾出液及殘渣浸出液中萃取並沉出二者所含金屬,該精製步驟另包含有一第一提取步驟及一第二提取步驟,該第一提取步驟係自該傾出液中萃取並沉出大量的鎳及少量鋁、鉬,且該第二提取步驟係將該殘渣體浸漬於一鹼液中,以生成該殘渣浸出液,再由該殘渣浸出液中萃取並沉出鉬及生成大量鋁渣,該第一提取步驟及該第二提取步驟係先以一萃取劑對該傾出液進行共萃取,以獲得一共萃液,再利用一鹼性溶液或一酸性溶液對該共萃液進行反萃,而取得一反萃液後,再以該反萃液沉出該傾出液中所含金屬。 Moreover, the method for leaching the metal contained in the waste catalyst by acid is used for treating a waste catalyst generated by the hydrodesulfurization process, comprising: a leaching step, soaking the waste catalyst mixture In a highly oxidizing acid liquid, the sulfur in the mixture is reacted with the acid liquid to produce a mixed liquid containing heavy oil, decanting liquid and residue body, and the decanting liquid and the residue are rich in the body Containing an oxidized metal, wherein the waste catalyst mixture is a HDS waste catalyst, and the HDS waste catalyst is rich in molybdenum, nickel, aluminum and heavy oil, and the highly oxidizing acid is nitric acid, Chloric acid, chloric acid, chlorous acid, perchloric acid, nitrous acid or concentrated sulfuric acid, another auxiliary acid is added in the leaching step, and the auxiliary acid is hydrochloric acid or sulfuric acid; a degreasing step, from the mixed liquid After removing the residue body, the layered liquid and the heavy oil are layered to filter the heavy oil by oil separation to obtain the decanting liquid; and a refining step, the metal in the residue body Leaching to obtain a residue leaching solution to extract and precipitate both from the decanting liquid and the residue leaching solution Metal-containing, the refining step further comprises a first extraction step and a second extraction step, the first extraction step extracting and depositing a large amount of nickel and a small amount of aluminum and molybdenum from the decanting liquid, and the second extraction The step of immersing the residue in an alkali solution to form the residue leaching solution, extracting and depositing molybdenum from the residue leaching solution and generating a large amount of aluminum slag, the first extraction step and the second extraction step are first An extractant co-extracts the decanted liquid to obtain a co-extracted solution, and then extracts the co-extracted solution with an alkaline solution or an acidic solution to obtain a stripping solution, and then the stripping solution The liquid precipitates the metal contained in the decanted liquid.
其中,該輔助酸添加於該酸液中的重量百分比濃度係為1~50%。 The concentration of the auxiliary acid added to the acid solution is 1 to 50% by weight.
其中,該酸液與混料之相對重量比值(酸液/混料)為1 至4。再且,該高氧化性酸液之濃度為5~40%。 Wherein the relative weight ratio of the acid to the mixture (acid/mix) is 1 To 4. Further, the concentration of the highly oxidizing acid liquid is 5 to 40%.
其中,該第二提取步驟係直接以一鹼液浸泡該殘渣體,使得該殘渣體內所含之鉬浸出於該殘渣浸出液中,且依該第一提取步驟萃取該殘渣浸出液以沉岀其所含金屬。 Wherein, the second extraction step directly soaks the residue body in an alkali solution, so that the molybdenum contained in the residue body is immersed in the residue leaching liquid, and the residue leaching liquid is extracted according to the first extraction step to sink the contained metal.
其中,該鹼液可以為碳酸鈉、氫氧化鈉或氯化鈉等溶液。該萃取劑可以選自由N-235、Alamine336、Aliquit306、P204、P507、N236及TOA所組成之群組。另外,該萃取用之鹼性溶液係為氨水、氫氧化鈉、氯化鈉或碳酸鈉,且該萃取用之酸性溶液係為硫酸、鹽酸、磷酸或過氯酸。 The lye may be a solution of sodium carbonate, sodium hydroxide or sodium chloride. The extractant may be selected from the group consisting of N-235, Alamine 336, Aliquit 306, P204, P507, N236, and TOA. Further, the alkaline solution for extraction is ammonia water, sodium hydroxide, sodium chloride or sodium carbonate, and the acidic solution for extraction is sulfuric acid, hydrochloric acid, phosphoric acid or perchloric acid.
