CN1879960A - Heavy metal resistant catalytic cracking adjuvant and process for preparing same - Google Patents
Heavy metal resistant catalytic cracking adjuvant and process for preparing same Download PDFInfo
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- CN1879960A CN1879960A CN 200510076790 CN200510076790A CN1879960A CN 1879960 A CN1879960 A CN 1879960A CN 200510076790 CN200510076790 CN 200510076790 CN 200510076790 A CN200510076790 A CN 200510076790A CN 1879960 A CN1879960 A CN 1879960A
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Abstract
The invention relates to a FCC agent of solid anti-heavy metal and relative preparation, wherein it is characterized in that: the agent comprises Na2O at 0.3-0.8%, Al2O3 at 35-50%, MgO at 1-10% and RE2O3 at 1-10%; said agent has high specific surface and porous volume, stable structure and flexible application; the inventive preparation comprises: using caoline as raw material; when pulping caoline, adding additive and magnesia or its precursor, to be sprayed into micro balls; the micro ball is mainly at 40-80micrometer; the micro ball is baked at 900-1100Deg. C; the baked micro ball via alkali solution is extracted and washed to deposit sodium; processing it with rare earth precursor, to obtain the FCC agent. The invention can improve the reaction activity of FCC base agent.
Description
Technical field
The present invention is assistant for calalytic cracking of a kind of preventing from heavy metal and preparation method thereof, is suitable for the higher catalytic cracking unit of nickel content of vanadium in the charging.
Background technology
Along with the world's crude oil heaviness and poor qualityization day by day, the refinery, various countries all greatly develops fluid catalytic cracking (FCC) technology of mixing refining or refining heavy oil and residual oil entirely, to widen FCC feedstock oil source, satisfy the demand of world market to light-end products, increase economic efficiency to greatest extent.(as AGO and VGO) compares with conventional FCC feedstock oil, tenors such as Ni, V, Fe, Cu are obviously higher in residual oil or the heavy oil, severe contamination FCC catalyst, and what wherein have the greatest impact is nickel and vanadium, they are deposited on the catalyst, cause the catalyst cracking activity to descend, the selectivity of product variation, yield of gasoline reduces, hydrogen output rises in the dry gas, coke content increases, and can also make molecular sieve structure cave in the catalyst complete deactivation when content of vanadium is very high.In addition, nickel and vanadium also can cause the gas compressor and the air blast excess load of FCC apparatus, and regenerator temperature improves, and fresh catalyst replenishes and speeds up, and increases energy consumption, reduces the FCC apparatus conversion per pass.Therefore, in the development of whole fluid catalytic cracking, the metallic pollution of catalyst is a problem that comes into one's own always.The key that solves metallic pollution is exactly to suppress the pollution to catalyst of nickel and vanadium, can be by improving approach such as technical process, the anti-metal ability that improves catalyst and applied metal passivator, wherein using passivator is to address the above problem most economical and extensive effective method.This method also is to improve the important means of the catalyst market competitiveness simultaneously.
US 5147836, US 5304526, US5306417 are the Ni/V trapping agent of Davison company exploitation, and it is to use SiO
2Bayerite/ η-the Al of modification
2O
3, have very high hydrothermal stability, heavy metal Ni/V there is passivation ability preferably.
US 5300469 is the vanadium assistants of catching of Engelhard company exploitation, it is with fine grained, low surperficial MgO, kaolin and waterglass are that raw material mixes, wear out a night at normal temperatures and pressures, magnesia sub-fraction original position of introducing in the system and sodium metasilicate have formed the amorphous silicic acid magnesium with adhesive property, most of magnesia does not react with sodium metasilicate, to reach heavy metal-passivated effect, this particle has low specific surface and minimum cracking activity, adding Ludox or kaolin or the two after aging in this particle adds simultaneously, after spray-dried, roasting under the condition of gentleness, the condition of roasting is to make the kaolin dehydration change into metakaolin, will avoid or maximize the formation that reduces crystallization magnesium silicate or magnesium aluminate simultaneously, so promptly can be made into vanadium traps, this agent has the higher vanadium ability of catching, when vanadium reached 5500ppm on poising agent, vanadium traps made the activity of poising agent improve 4 units.The key point of this patented technology has avoided magnesium silicate only to exist in one way exactly, and another key problem in technology point is exactly in the temperate condition roasting, even kaolin changes into metakaolin.
