CN108160109A - A kind of microwave-assisted regeneration FCC dead catalyst methods - Google Patents
A kind of microwave-assisted regeneration FCC dead catalyst methods Download PDFInfo
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- CN108160109A CN108160109A CN201711147278.1A CN201711147278A CN108160109A CN 108160109 A CN108160109 A CN 108160109A CN 201711147278 A CN201711147278 A CN 201711147278A CN 108160109 A CN108160109 A CN 108160109A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 65
- 238000000034 method Methods 0.000 title claims abstract description 28
- 230000008929 regeneration Effects 0.000 title claims abstract description 16
- 238000011069 regeneration method Methods 0.000 title claims abstract description 16
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 48
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 36
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 35
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000003513 alkali Substances 0.000 claims abstract description 30
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 26
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 25
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 24
- 150000002910 rare earth metals Chemical class 0.000 claims abstract description 21
- 229910052742 iron Inorganic materials 0.000 claims abstract description 20
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000002386 leaching Methods 0.000 claims description 33
- 229910000329 aluminium sulfate Inorganic materials 0.000 claims description 19
- -1 silicon metal aluminium salt Chemical class 0.000 claims description 14
- 239000007787 solid Substances 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 10
- 239000003610 charcoal Substances 0.000 claims description 8
- 229910052684 Cerium Inorganic materials 0.000 claims description 7
- 229910052746 lanthanum Inorganic materials 0.000 claims description 7
- 150000003839 salts Chemical class 0.000 abstract description 9
- 238000004064 recycling Methods 0.000 abstract description 6
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 abstract description 6
- 229910052751 metal Inorganic materials 0.000 abstract description 5
- 239000002184 metal Substances 0.000 abstract description 5
- 239000002808 molecular sieve Substances 0.000 abstract description 5
- 230000005855 radiation Effects 0.000 abstract description 5
- 239000002904 solvent Substances 0.000 abstract description 4
- 230000000717 retained effect Effects 0.000 abstract description 2
- 239000000126 substance Substances 0.000 description 7
- 239000002253 acid Substances 0.000 description 5
- 238000011084 recovery Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 239000002699 waste material Substances 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 239000004411 aluminium Substances 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000010779 crude oil Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- XJQKGCFZPMQNIQ-UHFFFAOYSA-N [V].[Fe].[Ni] Chemical compound [V].[Fe].[Ni] XJQKGCFZPMQNIQ-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000004523 catalytic cracking Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000005660 chlorination reaction Methods 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 239000003546 flue gas Substances 0.000 description 2
- 239000000295 fuel oil Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- HBVFXTAPOLSOPB-UHFFFAOYSA-N nickel vanadium Chemical compound [V].[Ni] HBVFXTAPOLSOPB-UHFFFAOYSA-N 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000010457 zeolite Substances 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
- 238000003723 Smelting Methods 0.000 description 1
- 229910021550 Vanadium Chloride Inorganic materials 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical group [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 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
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000012320 chlorinating reagent Substances 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- RPESBQCJGHJMTK-UHFFFAOYSA-I pentachlorovanadium Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[V+5] RPESBQCJGHJMTK-UHFFFAOYSA-I 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/48—Liquid treating or treating in liquid phase, e.g. dissolved or suspended
- B01J38/64—Liquid treating or treating in liquid phase, e.g. dissolved or suspended using alkaline material; using salts
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/90—Regeneration or reactivation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/48—Liquid treating or treating in liquid phase, e.g. dissolved or suspended
- B01J38/60—Liquid treating or treating in liquid phase, e.g. dissolved or suspended using acids
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
Abstract
The present invention relates to a kind of microwave-assisted regeneration FCC dead catalyst methods, belong to secondary resource comprehensive reutilization technical field.This method is first by FCC dead catalyst, and using the sodium hydroxide solution of a concentration of 0.1 ~ 0.8mol/L as solvent, alkali soaks vanadium a part of in 10 ~ 60min removing FCC dead catalyst under the conditions of microwave radiation, 50 ~ 100 DEG C, obtains leached mud and the leachate containing vanadium.Leached mud is obtained after alkali is soaked, using the hydrochloric acid solution of a concentration of 1wt% ~ 8wt% as solvent, 10 ~ 60min of acidleach under the conditions of microwave radiation, 50 ~ 100 DEG C, it obtains being rich in the leached mud that rare earth, iron, vanadium, the leachate of nickel and the sial molecules of salt with lattice structure are sieved, so as to fulfill the recycling of rare earth element, the removing of iron, vanadium, nickel metal, and the structure of molecular sieve can also be most importantly retained, it can be used for preparing new FCC catalyst.This method is simple with treatment process, and the operating time is short, and it is complete to obtain sial molecules of salt sieve structure in leached mud.