為讓本發明之上述及其他目的、特徵及優點能更明顯易懂,下文特舉本發明之較佳實施例,並配合所附圖式,作詳細說明如下:本發明所指之廢觸媒係為經加氫脫硫製程後所產出之RDS或HDS廢觸媒〔於本發明中統稱為〝廢觸媒混料〞〕,RDS廢觸媒中富含有釩、鉬、鎳、鋁及重油,HDS廢觸媒中富含有鉬、鎳、鋁及重油,且該廢觸媒混料亦可以為RDS廢觸媒混合HDS廢觸媒。 The above and other objects, features and advantages of the present invention will become more <RTIgt; It is a RDS or HDS waste catalyst produced after the hydrodesulfurization process (collectively referred to as a waste catalyst mixture in the present invention), and the RDS waste catalyst is rich in vanadium, molybdenum, nickel, aluminum. And heavy oil, HDS waste catalyst is rich in molybdenum, nickel, aluminum and heavy oil, and the waste catalyst mixture can also be RDS waste catalyst mixed HDS waste catalyst.
請參照第1圖所示,其係為本發明一較佳實施例,該以酸浸出廢觸媒中所含金屬之方法包含一酸浸步驟S1、一除油步驟S2及一精製步驟S3。其中,依據酸浸及除油後的產物屬性係可於該精製步驟S3中選擇作適當之處理,容後再予以詳述之。 Referring to FIG. 1, which is a preferred embodiment of the present invention, the method for acid leaching the metal contained in the spent catalyst comprises an acid leaching step S1, a degreasing step S2, and a refining step S3. Wherein, the product properties according to the acid leaching and degreasing can be selected in the refining step S3 for appropriate treatment, which will be described in detail later.
該浸出步驟S1係將該廢觸媒混料浸泡於一高氧化性 之酸液中,使得該廢觸媒混料中之硫與該酸液反應,以產出包含有重油、傾出液及殘渣體的一混合液,且該傾出液及殘渣體內富含有氧化態金屬。其中,該酸液係可以選擇如硝酸、次氯酸、氯酸、亞氯酸、高氯酸、亞硝酸、濃硫酸、…等高氧化性之酸性液。 The leaching step S1 is to soak the waste catalyst mixture in a high oxidation property. In the acid liquid, the sulfur in the waste catalyst mixture is reacted with the acid liquid to produce a mixed liquid containing heavy oil, decanting liquid and residual body, and the decanting liquid and the residue are rich in the body Oxidized metal. Among them, the acid liquid system may select a highly oxidizing acidic liquid such as nitric acid, hypochlorous acid, chloric acid, chlorous acid, perchloric acid, nitrous acid, concentrated sulfuric acid, or the like.
此外,本發明於該浸出步驟S1中另添加一輔助酸,藉由該輔助酸降低該酸液的酸鹼值,以提升該混料浸泡於該酸液中的金屬傾出率。其中,該輔助酸可以選擇如鹽酸、硫酸等強酸性溶液,且該輔助酸添加於該酸液中的重量百分比濃度較佳為1~50%。 In addition, the present invention further adds an auxiliary acid in the leaching step S1, and the acid value of the acid solution is lowered by the auxiliary acid to increase the metal pouring rate of the mixture immersed in the acid solution. The auxiliary acid may be selected from a strongly acidic solution such as hydrochloric acid or sulfuric acid, and the concentration of the auxiliary acid added to the acid solution is preferably from 1 to 50% by weight.
