CN106378204A - Preparation method for metal capturing agent - Google Patents
Preparation method for metal capturing agent Download PDFInfo
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- CN106378204A CN106378204A CN201610665466.2A CN201610665466A CN106378204A CN 106378204 A CN106378204 A CN 106378204A CN 201610665466 A CN201610665466 A CN 201610665466A CN 106378204 A CN106378204 A CN 106378204A
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- 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
- B01J33/00—Protection of catalysts, e.g. by coating
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- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/847—Vanadium, niobium or tantalum or polonium
- B01J23/8472—Vanadium
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- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/90—Regeneration or reactivation
- B01J23/94—Regeneration or reactivation of catalysts comprising metals, oxides or hydroxides of the iron group metals or copper
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- 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
- B01J38/485—Impregnating or reimpregnating with, or deposition of metal compounds or catalytically active elements
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- 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
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- 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
- B01J38/62—Liquid treating or treating in liquid phase, e.g. dissolved or suspended using acids organic
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- 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
- B01J38/66—Liquid treating or treating in liquid phase, e.g. dissolved or suspended using alkaline material; using salts using ammonia or derivatives thereof
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
- C10G11/02—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils characterised by the catalyst used
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/205—Metal content
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/70—Catalyst aspects
- C10G2300/701—Use of spent catalysts
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Catalysts (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention relates to a preparation method for a metal capturing agent and also relates to a recycling method for a waste catalyst. The metal capturing agent is applicable to the catalytic cracking process of hydrocarbons with vanadium pollutants. The preparation method comprises the following steps: subjecting waste FCC catalyst, water and an oxalic acid-ammonium fluorosilicate solution to mixing, exchanging and filtering so as to obtain a filter cake; smashing the filter cake and adding a magnesium compound; adjusting a pH value by using hydrochloric acid; subjecting a rare earth compound to filtering and leaching; and drying a filter cake obtained in the previous step so as to obtain the metal capturing agent. The method enables the waste FCC catalyst to be reused; and the prepared metal capturing agent can protect a catalyst, reduce poisoning effect of vanadium on the catalyst and obviously improve the yield of products with value.
Description
Technical field：The present invention relates to a kind of preparation method of metal traps, belong to catalytic cracking catalyst auxiliary agent
Category.
Background technology
At present, continue to increase with oil extraction depth, the quality of crude oil is also deteriorated further, and occupy in crude oil price
In the case that height is lower, refinery needs processing heavy oil or low grade oilses for reduces cost so that maximizing the benefits.
General higher, the especially vanadium of content of beary metal in poor oil, typically with the shape of porphyrin vanadium and non-porphyrin vanadium in crude oil
Formula exists.In FCC regenerator, the compound of vanadium is oxidized to V2O5, the surface of catalyst is flowed through with liquid and enters molecular sieve
Inside, destroy crystal structure of molecular sieve, when on catalyst deposition vanadium reach 10000 μ g/g about when, catalyst activity can be led to
Substantially reduce and even completely lose, and vanadium plays catalytic dehydrogenation to raw material, lead to hydrogen and coking yield to increase.
Over nearly 30 years, catalytic cracking process priority develops multiple promoters, usually will be added in raw oil
The liquid analog assistant of passivating vanadium harm is referred to as passivator, and will be added to rise the independent granular solids of identical function in catalyst
Referred to as vanadium traps.
Magnesium aluminate spinel is conventional metal traps, and such as US5603823A discloses a kind of vanadium trapping agent, consisting of
The Al of MgO (b) 30-60wt% of (a) 15-60wt%2O3And (c) 10-30wt% rare earth, rare earth be selected from lanthanum-oxides and/or
Neodymium oxides, wherein, at least part of MgO and Al2O3Define magnesium aluminate spinel.
US5057205 discloses a kind of vanadium trapping agent for catalytic cracking process, consist of alkaline earth oxide and
Alkaline-earth metal spinelle, its weight compares 90:10-10:90, but it needs two regeneratoies, complex process, and Conventional catalytic device is no
Method is realized.
CN1148256C discloses a kind of compositionss containing magnesium aluminate spinel and preparation method thereof, containing 25-30wt%'s
The Al of MgO, 60-70wt%2O3With the rare-earth oxide of the except cerium of 5-15wt%, the content of free magnesium is less than
5wt%, described compositionss can and bore dia be not less than 10nm.