US 5141624 is patents of invention of Phillips company exploitation, what this invention related to is the process of a catalytic cracking, set about from technology and catalyst two aspects, from the angle of catalyst, it mainly is that aluminium oxide with Large ratio surface and big hole body is as carrier, above magnesium acetate is impregnated into, after the drying, the catalyst B component that is loaded with MgO on the aluminium oxide is made in roasting, mix with the A component that contains zeolite molecular sieve and carrier, come trap heavy metals.
EP 176150 be Catalyst/Chemical Co., Ltd exploitation handle Al with P
2O
3Catch the Ni/V agent, when it and FCC catalyst are used, activity of such catalysts when having improved Ni/V and polluting, yield of gasoline improves greatly, H
2Descend with coke.
Prior art is all in the function of the trap heavy metals nickel vanadium that has strengthened catalyst in varying degrees, but the common drawback that exists is, prepared auxiliary agent or at the poor stability of catalyst, the effective active of major catalyst is reduced, thereby can have influence on the reactivity worth of major catalyst.
Summary of the invention
Purpose of the present invention is exactly the deficiency that is to avoid above-mentioned technology, and assistant for calalytic cracking of a kind of preventing from heavy metal and preparation method thereof is provided.
A kind of assistant for calalytic cracking of preventing from heavy metal, be to adopt the kaolin slurry spray shaping to become kaolin microsphere, kaolin microsphere through 900～1100 ℃ of roastings after, carry out in alkaline system that the alkali extracting makes, it is characterized in that in the auxiliary agent that (as follows) contains Na by weight percentage
2O0.3～0.8%, Al
2O
335～50%, MgO1～10%, RE
2O
31～10%, specific surface is 120～200m
2/ g, pore volume are 0.12～0.30ml/g.
The present invention also provides a kind of method for preparing the assistant for calalytic cracking of this preventing from heavy metal: after kaolin is added water, additive and magnesia or the making beating evenly of its precursor, carry out spray drying forming, make kaolin microsphere, atomized microball is made the roasting microballoon at 900～1100 ℃ of roasting temperatures, the roasting kaolin microballoon is carried out the alkali extracting in alkali lye, extract product removes by filter mother liquor, wash again and fall sodium, after the precursor of mixed rare-earth oxide is handled, can obtain the FCC auxiliary agent of novel solid preventing from heavy metal.
Concrete preparation method is as follows:
(1) kaolin spraying
Kaolin is added water, and to make solid content be 20～55% slurries, add 1～10% additive, additive is generally dispersant, binding agent, add 1～10% magnesia or its precursor, make atomized microball after the spray-dried moulding, this atomized microball size is generally 20～111 μ m, the overwhelming majority at 40～80 μ m.The general inlet temperature of spray tower is 700～800 ℃, and outlet temperature is 120～400 ℃.
(2) roasting
Atomized microball was 900～1100 ℃ of following roastings 0.5～4 hour, kaolin microsphere is changed into based on spinelle and with the roasting microballoon of mullite on a small quantity through the heat release phase transformation, mullite content had better not surpass 20% in the roasting microballoon, is preferably lower than 16%, and abrasion index is less than 4%.
(3) aqueous slkali extracting
The kaolin roasting microballoon that step (2) is obtained in 70～95 ℃ of alkali extractings 1～10 hour, obtains extract product under stirring.
(4) washing
The extract product that step (3) is obtained removes by filter mother liquor, washes and falls sodium, the extract product after can obtaining washing.