詳言之,具高氧化性之酸液會與該廢觸媒混料中之硫產生硫化反應,且浸泡於該酸液中的廢觸媒混料更會伴隨硫化反應,而經酸溶出大量釩、鎳及少量鋁、鉬金屬,並且透過該酸液的高氧化特性,使釩、鉬、鎳、鋁及未反應完全之硫元素,經氧化反應而轉變為易萃取之氧化態。因此,經該酸液處理所生成之混合液,除了殘存有重油之外,更同時產生富含有氧化態金屬之傾出液及殘渣體。且,該傾出液中具有大量釩、鎳及少量鋁、鉬,該殘渣體中則具有大量鋁渣及鉬。 In particular, the highly oxidizing acid solution will sulphurize with the sulfur in the waste catalyst mixture, and the waste catalyst mixture immersed in the acid solution will be accompanied by a vulcanization reaction, and a large amount of acid is dissolved. Vanadium, nickel and a small amount of aluminum, molybdenum metal, and through the high oxidation characteristics of the acid, vanadium, molybdenum, nickel, aluminum and unreacted sulfur element are converted into an easily extractable oxidation state by oxidation reaction. Therefore, the mixed liquid produced by the acid treatment produces a decanted liquid and a residue body rich in the oxidized metal in addition to the heavy oil remaining. Moreover, the pour liquid has a large amount of vanadium, nickel and a small amount of aluminum and molybdenum, and the residue body has a large amount of aluminum slag and molybdenum.
特別地,於該浸出步驟S1中,亦會因硫化反應而生成含硫化合物及汽化物。其中,該汽化物係可以重新反應為該高氧化性之酸液,以再利用於該浸出步驟S1中。詳言之,該汽化物是為經該酸液氧化後所生成之氧化態酸根,故可與水作用重新反應為該酸液,以重新再利用於該浸出步驟S1中;且,該含硫化合物亦可以降低該酸液的pH值, 以提升該廢觸媒混料於酸液中的金屬傾出效果。 In particular, in the leaching step S1, a sulfur-containing compound and a vapor compound are also formed by the sulfurization reaction. Wherein, the vaporized product can be re-reacted into the highly oxidizing acid to be reused in the leaching step S1. In detail, the vaporized product is an oxidized acid radical formed by oxidation of the acid solution, so that it can be re-reacted with water to form the acid liquid for reuse in the leaching step S1; The compound can also lower the pH of the acid solution. In order to enhance the metal pouring effect of the waste catalyst mixture in the acid solution.
請續參閱第1圖所示,經該浸出步驟S1所產生之混合液係包含重油、傾出液及殘渣體,為了避免重油影響後續的金屬提取效果且能將重油直接回收再利用,故選擇於該浸出步驟S1後先操作該除油步驟S2。 Please refer to FIG. 1 again, the mixed liquid produced by the leaching step S1 includes heavy oil, decanted liquid and residue body. In order to avoid the heavy metal affecting the subsequent metal extraction effect and can directly recycle and reuse the heavy oil, it is selected. The degreasing step S2 is operated after the leaching step S1.
該除油步驟S2係自該混合液中移除該殘渣體後,靜待該傾出液與重油產生分層,以透過油液分離將該重油予以濾除,而得該傾出液。詳言之,當以濾網自該混合液中分離該殘渣體後,由於該傾出液與重油各具有不同比重,故利用二者比重之不同,便能順利透過重力流方式輕易將該重油予以分離。如此一來,重油即能回收再利用,且省去傳統高溫燃燒所耗費的時間與能源;另外,先行分離之殘渣體及不含重油之傾出液則可再於後續之精製步驟S3中,依據二者的不同屬性選擇適當方式,以提出其中所含之金屬,方能全面性地將金屬重新回收再利用。 The degreasing step S2 removes the residue from the mixed solution, and waits for the decanted liquid to form a layer with the heavy oil to filter out the heavy oil by oil separation to obtain the decanted liquid. In detail, when the residue body is separated from the mixed liquid by a sieve, since the decanted liquid and the heavy oil each have different specific gravities, the heavy oil can be easily passed through the gravity flow method by utilizing the difference in the specific gravity of the two. Separate. In this way, the heavy oil can be recycled and reused, and the time and energy consumed by the conventional high-temperature combustion are eliminated; in addition, the residue which is separated first and the decanted liquid which does not contain heavy oil can be further purified in the subsequent step S3. According to the different attributes of the two, the appropriate way is selected to propose the metal contained in it, so that the metal can be recycled and reused comprehensively.