CN103789014B discloses a kind of metal traps and its preparation method and application, contains in described metal traps
There are magnesium oxide, aluminium oxide and lanthanide rare metal-oxide and/or transition metal oxide, its bulk density is 0.85-1.2g/
cm3.
CN1879960A is added water using Kaolin and magnesium oxide or its precursor after pulling an oar and sprays into microsphere, then in 900-
Roasting at 1100 DEG C, roasting microsphere washing fall sodium after aqueous slkali extracting, then processed thus obtaining containing oxidation with rare earth precursor
Magnesium and the heavy metal resistant auxiliary agent of rare earth oxide.
USP5141624 using dipping magnesium compound macroporous aluminium oxide as catching metal agent.
And catalytic cracking spent catalyst be used in the process of crude oil catalytic cracking catalyst because naturally run damage, life-time service loses
Live, the solid waste that periodically draws off and formed, its main chemical compositions is aluminium oxide and silicon oxide, contain simultaneously a small amount of ferrum,
Nickel, vanadium, calcium, magnesium and micro heavy oxide.Generally to be filled out as " danger is useless " material currently for these dead catalyst
Bury process, so existing very high security landfill cost, waste resource again, thus the recycling of dead catalyst becomes urgently
Problem to be solved.
Yet there are no the report preparing metal traps using dead catalyst.
Content of the invention：
Catalytic cracking spent catalyst be used in the process of crude oil catalytic cracking catalyst because naturally run damage, life-time service loses
Live, the solid waste that periodically draws off and formed, its main chemical compositions is aluminium oxide and silicon oxide, contain simultaneously a small amount of ferrum,
Nickel, vanadium, calcium, magnesium and micro heavy oxide.Generally to be filled out as " danger is useless " material currently for these dead catalyst
Bury process, so existing very high security landfill cost, waste resource again, thus the recycling of dead catalyst becomes urgently
Problem to be solved.
Yet there are no the report preparing metal traps using dead catalyst.
It is an object of the invention to provide a kind of preparation method of metal traps, also provide for a kind of circulation profit of dead catalyst
Use method.
A kind of preparation method of metal traps, the method comprises the following steps：
(1) dead catalyst that FCC apparatus unload and water are pulled an oar, and add a certain proportion of oxalic acid-ammonium fluosilicate solution, room temperature
Lower exchange 1-3h.
(2) step (1) is exchanged the serosity finishing to filter, filter cake is pulled an oar with water, adds magnesium compound, adjusts slurry with hydrochloric acid
Liquid pH value, between 3.0-3.5, exchanges 1-3h under room temperature.
(3) step (2) is exchanged the serosity finishing to filter, and drip washing rare earth compound solution, filter cake is dried, and obtains final product title
Thing.
Dead catalyst described in step (1) can be the poising agent drawing off in regenerator or three rotations drawing off
Fine powder.
The ratio of water described in step (1) and step (2) is water/dead catalyst butt=7-10:1
Oxalic acid-ammonium fluosilicate solution described in step (1), wherein, H2C2O4/(NH4)2SiF6=0.1-10:1, it is dense
Degree is with C2O4 2-It is calculated as 50-120g/L.
Oxalic acid described in step (1)-ammonium fluosilicate solution additional proportion is with C2O4 2-Meter, its C2O4 2-/ dead catalyst butt
Mass ratio be 0.01-0.5:1.
Magnesium compound described in step (2) is magnesium chloride, magnesium nitrate and/or magnesium sulfate, preferably magnesium nitrate, additional proportion
In terms of MgO, MgO/ dead catalyst butt=20-36wt%：1.
Rare earth compound described in step (3) is lanthanum chloride, cerium chloride and/or lanthanum-cerium chloride, and preferably lanthanum chloride adds
Ratio is with RE2O3Meter RE2O3/ dead catalyst butt=8-15wt%：1.
The concentration of the rare earth compound solution described in step (3) is with RE2O3Meter 100-150g/L.
The ratio that Kaolin accounts in catalytic cracking catalyst is very high, and in FCC apparatus regenerator, temperature is generally higher than
650 DEG C, at this temperature, the aluminium oxide in Kaolin has obtained activity, possesses the bar forming magnesium aluminate spinel with magnesium oxide
Part.Magnesium oxide can form magnesium aluminate spinel with aluminium oxide therein, and MgO can be with vanadic acid H3VO4Reaction generates MgV2O6, Mg2V2O7,
Mg3V2O8Deng vanadic acid magnesium oxide, RE2O3Generation REVO is then reacted with vanadic acid4, the generation of these compounds, make with animal migration
Vanadium fixed, therefore catalyst structure is protected, and activity and selectivity is maintained.