Description
Technical field
The present invention relates to a kind of microwave-assisted regeneration FCC dead catalyst methods, belong to secondary resource comprehensive reutilization skill
Art field.
Background technology
Catalytic cracking (FCC) is oil refining enterprise by high-value products such as heavy oils production gasoline, diesel oil, low-carbon alkenes
One of core technology.FCC catalyst is the catalyst of usage amount maximum during petroleum refining, at present China's FCC catalyst
Usage amount is at 150,000 tons/year or more.With crude oil increasingly heaviness and in poor quality, crude oil is in catalytic cracking process, in crude oil
Metallic compound can decompose completely, and accumulate on FCC catalyst.With constantly recycling for FCC catalyst, FCC is urged
The metal deposited in agent can gradually increase, and activity and heavy oil conversion performance is caused all to decline, therefore crack factory's daily requirement
A large amount of dead catalyst is discharged, and supplements the raw catelyst of equivalent.It is expected that the incrementss of annual FCC dead catalyst are about 5%, very
The annual FCC dead catalyst for generating 200,000 tons will be broken through soon.
First, FCC dead catalyst is by zeolite（Molecular sieve）It forms, is with SiO2And Al2O3It is as main component, there is crystalline substance
The silicon metal aluminium salt of lattice structure has larger specific surface area and pore volume.Although FCC dead catalyst loses catalytic activity,
But simultaneously complete destruction is encountered in its internal structure, still there is certain utility value.Secondly, China's rare earth is in Effect of Catalysis In Petrochemistry field
In consumption figure account for more than the 10% of rare earth aggregate consumption.With the worsening shortages of resource, returned from petrochemical catalyst waste material
Valuable rare earth composition is received with good social and economic benefit.In addition, the gold of higher proportion is typically contained in spent FCC catalyst
Belong to, such as vanadium, nickel, iron, calcium.These tenors are high, the serious spent FCC catalyst of poisoning is generally difficult regeneration, and by conduct
Solid waste is filled, and can not only waste a large amount of resource in this way, and can constitute a serious threat to the living environment of the mankind.
Therefore, this kind of FCC dead catalyst how is effectively treated, very big important function is played to petroleum chemical industry.
Chinese patent CN201310290526.3 discloses one kind and uses salt Ore Leaching-chlorination of hydrochloric acid-from spent FCC catalyst
Extraction-selective precipitation and etc. recycling Ni, the Ni rate of recovery is up to 72.7%.Chinese patent CN 201310290760.6 is public
One kind is opened from spent FCC catalyst using salt acid extraction-hydrochloric acid acidification-extraction-ion-exchange recycling vanadium, this method obtains V2O5
Product purity it is high, reach 97%.Chinese patent CN201610920734.0 disclose it is a kind of by spent FCC catalyst and chlorinating agent, also
Former agent and slag former carry out 30 ~ 300min of chlorination at 1250 ~ 1700 DEG C in smelting furnace after mixing, will obtain containing nickel,
The flue gas of vanadium chloride incorporates flue gas washing system and carries out nickel vanadium separation, it is achieved thereby that the recycling of nickel vanadium.Chinese patent
CN201610921636.9 disclose it is a kind of by spent FCC catalyst, melting prepares nickel vanadium iron melt at high temperature, be then cast into nickel
Vanadium iron ingot recycles ferro-aluminum nickel.Chinese patent CN 201110352617.6 is disclosed a kind of to be touched from the useless FCC/ROC of the nickel containing vanadium
The method of recovering rare earth, vanadium, nickel in matchmaker.By dead catalyst, in 1 ~ 5mol sulfuric acid solutions at 90 ~ 95 DEG C acidleach 1 ~ 4 hour
Afterwards, by containing the re dip solution of aluminium, vanadium, nickel carry out double salt precipitation reaction after obtain double salt of rare earth filter cake and containing aluminium, vanadium, nickel it is expensive
Liquid.Extraction of rare eart rate of the present invention is 88 ~ 91%；V, the Ni rate of recovery is more than 95%.As it can be seen that these method flows it is complicated, operation when
Between the use of long, high energy consumption and a large amount of concentrated acid lead to original in catalyst zeolite structured be destroyed completely, it is impossible to repeat
It utilizes.According to Chinese patent CN1686813 and experimental study, the aluminium element activity in molecular sieve waste material is high, directly using a large amount of
During Leaching by strong acid curing, co-dissolve is not only consumed a large amount of leachings acid, the also complete destruction original knot of molecular sieve by rare earth and aluminium
Structure.