承上,該精製步驟S3係將該殘渣體內之金屬浸出,取得一殘渣浸出液,以分別由該傾出液及殘渣浸出液中萃取並沉出金屬。詳言之,由於經該浸出步驟S1後,該廢觸媒混料所含的大量釩、鎳及少量鋁、鉬已傾出於該傾出液中,故該傾出液可以選擇直接將該些金屬萃取沉出;但殘留於該殘渣體內的大量鋁及鉬,經鹼液浸出鉬,再經萃取後,以沉出鉬。 The purification step S3 is performed by leaching the metal in the residue to obtain a residue leaching solution for extracting and depositing the metal from the decanting liquid and the residue leaching solution, respectively. In detail, since a large amount of vanadium, nickel and a small amount of aluminum and molybdenum contained in the waste catalyst mixture have been poured into the decanting liquid after the leaching step S1, the decanting liquid may be selected directly. Some of the metal is extracted and precipitated; however, a large amount of aluminum and molybdenum remaining in the residue are leached out of the molybdenum by the alkali solution, and then extracted to precipitate the molybdenum.
於本實施例中,該精製步驟S3還可以如第2圖所示包含有一第一提取步驟S31及一第二提取步驟S32。 In this embodiment, the refining step S3 may further include a first extracting step S31 and a second extracting step S32 as shown in FIG. 2 .
該第一提取步驟S31係自該傾出液中萃取並沉出大量 的釩、鉬、鎳及少量鋁、鉬。詳言之,該第一提取步驟S31係先以一萃取劑對該傾出液中之釩、鉬金屬進行共萃取,以獲得一共萃液,再利用一鹼性溶液或一酸性溶液對該共萃液進行反萃,而取得一反萃液後,再以該反萃液分別沉釩及沉鉬,而獲得回收之釩、鉬金屬;接著,將萃出釩、鉬金屬後的一餘液,以碳酸鈣去除其中硫份後,即可產出硫酸鈣,並經pH值調整至7~8,以水解獲得鎳鋁精礦。其中,該萃取劑係可以選自由N-235、Alamine336、Aliquit306、P204、P507、N236及TOA所組成之群組;萃取用之鹼性溶液可以為氨水、氫氧化鈉、氯化鈉或碳酸鈉等;萃取用之酸性溶液可以為硫酸、鹽酸、磷酸或過氯酸。 The first extraction step S31 extracts and precipitates a large amount from the decanted liquid Vanadium, molybdenum, nickel and a small amount of aluminum, molybdenum. In detail, the first extraction step S31 is first co-extracting the vanadium and molybdenum metal in the decanting liquid with an extracting agent to obtain a total extraction liquid, and then using an alkaline solution or an acidic solution. The extract is subjected to stripping, and after obtaining a stripping solution, vanadium and molybdenum are separately precipitated by the stripping solution to obtain recovered vanadium and molybdenum metal; then, a residual liquid of vanadium and molybdenum metal is extracted. After the calcium is removed by calcium carbonate, calcium sulfate can be produced, and the pH is adjusted to 7-8 to obtain a nickel-aluminum concentrate by hydrolysis. Wherein, the extracting agent may be selected from the group consisting of N-235, Alamine 336, Aliquil 306, P204, P507, N236 and TOA; the alkaline solution for extraction may be ammonia water, sodium hydroxide, sodium chloride or sodium carbonate. Etc. The acidic solution for extraction may be sulfuric acid, hydrochloric acid, phosphoric acid or perchloric acid.
該第二提取步驟S32係將該殘渣體浸漬於一鹼液中,以生成該殘渣浸出液,再由該殘渣浸出液中萃取並沉出鉬及大量鋁渣。詳言之,該第二提取步驟S32係直接以一鹼液浸泡該殘渣體,使得該殘渣體內所含之鉬浸出於該殘渣浸出液中;接著,再利用相同於該第一提取步驟S31之技術手段,萃取該殘渣浸出液並沉岀其中所存有鉬。其中,該鹼液可以為碳酸鈉、氫氧化鈉或氯化鈉等溶液。 The second extraction step S32 is performed by immersing the residue in an alkali solution to form the residue leaching solution, and extracting and depositing molybdenum and a large amount of aluminum slag from the residue leaching solution. In detail, the second extraction step S32 directly soaks the residue body in an alkali solution so that the molybdenum contained in the residue is immersed in the residue leaching solution; and then, the same technique as the first extraction step S31 is utilized. Means extracting the residue leachate and depositing molybdenum therein. The lye may be a solution of sodium carbonate, sodium hydroxide or sodium chloride.