(5) rare earth is handled
Add the precursor of rare earth oxide in the washing extract product that step (4) obtains, the pH value of regulation system makes them in 6.0～9.0 scopes, 20～90 ℃ of temperature, and time 10～90min, its addition is counted with its rare earth oxide weight: RE
2O
3/ microballoon=0.01～0.10, product are after filtration, drying can get the auxiliary agent of preventing from heavy metal FCC of the present invention.
Kaolin of the present invention comprises soft kaolin, hard Raolinite, gangue, its meso-position radius generally be not higher than 4.0 μ m, crystal kaolinite content greater than 80%, quartz is lower than 1.2%, iron oxide is lower than 1.0%, sodium oxide molybdena and potassium oxide sum are lower than 0.6%.
Additive of the present invention can be dispersant, bonding agent, comprises sodium metasilicate, NaOH, sodium pyrophosphate, calgon, sodium carbonate etc., can be one or more, and its addition is 1～10% of a kaolin quality.
Magnesia of the present invention or its precursor comprise light magnesium oxide powder, magnesium hydroxide, magnesium chloride etc.
The used solution of the described alkali extracting of step of the present invention (3) is NaOH, and its concentration is 10～30%.
The Na that makes extract product behind the sodium falls in the washing of the described method of step of the present invention (4)
2O content is lower than 0.8%, General N a
2O is 0.3～0.8%.
The precursor of the described rare earth oxide of step of the present invention (5) can be one or more in mixed chlorinated rare earth, the mixeding acid rare-earth.
Major advantage of the present invention and effect:
In the preparation of auxiliary agent, owing to introduce magnesia before having adopted the kaolin spraying, atomized microball is in 900～1100 ℃ of following roastings of process kaolin, part magnesia forms Magnesiumaluminumsilicate, a part with magnesian independent phase form exist (from Fig. 2 kaolin with add behind the magnesia XRD spectra after 950 ℃ of following roastings as can be seen), make the ability that has good capture nickel vanadium in the auxiliary agent; Kaolin makes the roasting kaolin microballoon have bigger pore volume and specific surface after the alkali extracting in addition; The microballoon of alkali extracting simultaneously makes that to catch the vanadium component in the auxiliary agent more abundant after rare earth is handled.Adopt this preparation method, existing trap heavy metals component has possessed the required high-quality matrix of additional residual oil cracking process again simultaneously, makes it both have good trap heavy metals ability, and the performance that improves cracking mink cell focus ability is arranged again.
Description of drawings
Fig. 1 be in the Comparative Examples 1 kaolin with add the XRD spectra after 800 ℃ of following roastings behind the magnesia;
Fig. 2 is the XRD spectra after 950 ℃ of following roastings behind kaolin of the present invention and the adding magnesia.
The specific embodiment
Further specify characteristics of the present invention with embodiment below, but the present invention is not limited in these examples.
(1) used analytical test assessment method in the embodiment of the invention.
1. sodium oxide content: flame spectrometry.
2. alumina content: compleximetry.
3. content of magnesia: x-ray fluorescence method.
4. rare earth oxide content: colorimetric method.
5. specific surface: thermal desorption chromatography.
6. pore volume: carbon tetrachloride absorption method.
7. abrasion index: gas lift method.
8. bulk density: graduated cylinder method.
9. meso-position radius: laser particle analyzer method.
10. mullite content: X-ray diffraction method.
11. micro-activity performance evaluation: adopt miniature fixed bed reaction method to measure.Feedstock oil adopts the huge port light diesel fuel, and assessing terms is: catalyst is through aging 4 hours of 800 ℃, 100% steam, 460 ℃ of temperature, 70 seconds oil-feed time.