Invention content
For the above-mentioned prior art there are the problem of and deficiency, the present invention using microwave heating technique rapidly, selectivity
The advantages that with being evenly heated, and consider that the use of a large amount of concentrated acids will destroy the structure of molecular sieve, the present invention provides a kind of micro-
Wave assisted Regeneration FCC dead catalyst methods.This method is first by FCC dead catalyst, with the hydrogen-oxygen of a concentration of 0.1 ~ 0.8mol/L
Change sodium solution is solvent, a part of in alkali leaching 10 ~ 60min removing FCC dead catalyst under the conditions of microwave radiation, 50 ~ 100 DEG C
Vanadium obtains leached mud and the leachate containing vanadium.Leached mud is obtained after alkali is soaked, using the hydrochloric acid solution of a concentration of 1wt% ~ 8wt% as
Solvent, 10 ~ 60min of acidleach under the conditions of microwave radiation, 50 ~ 100 DEG C, obtain rich in rare earth, iron, vanadium, nickel leachate and tool
There is the leached mud of the sial molecules of salt sieve of lattice structure, so as to fulfill the recycling of rare earth element, the removing of iron, vanadium, nickel metal, and
And the structure of molecular sieve can also be most importantly retained, it can be used for preparing new FCC catalyst.This method has treatment process
Simply, the operating time is short, and it is complete to obtain sial molecules of salt sieve structure in leached mud, and rare earth yield is high, while can remove FCC
Iron, vanadium, nickel metal, highly beneficial to the regeneration of FCC catalyst in dead catalyst.
A kind of microwave-assisted regeneration FCC dead catalyst methods, are as follows：
Step 1, first by the sodium hydroxide solution of FCC dead catalyst and a concentration of 0.1 ~ 0.8mol/L according to liquid-solid ratio for 3 ~
15：1mL/g mixing after microwave irradiation power be 400 ~ 2000W, microwave leaching temperature be 50 ~ 100 DEG C under conditions of alkali leaching 10 ~
60 min obtain alkali leached mud and the leachate containing vanadium；
The hydrochloric acid solution of step 2, the alkali leached mud that step 1 is obtained and a concentration of 1wt% ~ 8wt% is 3 ~ 15 according to liquid-solid ratio：
1mL/g mixing after microwave irradiation power be 400 ~ 2000W, microwave leaching temperature be 50 ~ 100 DEG C under conditions of acidleach 10 ~
60min obtains rich rare earth, iron, vanadium, the leachate of nickel and the silicon metal aluminium salt leached mud with lattice structure.
FCC dead catalyst in the step 1 for not de- charcoal or after at 600 ~ 700 DEG C taking off 1 ~ 4h of charcoal in Muffle furnace
FCC dead catalyst.
FCC dead catalyst rare earth elements in the step 1 are mainly La and Ce.
The beneficial effects of the invention are as follows：
（1）Microwave radiation technology leaching-out technique is introduced into dead catalyst comprehensive reutilization field by the present invention, has treatment process letter
It is single, easy to operate, the advantages that extraction time is short.
（2）The crystal silicon aluminium salt molecular sieve structure that the present invention obtains is complete, can be used for preparing new FCC catalyst.
（3）For the present invention from FCC waste catalyst recovery rare earth elements, the rate of recovery is higher.
（4）The present invention effectively removes iron, vanadium, nickel metal from FCC dead catalyst, you can with comprehensive recovery of iron, vanadium, nickel, again
The activity of FCC catalyst after regenerating can be improved.
Description of the drawings
Fig. 1 is present invention process flow chart；
Fig. 2 is the silicon metal aluminium salt leached mud SEM figures that the embodiment of the present invention 1 obtains.
Specific embodiment
With reference to the accompanying drawings and detailed description, the invention will be further described.