特別地,於該第一提取步驟S31及第二提取步驟S32中,利用萃取、反萃,以沉出釩、鉬、鎳或鋁之技術手段係為本領域技術人員可以輕易理解,且非本發明之主要技術特徵所在,故於此容不再詳加贅述。 In particular, in the first extraction step S31 and the second extraction step S32, the technical means for precipitating vanadium, molybdenum, nickel or aluminum by extraction and stripping can be easily understood by those skilled in the art, and is not The main technical features of the invention are located, so the details are not described in detail herein.
綜上所述,本發明不僅可透過高氧化性酸液浸出該廢觸媒混料中所含之釩、鉬、鎳及鋁,並且使釩、鉬、鎳及 鋁經酸液的高氧化作用而轉變為易萃取之氧化態,以降低後續萃取並沉出金屬之困難度,達到提升金屬傾出率並能將金屬全面性回收再利用之功效。此外,透過本發明提升金屬傾出率的同時,還可選擇直接利用物質的比重差異,以經油液分離方式濾出該廢觸媒混料所挾帶之重油,特別係選擇本發明處理含大量重油之RDS廢觸媒時,更能夠將大量重油重新回收再利用,以產出新的經濟價值。如此,不但可省去傳統燃燒重油所產生之耗能、耗時,更可避免因燃燒而導致溶於重油內之硫或其化合物隨之飄散於空氣中,以進一步解決空污問題並達到降低環境污染之功效。 In summary, the present invention not only leaches vanadium, molybdenum, nickel and aluminum contained in the waste catalyst mixture through a highly oxidizing acid liquid, but also makes vanadium, molybdenum, nickel and Aluminum is converted into an easily extractable oxidation state by the high oxidation of the acid to reduce the difficulty of subsequent extraction and precipitation of the metal, thereby improving the metal pouring rate and recycling the metal comprehensively. In addition, by increasing the metal pouring rate by the present invention, it is also possible to directly use the difference in specific gravity of the material to filter out the heavy oil carried by the waste catalyst mixture by means of oil separation, in particular, selecting the treatment of the present invention. When a large amount of heavy oil RDS waste catalyst is used, it is possible to recycle and reuse a large amount of heavy oil to produce new economic value. In this way, not only the energy consumption and time consumption of traditional heavy oil burning can be saved, but also the sulfur dissolved in the heavy oil or its compound can be prevented from being dispersed in the air due to combustion, so as to further solve the problem of air pollution and achieve the reduction. The effect of environmental pollution.
為了證實本發明確實能有效分離重油,以避免重油影響傾出效果,而能進一步達到提升釩、鉬、鎳及鋁金屬傾出率之功效,本實施例係以硝酸為主要酸浸系統,並採RDS廢觸媒為實施例,進行下述實驗分析。 In order to prove that the present invention can effectively separate heavy oil to avoid the effect of heavy oil on the pouring effect, and further improve the pour rate of vanadium, molybdenum, nickel and aluminum metal, the present embodiment uses nitric acid as the main acid leaching system, and Taking the RDS waste catalyst as an example, the following experimental analysis was performed.
本發明具體實施例一,係將1000克之RDS廢觸媒浸泡於濃度為20%之硝酸溶液,且調配該硝酸溶液與混料之相對重量比值(硝酸/混料)為1至4,以各自反應4小時。於此,先以抽氣設備將經化學式一汽化後之氮酸根收集,且於該上述反應中經化學式二生成硝酸再利用。 In a specific embodiment of the present invention, 1000 g of the RDS waste catalyst is immersed in a nitric acid solution having a concentration of 20%, and the relative weight ratio (nitrate/mixture) of the nitric acid solution to the mixture is adjusted to be 1 to 4, respectively. Reaction for 4 hours. Herein, the chemically vaporized nitrogenate is first collected by a pumping device, and the nitric acid is produced by the chemical formula 2 in the above reaction.