12. cracking reaction performance evaluation: adopt the small fixed flowing bed device to carry out the cracking reaction evaluation.Catalyst is through 800 ℃, 100% steam after aging 10 hours, is raw material with the Xinjiang decompression residuum of 70% Xinjiang decompression long distillate oil and 30%, 500 ℃ of reaction temperatures, and oil ratio is 4.0, air speed 15h
-1
13. the method for pollution of vanadium: dissolved solid ammonium metavanadate in 3% oxalic acid solution, be mixed with the solution that content of vanadium is 5mg/g, the ratio that in the auxiliary agent content of vanadium is 0.5-0.8% joins ammonium metavanadate solution in the sample, it is saturated that the adding low amounts of water is adsorbed to catalyst, leaves standstill 4 hours, 540 ℃ roastings of 16 hours, 120 ℃ dryings and got the pollution of vanadium sample in 4 hours under room temperature.
14. the method for nickel contamination: be mixed with nickel content and be 3.74% nickel nitrate solution, in auxiliary agent nickel content is that the ratio of 0.5-0.8% joins nickel nitrate solution in the sample, it is saturated that the adding low amounts of water is adsorbed to catalyst, leaves standstill 4 hours, 540 ℃ roastings of 16 hours, 120 ℃ dryings and got the nickel contamination sample in 4 hours under room temperature.
(2) raw materials used specification in the embodiment of the invention
1. Suzhou kaolin: industrial goods.Suzhou soil is based on kaolinite, contains a small amount of first feldspar, hydromica and quartz, meso-position radius 2.6 μ m, crystal kaolinite content 85%, quartz 1.0%, iron oxide 0.56%, sodium oxide molybdena 0.07%, potassium oxide 0.42%.
2. Hancheng kaolin: industrial goods.Hancheng soil is based on kaolinite, contains a small amount of A-TiO
2And rutile, contain the minute quantity quartz, meso-position radius 2.2 μ m, crystal kaolinite content 82%, quartz 0.1%, iron oxide 0.94%, sodium oxide molybdena 0.07%, potassium oxide 0.46%.
3. Guizhou kaolin: industrial goods.Guizhou clay is based on galapectite, contains a small amount of gibbsite, and meso-position radius 3.1 μ m, quartz do not detect, iron oxide 0.27%, sodium oxide molybdena 0.03%, potassium oxide 0.12%.
4. sodium metasilicate: industrial goods contain 19.84% SiO
2, 6.98% Na
2O, modulus is 2.9～3.1.
5. sodium pyrophosphate: solid, chemical reagent.
6. light magnesium oxide: solid, chemical reagent.
7. magnesium hydroxide: solid, chemical reagent.
8. magnesium chloride: solid, chemical reagent.
9. mixed chlorinated rare earth: industrial goods.RE
2O
3Concentration 150～250g/l.
10. bodying agent 1:LCS-7B takes from Lanzhou petrochemical industry catalyst plant, and character sees Table 2.
11. bodying agent 2:LANK-98 takes from Lanzhou petrochemical industry catalyst plant, character sees Table 2.
Embodiment 1
With 5kg (butt) meso-position radius is that the Suzhou kaolin of 2.6 μ m adds water to make solid content is 38% slurries, add the 1400ml sodium metasilicate as additive, and adding 250g light magnesium oxide, spray shaping is a kaolin microsphere, altogether the kaolin atomized microball of 3.9kg, atomized microball 980 ℃ of roastings in Muffle furnace were got the roasting kaolin microballoon in 3 hours, wherein contain 10% mullite, abrasion index is 1.0%.Under stirring roasting microballoon 500g put in the stainless steel reactor and NaOH alkali lye hybrid reaction, be warming up to 90 ℃ and constant temperature 2 hours, extracting removes by filter mother liquor after finishing, and washs to Na
2O 0.63%, adds in the washing material and contains 37.7g RECl
3Mixed chlorinated rare earth solution, regulate the pH value with ammoniacal liquor, pH=6.9,60 ℃ of temperature, time 30min, product are after filtration, be auxiliary agent A after the drying.