The MgO of free state, as basic anhydride, can neutralize the strong acid center on carrier so as to lose cracking activity,
Non-selective cracking reaction will not occur, improve its coke selectivity.
The present invention provides a kind of method that utilization dead catalyst prepares metal traps, has advantages below：
1st, process dead catalyst：By dead catalyst as the raw material of preparation metal traps, consume industrial solid castoff
Dead catalyst, solves the environmental problem of the difficult difficult landfill of dead catalyst, and turns waste into wealth, reduce being prepared into of metal traps
This.
2nd, concise in technology：Dead catalyst is mixed with oxalic acid-ammonium fluosilicate solution, by the part heavy metal in dead catalyst and
Non-framework aluminum in duct removes so that the duct of dead catalyst is recovered.
3rd, the ratio that Kaolin accounts in catalytic cracking catalyst is very high, and in FCC apparatus regenerator, temperature is generally higher than
650 DEG C, at this temperature, the aluminium oxide in Kaolin has obtained activity, possesses the bar forming magnesium aluminate spinel with magnesium oxide
Part.
The metal traps of the present invention have good metal trapping effect, for high vanadium RFCC, Ke Yiming
Show and slow down the destruction to catalytic cracking catalyst for the vanadium, improve liquid product yield, reduce dry gas and coking yield.For example at certain
When the metal traps addition of the FCC apparatus present invention accounts for system general reserve 10%, Ni content 7658ppm on poising agent, V content
During 9981ppm, compared with when being not added with, leveler activity is improved to 64.8% by 51.5%, and heavy oil yield is subtracted by 9.15wt%
As little as 5.86wt%, total liquid yield is improved to 81.01wt% by 78.10wt%, and dry gas and coke selectivity are also clearly better,
As can be seen here, the metal traps that the present invention provides can more effectively convert heavy oils into into high-value product.
Specific embodiment
Hereinafter the specific embodiment of the present invention is described in detail it should be appreciated that described herein concrete
Embodiment is merely to illustrate and explains the present invention, but is not limited to the present invention.
In the present invention, raw materials specification is as follows：
(1) dead catalyst：Choose the poising agent that three producer's FCC apparatus draw off, its analytical test result such as table 1：
The analytical test result of the poising agent that 1 three producer's FCC apparatus of table draw off
(2) boehmite：Igloss 35wt%；
(3) heavy-burned magnesia：99.5wt%.
(4) magnesium nitrate hexahydrate：It is prepared into the solution of 150g/L in terms of MgO.
(5) six water lanthanum chloride：It is prepared into RE2O3The solution of meter 150g/L.
(6) oxalic acid：Qingdao Na Diou Trade Co., Ltd., 75wt% in terms of phosphoric acid.
(7) ammonium fluosilicate：Yancheng Tian Ying Chemical Co., Ltd., 98wt%.
In the present invention, mensure analysis method used is as follows：
(1) chemical composition：Xray fluorescence spectrometer, German Brooker, S8Tiger 3KW.Experiment adopts S8 type X-ray
Fluorescence spectrophotometer carries out sample element chemistry composition analysis and characterizes, and x-ray source is Rh target, and sample is strafed by the X-ray of initial stage
The exclusive characteristic spectral line of each element ejects afterwards, and the X-ray of every kind of specific wavelength is recorded, and thus calculates difference
Concentration corresponding to element.Sample tablet machine is ZHY401/601 type.
(2) abrasion index：Gooseneck tube method, RIPP.
(3) specific surface：Nitrogen adsorption instrument, Kang Ta company of the U.S. produces.Experiment adopts QUADRASORB SI type physical absorption
Instrument carries out sample specific surface and pore structure study characterizes.By catalyst in 300 DEG C of applications of vacuum 3 hours before measurement, then in liquid
Nitrogen temperature 77K is adsorbed to High Purity Nitrogen and is desorbed.
(4) laboratory pollution of vanadium catalyst method：FCC catalyst and metal traps carry out mechanical mixture by a certain percentage
Afterwards, with vanadyl oxalate aqueous impregnation sample, the addition of vanadyl oxalate calculates according to actual vanadium carrying capacity, impregnated after sample
4h is dried at 120 DEG C, then at 600 DEG C, burns 4h, then at 780 DEG C, burin-in process 4h under 100% water vapor atmosphere, system
Obtain pollution of vanadium sample.