HO-NO2+2H2SO4→NO2 ++2H2SO4 -+H3O+ [化學式1] HO-NO 2 +2H 2 SO 4 →NO 2 + +2H 2 SO 4 - +H 3 O + [Chemical Formula 1]
NO2 ++H2O→HNO3 [化學式2] NO 2 + +H 2 O→HNO 3 [Chemical Formula 2]
待該傾出液及殘渣體中所含的金屬個別沉出後,係針對最後的尾渣進行分析,以測得該尾渣中釩、鉬、鎳及鋁金屬之含量,詳列於表一。 After the metal contained in the decanting liquid and the residue body is separately precipitated, the final tailings are analyzed to determine the content of vanadium, molybdenum, nickel and aluminum in the tailings, as shown in Table 1. .
表一:硝酸/混料比值不同時測得之金屬含量。
由表一得知,當該硝酸溶液與混料之相對重量比(硝酸:混料)高於2:1時,其中該釩、鉬及鎳金屬之回收率均可高達99%以上。 It can be seen from Table 1 that when the relative weight ratio of the nitric acid solution to the mixture (nitrogen:mixture) is higher than 2:1, the recovery of the vanadium, molybdenum and nickel metal can be as high as 99% or more.
本發明具體實施例二,係於該硝酸溶液與混料之相對重量比(硝酸:混料)為3:1之條件下,將1000克之RDS廢觸媒浸泡於濃度為5~40%之硝酸溶液,以各自反應4小時,並待該傾出液及殘渣體中所含的金屬個別沉出後,係針對最後的尾渣進行分析,以測得該尾渣中釩、鉬、鎳及鋁金屬之含量,詳列於表二。 In a second embodiment of the present invention, 1000 g of the RDS waste catalyst is immersed in a nitric acid having a concentration of 5 to 40% under the condition that the relative weight ratio of the nitric acid solution to the mixture (nitrogen:mixing) is 3:1. The solution is reacted for 4 hours each, and after the metal contained in the decanting liquid and the residue body is separately precipitated, the final tailings are analyzed to determine vanadium, molybdenum, nickel and aluminum in the tailings. The content of metal is detailed in Table 2.
由表二得知,當該硝酸濃度高於10%時,其中該釩、鉬及鎳金屬之回收率便可高達99%以上。 It can be seen from Table 2 that when the concentration of nitric acid is higher than 10%, the recovery rate of the vanadium, molybdenum and nickel metal can be as high as 99% or more.
藉此,由表一及表二證實本發明以硝酸為主之酸浸系統,可以提升該釩、鉬及鎳金屬的回收效率,且不會受到重油之影響,以能在低耗能、低耗時之情況下,達到全面性回收RDS廢觸媒中金屬之功效。 Therefore, it is confirmed from Table 1 and Table 2 that the nitric acid-based acid leaching system of the present invention can improve the recovery efficiency of the vanadium, molybdenum and nickel metal without being affected by heavy oil, so as to be low in energy consumption and low in energy consumption. In a time-consuming manner, the full recovery of the metal in the RDS waste catalyst is achieved.
另外,由表一及表二顯示最後尾渣中具有達90-95%的鋁,故證實釩、鉬及鎳金屬的傾出過程,係不會受到鋁同時傾出之干擾,而可以確保傾出後的金屬品質。甚至,以該硝酸酸浸該RDS廢觸媒後,由該尾渣中所測得的硫僅不到2%,可知該RDS廢觸媒中所含有的硫,大部分係被硝酸轉換成硫酸,而重新混合於該酸液中。 In addition, Tables 1 and 2 show that the final tailings have up to 90-95% of aluminum, so it is confirmed that the vanadium, molybdenum and nickel metal are not subjected to the simultaneous dumping of aluminum, and can ensure the inclination. The quality of the metal after the out. Even after immersing the RDS waste catalyst with the nitric acid, the sulfur measured in the tail slag is less than 2%, and it is known that most of the sulfur contained in the RDS waste catalyst is converted into sulfuric acid by nitric acid. And remixed in the acid.