Embodiment 2
With 2kg (butt) meso-position radius is that the Hancheng kaolin of 2.2 μ m adds water to make solid content is 42% slurries, add the 240g sodium pyrophosphate as additive, and adding 332g magnesium chloride, spray shaping is a kaolin microsphere, altogether the kaolin atomized microball of 1.7kg, atomized microball 1050 ℃ of roastings in Muffle furnace were got the roasting kaolin microballoon in 2 hours, wherein contain 12% mullite, abrasion index is 0.5%.Under stirring roasting microballoon 1500g put in the stainless steel reactor and NaOH alkali lye hybrid reaction, be warming up to 70 ℃ and constant temperature 5 hours, extracting removes by filter mother liquor after finishing, and washs to Na
2O 0.52%, adds in the washing material and contains 67.9g RECl
3Mixed chlorinated rare earth solution, regulate the pH value with ammoniacal liquor, pH=8.1,90 ℃ of temperature, time 10min, product are after filtration, be auxiliary agent B after the drying.
Embodiment 3
With 4kg (butt) meso-position radius is that the Suzhou kaolin of 2.6 μ m adds water to make solid content is 35% slurries, add 160ml sodium metasilicate and 70g sodium carbonate as additive, and adding 116g magnesium hydroxide, spray shaping is a kaolin microsphere, altogether the kaolin atomized microball of 2.8kg, atomized microball 990 ℃ of roastings in muffle furnace were got the roasting kaolin microballoon in 3 hours, wherein contain 8% mullite, abrasion index is 0.7%.Under stirring roasting microballoon 200g put in the stainless steel reactor and NaOH alkali lye hybrid reaction, be warming up to 80 ℃ and constant temperature 3 hours, extracting removes by filter mother liquor after finishing, and washs to Na
2O 0.50%, adds in the washing material and contains 24.2g RECl
3Mixed chlorinated rare earth solution, regulate the pH value with ammoniacal liquor, pH=8.6,25 ℃ of temperature, time 60min, product are after filtration, be auxiliary agent C after the drying.
Embodiment 4
With 1kg (butt) meso-position radius is that the Guizhou kaolin of 3.1 μ m adds water to make solid content is 37% slurries, add 50g NaOH as additive, and adding 90g light magnesium oxide, spray shaping is a kaolin microsphere, altogether the kaolin atomized microball of 720g, atomized microball 960 ℃ of roastings in muffle furnace were got the roasting kaolin microballoon in 2 hours, wherein contain 5% mullite, abrasion index is 0.9%.Under stirring roasting microballoon 100g put in the stainless steel reactor and NaOH alkali lye hybrid reaction, be warming up to 85 ℃ and constant temperature 1 hour, extracting removes by filter mother liquor after finishing, and washs to Na
2O 0.68%, adds in the washing material and contains 5.0g RECl
3Mixed chlorinated rare earth solution, regulate the pH value with ammoniacal liquor, pH=7.6,50 ℃ of temperature, time 45min, product are after filtration, be auxiliary agent D after the drying.
Comparative Examples 1
Kaolin atomized microball 800 ℃ of roastings in Muffle furnace of embodiment 1 gained were got the roasting kaolin microballoon in 3 hours, and abrasion index is 4.6%.Under stirring roasting microballoon 500g put in the stainless steel reactor and NaOH alkali lye hybrid reaction, be warming up to 90 ℃ and constant temperature 2 hours, extracting removes by filter mother liquor after finishing, and washs to Na
2O 0.56%, adds in the washing material and contains 37.7g RECl
3Mixed chlorinated rare earth solution, regulate the pH value with ammoniacal liquor, pH=6.9,60 ℃ of temperature, time 30min, product are after filtration, be contrast medium 1 after the drying.