(5) metal traps effect assessment：
Micro-activity adopts the micro- anti-experimental provision of the MAT-11 catalyst that Beijing Wei Kendu Science and Technology Ltd. produces to measure,
Reaction raw materials are huge port straight distillation light diesel oil (235-337 DEG C of fraction), 460 DEG C of reaction temperature, response time 70s, catalyst loading amount
5g, oil inlet quantity 1.56g.Reaction end gas are collected with ice bath condensing tube, weigh, calculate liquid receipts amount.
Reactivity worth is evaluated using the heavy oil microreactor that Beijing Wei Kendu Science and Technology Ltd. produces, use device
Raw materials used oil as evaluation raw oil, aging dose of loadings 5.0g, analyzed by on-line gas chromatography by cracked gas composition,
The hydro carbons composition of product liquid is analyzed by offline chromatograph.
Embodiment 1
(1) 100 gram of dead catalyst A and 800 grams of water making beating, add 150mL oxalic acid-ammonium fluosilicate solution, this solution
H2C2O4/(NH4)2SiF6=8:1, its concentration is with C2O4 2-It is calculated as 100g/L, under room temperature, react 1h.
(2) step (1) is exchanged the serosity finishing to filter, filter cake is pulled an oar with 800 grams of water, adds 240mL magnesium nitrate solution,
Adjusting slurry pH value with hydrochloric acid is 3.1, exchanges 1h under room temperature.
(3) step (2) is exchanged the serosity finishing to filter, and drip washing 53.3mL lanthanum chloride solution, filter cake is dried, and obtains final product mark
Topic thing, is designated as SL-1.
Embodiment 2
(1) 100 gram of dead catalyst B and 850 grams of water making beating, add 300mL oxalic acid-ammonium fluosilicate solution, this solution
H2C2O4/(NH4)2SiF6=4.5:1, its concentration is with C2O4 2-It is calculated as 100g/L, under room temperature, react 2h.
(2) step (1) is exchanged the serosity finishing to filter, filter cake is pulled an oar with 800 grams of water, adds 186.6mL magnesium nitrate molten
Liquid, adjusting slurry pH value with hydrochloric acid is 3.2, exchanges 2h under room temperature.
(3) step (2) is exchanged the serosity finishing to filter, and drip washing 80.0mL lanthanum chloride solution, filter cake is dried, and obtains final product mark
Topic thing, is designated as SL-2.
Embodiment 3
(1) 100 gram of dead catalyst C and 900 grams of water making beating, add 450mL oxalic acid-ammonium fluosilicate solution, this solution
H2C2O4/(NH4)2SiF6=1:1, its concentration is with C2O4 2-It is calculated as 100g/L, under room temperature, react 3h.
(2) step (1) is exchanged the serosity finishing to filter, filter cake is pulled an oar with 800 grams of water, adds 133.3mL magnesium nitrate molten
Liquid, adjusting slurry pH value with hydrochloric acid is 3.2, exchanges 3h under room temperature.
(3) step (2) is exchanged the serosity finishing to filter, and drip washing 100.0mL lanthanum chloride solution, filter cake drying, obtain final product
Title thing, is designated as SL-3.
Comparative example 1
1846 grams of boehmites, 2572 grams of water making beating, add 600 grams of heavy-burned magnesias, stir, add 1.3L chlorine
Change lanthanum solution, 240 grams of 15wt% hydrochloric acid are acidified, and colloid is sprayed, and sample is labeled as DB-1.
Metal traps analysis result such as table 2 below in embodiment and comparative example
Table 2 metal traps analysis of physical and chemical property
Laboratory pollution of vanadium catalyst method：(trade mark AIC-950, Hui Cheng environmental protection science and technology share in Qingdao is limited for FCC catalyst
Company produces) carry out mechanical mixture with metal traps (addition 8.0wt%) after, with vanadyl oxalate aqueous impregnation sample,
The addition of vanadyl oxalate calculates according to actual vanadium carrying capacity, impregnated after sample 4h is dried at 120 DEG C, then at 600 DEG C
Lower burning 4h, then at 780 DEG C, burin-in process 4h under 100% water vapor atmosphere, prepared pollution of vanadium sample.