此上述外,本發明具體實施例三,係於該硝酸溶液與混料之相對重量比(硝酸:混料)為3:1之條件下,將1000克之RDS廢觸媒浸泡於濃度為20%之硝酸溶液,且於其中另外添加1~25%之強酸〔如鹽酸〕,以各自反應4小時,並待反應完成後,針對浸出後之傾出液進行分析,測得最終釩、鉬、鎳及鋁金屬之回收率,詳列於表三。 In addition to the above, in the third embodiment of the present invention, 1000 g of the RDS waste catalyst is immersed in a concentration of 20% under the condition that the relative weight ratio of the nitric acid solution to the mixture (nitrogen:mixing) is 3:1. a nitric acid solution, and additionally adding 1 to 25% of a strong acid (such as hydrochloric acid) to react for 4 hours, and after the reaction is completed, the decanted liquid after the leaching is analyzed to determine the final vanadium, molybdenum, and nickel. And the recovery rate of aluminum metal is detailed in Table 3.
由表三得知,當於該硝酸酸浸系統中輔助有強酸時, 其中該釩、鉬及鎳金屬的浸出回收效果係明顯提升。藉此,證實該輔助酸(如鹽酸、硫酸等強酸性物質)的添加,係可有效提升該釩、鉬及鎳金屬的回收率。 It is known from Table 3 that when a strong acid is assisted in the nitric acid leaching system, Among them, the leaching recovery effect of the vanadium, molybdenum and nickel metal is significantly improved. Thereby, it is confirmed that the addition of the auxiliary acid (such as strong acid such as hydrochloric acid or sulfuric acid) can effectively improve the recovery rate of the vanadium, molybdenum and nickel metal.
經上,本發明以酸浸出廢觸媒中所含金屬之方法,係能夠全面回收其中所含金屬,且同時將富含之重油直接回收再利用,以達到減少耗能並降低環境污染之功效。且,本發明以酸浸出廢觸媒中所含金屬之方法,還能夠直接傾出氧化態之金屬,以降低後續處理之困難度,進而達到提升金屬傾出率之功效。 According to the above method, the method for acid leaching the metal contained in the waste catalyst can completely recover the metal contained therein, and at the same time directly recover and reuse the rich heavy oil to reduce the energy consumption and reduce the environmental pollution. . Moreover, in the method of acid leaching the metal contained in the waste catalyst, the metal can be directly decanted in the oxidation state to reduce the difficulty of subsequent treatment, thereby achieving the effect of improving the metal pouring rate.
雖然本發明已利用上述較佳實施例揭示,然其並非用以限定本發明,任何熟習此技藝者在不脫離本發明之精神和範圍之內,相對上述實施例進行各種更動與修改仍屬本發明所保護之技術範疇,因此本發明之保護範圍當視後附之申請專利範圍所界定者為準。 While the invention has been described in connection with the preferred embodiments described above, it is not intended to limit the scope of the invention. The technical scope of the invention is protected, and therefore the scope of the invention is defined by the scope of the appended claims.
〔本發明〕 〔this invention〕
S1‧‧‧浸出步驟 S1‧‧‧ leaching step
S2‧‧‧除油步驟 S2‧‧‧Degreasing step
S3‧‧‧精製步驟 S3‧‧‧ refining steps
S31‧‧‧第一提取步驟 S31‧‧‧First extraction step
S32‧‧‧第二提取步驟 S32‧‧‧Second extraction step
第1圖:本發明之操作流程圖一。 Figure 1 is a flow chart 1 of the operation of the present invention.
第2圖:本發明之操作流程圖二。 Figure 2: Flow chart 2 of the operation of the present invention.