Embodiment 1
As shown in Figure 1, microwave-assisted regeneration FCC dead catalyst methods, are as follows：
Step 1, first by FCC dead catalyst（Chemical composition includes following mass percent component：Al25.95%、Si18.39%、
Ce2.05%、La1.09%、V0.59%、Fe0.48%、Ni0.56%）Charcoal 1h is taken off in Muffle furnace at 600 DEG C, then with it is a concentration of
The sodium hydroxide solution of 0.1mol/L is 5 according to liquid-solid ratio：1mL/g mixing after microwave irradiation power be 1600W, microwave leaching
Alkali leaching 30min obtains alkali leached mud and the leachate containing vanadium under the conditions of at a temperature of 90 °C；The removal efficiency of V is 32.3% after alkali leaching；
The hydrochloric acid solution of step 2, the alkali leached mud that step 1 is obtained and a concentration of 5wt% is 10 according to liquid-solid ratio：1mL/g is mixed
Afterwards microwave irradiation power be 1600W, microwave leaching temperature be 80 DEG C under conditions of acidleach 30min obtain rich rare earth, iron, vanadium,
The leachate of nickel and the silicon metal aluminium salt leached mud with lattice structure.
Above-mentioned rare earth La, Ce leaching rate be respectively 85.4%, 83.8%, and the removal efficiency of Fe, Ni and V be 53%, 41% He
55.8%。
The silicon metal aluminium salt leached mud SEM that the present embodiment obtains is schemed as shown in Fig. 2, from figure 2 it can be seen that in leached mud
Sial molecules of salt sieve structure keeps complete, can be used for preparing new FCC catalyst.
Embodiment 2
As shown in Figure 1, microwave-assisted regeneration FCC dead catalyst methods, are as follows：
Step 1, first by FCC dead catalyst（Chemical composition includes following mass percent component：Al26.04%、Si18.69%、
Ce2.01%、La1.11%、V0.59%、Fe0.46%、Ni0.52%）Charcoal 4h is taken off in Muffle furnace at 600 DEG C, then with it is a concentration of
The sodium hydroxide solution of 0.5mol/L is 5 according to liquid-solid ratio：1mL/g mixing after microwave irradiation power be 1800W, microwave leaching
Alkali leaching 30min obtains alkali leached mud and the leachate containing vanadium under conditions of temperature is 100 DEG C；The removal efficiency of V is after alkali leaching
35.59%；
The hydrochloric acid solution of step 2, the alkali leached mud that step 1 is obtained and a concentration of 6wt% is 5 according to liquid-solid ratio：1mL/g is mixed
Afterwards microwave irradiation power be 2000W, microwave leaching temperature be 100 DEG C under conditions of acidleach 20min obtain rich rare earth, iron, vanadium,
The leachate of nickel and the silicon metal aluminium salt leached mud with lattice structure.
Above-mentioned rare earth La, Ce leaching rate be respectively 92.4%, 88.8%, and the removal efficiency of Fe, Ni and V for 62.7%,
47.5%、54.2%.Aluminium salt molecular sieve structure keeps complete in silicon metal aluminium salt leached mud, can be used for preparing new FCC catalyst.
Embodiment 3
As shown in Figure 1, microwave-assisted regeneration FCC dead catalyst methods, are as follows：
Step 1, first by FCC dead catalyst（Chemical composition includes following mass percent component：Al26.04%、Si18.69%、
Ce2.01%、La1.11%、V0.59%、Fe0.46%、Ni0.52%）Charcoal 2h is taken off in Muffle furnace at 700 DEG C, then with it is a concentration of
The sodium hydroxide solution of 0.8mol/L is 15 according to liquid-solid ratio：1mL/g mixing after microwave irradiation power be 400W, microwave leaching
Alkali leaching 60min obtains alkali leached mud and the leachate containing vanadium under conditions of temperature is 50 DEG C；The removal efficiency of V is 27.7% after alkali leaching；
The hydrochloric acid solution of step 2, the alkali leached mud that step 1 is obtained and a concentration of 1wt% is 3 according to liquid-solid ratio：1mL/g is mixed
It is afterwards 400W in microwave irradiation power, acidleach 60min obtains rich rare earth, iron, vanadium, nickel under conditions of microwave leaching temperature is 50 DEG C
Leachate and with lattice structure silicon metal aluminium salt leached mud.
Above-mentioned rare earth La, Ce leaching rate be respectively 73.2%, 71.7%, and the removal efficiency of Fe, Ni and V for 46.2%,
32.3%、50.6%.Aluminium salt molecular sieve structure keeps complete in silicon metal aluminium salt leached mud, can be used for preparing new FCC catalyst.