Pollution of vanadium sample micro-activity adopts the micro- anti-reality of MAT-11 catalyst that Beijing Wei Kendu Science and Technology Ltd. produces
Experiment device measures, and reaction raw materials are huge port straight distillation light diesel oil (235-337 DEG C of fraction), 460 DEG C of reaction temperature, response time 70s,
Catalyst loading amount 5g, oil inlet quantity 1.56g.Reaction end gas are collected with ice bath condensing tube, weigh, calculate liquid receipts amount.Experimental result
It is shown in Table 2:
The trapping effect of metal traps during table 2 different vanadium carrying capacity
Reactivity worth is evaluated using the heavy oil microreactor that Beijing Wei Kendu Science and Technology Ltd. produces, using FCC
As evaluation raw oil, raw material oil nature is shown in Table 3 to the raw materials used oil of device, aging dose of loadings 5.0g, and cracked gas composition is logical
Cross on-line gas chromatography analysis, the hydro carbons composition of product liquid is analyzed by offline chromatograph, and evaluation result is shown in Table 4.
Table 3 raw material oil nature
The micro- converse result of table 4 heavy oil
As shown in Table 4, AIC-950 with the addition of 8% metal traps (SL-1/SL-2/SL-3) intermixture have brighter
Aobvious anti-vanadium effect,, compared with the addition of 8% contrast medium (DB-1), yield of light oil increases by 2.95～3.17% for it, and liquid is received and increased
Plus 2.95～3.05%, the conversion ratio of heavy oil improves 1.57～1.69%, but coke yield reduces by 1.15～1.29%.Therefore logical
Cross this patent method preparation metal traps can effective protection catalyst, reduce the toxic action to catalyst for the vanadium, can be obvious
Improve the yield of valuable product.
Claims (8)
1. a kind of preparation method of metal traps, the method comprises the following steps：
(1) dead catalyst that FCC apparatus unload and water are pulled an oar, and add a certain proportion of oxalic acid-ammonium fluosilicate solution, hand under room temperature
Change 1-3h.
(2) step (1) is exchanged the serosity finishing to filter, filter cake is pulled an oar with water, adds magnesium compound, adjusts serosity pH with hydrochloric acid
Value, between 3.0-3.5, exchanges 1-3h under room temperature.
(3) step (2) is exchanged the serosity finishing to filter, and drip washing rare earth compound solution, filter cake is dried, and obtains final product title thing.
2. preparation method according to claim 1 it is characterised in that：Dead catalyst described in step (1) can be again
The poising agent drawing off or the three rotation fine powders drawing off in raw device.
3. preparation method according to claim 1 it is characterised in that：Described in step (1) and step (2), the ratio of water is
Water/dead catalyst butt=7-10:1.
4. preparation method according to claim 1 it is characterised in that：Oxalic acid-ammonium fluosilicate described in step (1) is molten
Liquid, wherein, H2C2O4/(NH4)2SiF6=0.1-10:1, its concentration is with C2O4 2-It is calculated as 50-120g/L.
5. preparation method according to claim 1 it is characterised in that：Oxalic acid-ammonium fluosilicate solution described in step (1)
Additional proportion is with C2O4 2-Meter, its C2O4 2-The mass ratio of/dead catalyst butt is 0.01-0.5:1.
6. preparation method according to claim 1 it is characterised in that：Magnesium compound described in step (2) be magnesium chloride,
Magnesium nitrate and/or magnesium sulfate, preferably magnesium nitrate, the additional proportion dead catalyst butt of MgO/ in terms of MgO=20-36wt%：1.
7. preparation method according to claim 1 it is characterised in that：Rare earth compound described in step (3) is chlorination
Lanthanum, cerium chloride and/or lanthanum-cerium chloride, preferably lanthanum chloride, additional proportion is with RE2O3Meter RE2O3/ dead catalyst butt=8-
15wt%：1.
8. preparation method according to claim 1 it is characterised in that：Rare earth compound solution described in step (3)
Concentration is with RE2O3Meter 100-150g/L.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112973786A (en) * | 2021-02-08 | 2021-06-18 | 润和催化材料(浙江)有限公司 | Reactivation method of high-vanadium low-rare earth catalytic cracking balancing agent |
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| CN114768783A (en) * | 2022-05-21 | 2022-07-22 | 山西腾茂科技股份有限公司 | Modification and recycling method of FCC (fluid catalytic cracking) waste catalyst |
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