S1‧‧‧浸出步驟 S1‧‧‧ leaching step
S2‧‧‧除油步驟 S2‧‧‧Degreasing step
S3‧‧‧精製步驟 S3‧‧‧ refining steps
Claims (16)
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| TW101127619A TWI542701B (en) | 2012-07-31 | 2012-07-31 | Method for soaking metal in waste catalyst by acid liquid |
| CN2012103844370A CN102925693A (en) | 2012-07-31 | 2012-10-12 | Method for extracting metal in waste catalyst RDS/HDS by acid leaching method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| TW101127619A TWI542701B (en) | 2012-07-31 | 2012-07-31 | Method for soaking metal in waste catalyst by acid liquid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| TW201404890A TW201404890A (en) | 2014-02-01 |
| TWI542701B true TWI542701B (en) | 2016-07-21 |
Family
ID=47640616
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| TW101127619A TWI542701B (en) | 2012-07-31 | 2012-07-31 | Method for soaking metal in waste catalyst by acid liquid |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN102925693A (en) |
| TW (1) | TWI542701B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110029224A (en) * | 2019-05-31 | 2019-07-19 | 宜昌银钒科技有限公司 | A kind of environment friendly and pollution-free vanadic anhydride high efficiency extraction technique |
| CN111154990B (en) * | 2019-12-27 | 2021-02-12 | 四川顺应动力电池材料有限公司 | Method for separating and recovering nickel in organic nickel catalyst |
| CN116287719A (en) * | 2023-02-23 | 2023-06-23 | 承德天大钒业有限责任公司 | A method for recovering aluminum, molybdenum and vanadium elements from aluminum-molybdenum-vanadium crushed alloy |
-
2012
- 2012-07-31 TW TW101127619A patent/TWI542701B/en active
- 2012-10-12 CN CN2012103844370A patent/CN102925693A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| TW201404890A (en) | 2014-02-01 |
| CN102925693A (en) | 2013-02-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| TWI427155B (en) | Method for recycling metal from molybdenum-containing waste catalyst | |
| CN102051483B (en) | Method for reclaiming metals from molybdenum-containing waste catalyst | |
| TWI432583B (en) | Method for recycling rare earth, vanadium and nickel from catalyst waste | |
| TWI465579B (en) | Method for recycling metal in waste catalyst comprised of aluminum | |
| CN102050492B (en) | Method for recovering metal from molybdenum-containing spent catalyst | |
| CN106868307B (en) | A kind of comprehensive utilization process of pyrite cinder arsenic removal enrichment gold and silver | |
| JPS5980737A (en) | Recovery of metals from waste hydrogenation catalyst | |
| TWI432584B (en) | A method for extracting metal from manganese residue | |
| CN101323915A (en) | A kind of molybdenum-nickel ore full-wet extraction molybdenum-nickel method | |
| JP6176491B2 (en) | Method for removing copper from aqueous nickel chloride solution | |
| CN107429317B (en) | Method for producing nickel/cobalt mixed sulfide and method for wet smelting nickel oxide ore | |
| RU2477327C1 (en) | Complex processing method of carbon-silicic black-shale ores | |
| AU2020408368A1 (en) | Recovery of vanadium from slag materials | |
| CN101831542A (en) | Method for extracting metallic elements of ferrum, magnesium and calcium from molybdenum milltailings | |
| Hu et al. | Efficient vanadium extraction from shale with high silicon content using a short flow process by roasting-water leaching: Laboratory and industrial scale research | |
| JP5375631B2 (en) | Method for removing metal elements from organic phase | |
| Kurniawan et al. | Intensified extraction of vanadium from vanadium-bearing titanomagnetite (VTM) concentrate via one-stage leaching and solvent extraction using acidic organophosphorus extractant | |
| TWI542701B (en) | Method for soaking metal in waste catalyst by acid liquid | |
| CN110678564A (en) | Method for preparing leaching feedstock | |
| CN104862487B (en) | A kind of resource high-efficiency method for transformation of non-ferrous metal zinc metallurgy flying dust | |
| Steinlechner et al. | PGM recycling from catalysts in a closed hydrometallurgical loop with an optional cerium recovery | |
| CN1827803A (en) | A method for extracting indium from iron-slag wet smelting zinc and producing zinc ferrite | |
| TWI427154B (en) | Method for recycling metal from tungsten-containing waste catalysis | |
| Shi et al. | Separation and recovery of nickel and copper from multi-metal electroplating sludge by co-extracting and selective stripping | |
| Ayinla et al. | Energy saving Chemical Beneficiation Method of Improving Low Grade Nigeria Chromite Ore for Use in Steel Industries |