Embodiment 4
As shown in Figure 1, microwave-assisted regeneration FCC dead catalyst methods, are as follows：
Step 1, first by FCC dead catalyst（Chemical composition includes following mass percent component：Al26.04%、Si18.69%、
Ce2.01%、La1.11%、V0.59%、Fe0.46%、Ni0.52%）Charcoal 3h is taken off in Muffle furnace at 680 DEG C, then with it is a concentration of
The sodium hydroxide solution of 0.6mol/L is 3 according to liquid-solid ratio：1mL/g mixing after microwave irradiation power be 2000W, microwave leaching
Alkali leaching 10min obtains alkali leached mud and the leachate containing vanadium under conditions of temperature is 80 DEG C；The removal efficiency of V is 30.6% after alkali leaching；
The hydrochloric acid solution of step 2, the alkali leached mud that step 1 is obtained and a concentration of 8wt% is 15 according to liquid-solid ratio：1mL/g is mixed
Afterwards microwave irradiation power be 1000W, microwave leaching temperature be 80 DEG C under conditions of acidleach 10min obtain rich rare earth, iron, vanadium,
The leachate of nickel and the silicon metal aluminium salt leached mud with lattice structure.
Above-mentioned rare earth La, Ce leaching rate be respectively 95.9%, 94.2%, and the removal efficiency of Fe, Ni and V for 72.3%,
56.6%、63.8%.Aluminium salt molecular sieve structure keeps complete in silicon metal aluminium salt leached mud, can be used for preparing new FCC catalyst.
Embodiment 5
As shown in Figure 1, microwave-assisted regeneration FCC dead catalyst methods, are as follows：
Step 1, first by FCC dead catalyst（Chemical composition includes following mass percent component：Al26.04%、Si18.69%、
Ce2.01%、La1.11%、V0.59%、Fe0.46%、Ni0.52%）Consolidate with the sodium hydroxide solution of a concentration of 0.8mol/L according to liquid
Than being 10：1mL/g mixing after microwave irradiation power be 1000W, microwave leaching temperature be 100 DEG C under conditions of alkali soak 10min
Obtain alkali leached mud and the leachate containing vanadium；The removal efficiency of V is 42.2% after alkali leaching；
The hydrochloric acid solution of step 2, the alkali leached mud that step 1 is obtained and a concentration of 6wt% is 12 according to liquid-solid ratio：1mL/g is mixed
Afterwards microwave irradiation power be 1200W, microwave leaching temperature be 80 DEG C under conditions of acidleach 10min obtain rich rare earth, iron, vanadium,
The leachate of nickel and the silicon metal aluminium salt leached mud with lattice structure.
Above-mentioned rare earth La, Ce leaching rate be respectively 90.7%, 88.2%, and the removal efficiency of Fe, Ni and V for 63.9%,
40.1%、52.2%.Aluminium salt molecular sieve structure keeps complete in silicon metal aluminium salt leached mud, can be used for preparing new FCC catalyst.
The specific embodiment of the present invention is explained in detail above in association with attached drawing, but the present invention is not limited to above-mentioned
Embodiment, within the knowledge of a person skilled in the art, can also be before present inventive concept not be departed from
Put that various changes can be made.
Claims (3)
- A kind of 1. microwave-assisted regeneration FCC dead catalyst methods, it is characterised in that be as follows：Step 1, first by the sodium hydroxide solution of FCC dead catalyst and a concentration of 0.1 ~ 0.8mol/L according to liquid-solid ratio for 3 ~ 15：1mL/g mixing after microwave irradiation power be 400 ~ 2000W, microwave leaching temperature be 50 ~ 100 DEG C under conditions of alkali leaching 10 ~ 60 min obtain alkali leached mud and the leachate containing vanadium；The hydrochloric acid solution of step 2, the alkali leached mud that step 1 is obtained and a concentration of 1wt% ~ 8wt% is 3 ~ 15 according to liquid-solid ratio： 1mL/g mixing after microwave irradiation power be 400 ~ 2000W, microwave leaching temperature be 50 ~ 100 DEG C under conditions of acidleach 10 ~ 60min obtains rich rare earth, iron, vanadium, the leachate of nickel and the silicon metal aluminium salt leached mud with lattice structure.
- 2. microwave-assisted regeneration FCC dead catalyst methods according to claim 1, it is characterised in that：In the step 1 FCC dead catalyst is not de- charcoal or at 600 ~ 700 DEG C in Muffle furnace after 1 ~ 4h of de- charcoal FCC dead catalyst.
- 3. microwave-assisted regeneration FCC dead catalyst methods according to claim 1 or 2, it is characterised in that：The step 1 In FCC dead catalyst rare earth elements be mainly La and Ce.
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Application publication date: 20180615 |