Comparative Examples 2
With 5kg (butt) meso-position radius is that the Suzhou kaolin of 2.6 μ m adds water to make solid content is 38% slurries, add the 1400ml sodium metasilicate as additive, spray shaping is a kaolin microsphere, altogether the kaolin atomized microball of 3.7kg, atomized microball 980 ℃ of roastings in Muffle furnace were got the roasting kaolin microballoon in 3 hours, wherein contain 9% mullite, abrasion index is 1.2%.Under stirring roasting microballoon 500g put in the stainless steel reactor and NaOH alkali lye hybrid reaction, be warming up to 90 ℃ and constant temperature 2 hours, extracting removes by filter mother liquor after finishing, and washs to Na
2O 0.57%, will wash the material adding and contain 37.7g RECl
3Mixed chlorinated rare earth solution, regulate the pH value with ammoniacal liquor, pH=6.9,60 ℃ of temperature, time 30min, product are after filtration, be contrast medium 2 after the drying.
Investigate various auxiliary agents and commercial FCC catalyst (bodying agent) reactivity and the cracking performance after composite, the addition of auxiliary agent is adjusted in the 1-20% scope, and the physicochemical property of auxiliary agent and base catalyst sees Table 1 respectively, table 2.Through 0.75% vanadium and 0.75% nickel contamination, wherein the addition of auxiliary agent is defined as 15% respectively for bodying agent and composite dose (auxiliary agent and bodying agent), and its active test result sees Table 3, the cracking reaction performance the results are shown in Table 4.
Table 3 result shows behind the composite a certain amount of auxiliary agent of the present invention of major catalyst, when having polluted the nickel vanadium of high-load, can obviously improve the catalytic activity of major catalyst, and auxiliary agent has demonstrated stronger anti-nickel vanadium performance.
Table 4 demonstrate auxiliary agent of the present invention and bodying agent composite after, can improve the selectivity such as gasoline, coke, dry gas of crackate, be a kind of good preventing from heavy metal auxiliary agent.
The physicochemical property of table 1 auxiliary agent
| Numbering | Auxiliary agent A | Auxiliary agent B | Auxiliary agent C | Auxiliary agent D |
| Na 2O m％ Al 2O 3 m％ MgO m％ RE 2O 3M% abrasion index m% bulk density g/ml specific surface m 2/ g pore volume ml/g | 0.50 43.61 4.72 4.87 1.0 0.81 163 0.23 | 0.46 43.12 6.53 2.73 0.8 0.78 176 0.20 | 0.43 43.45 1.74 7.76 0.7 0.80 158 0.22 | 0.52 42.15 8.74 3.23 0.9 0.85 145 0.21 |
The physicochemical property of table 2 bodying agent (uncontaminated)
| Catalyst | Bodying agent-1 | Bodying agent-2 |
| Na 2O m％ Al 2O 3M% abrasion index m% bulk density g/ml specific surface m 2The little m% alive of/g pore volume ml/g | 0.42 29.6 2.0 0.67 254 0.26 73 | 0.27 51.9 1.4 0.74 306 0.13 76 |
Table 3 auxiliary agent is to the influence of activity
(vanadium: 7500ppm; Nickel: 7500ppm)
| Host | Auxiliary agent | Little m% alive, 800 ℃ of 4h |
| Bodying agent-1 | Auxiliary agent A | 49 |
| Adding assistant not | 39 | |
| Bodying agent-2 | | 45 |
| Adding assistant not | 38 |
The influence that table 4 auxiliary agent distributes to product
| Catalyst | Bodying agent 2+ auxiliary agent A of the present invention | Bodying agent 2 |
| Dry gas m% liquefied gas m% gasoline m% diesel oil m% heavy oil m% coke m% conversion ratio m% | 2.55 15.33 47.94 13.38 8.74 7.48 73.30 | 2.30 14.69 47.71 12.54 9.43 7.52 72.22 |
The magnesian introducing of table 5 is for the preventing from heavy metal Effect on Performance
(vanadium: 7500ppm; Nickel: 7500ppm)
| Host | Auxiliary agent | Little m% alive, 800 ℃ of 4h |
| Bodying agent-1 | Auxiliary agent A | 49 |
| Contrast medium 1 | 40 | |
| Contrast medium 2 | 41 | |
| Adding assistant not | 39 |
Claims (9)
1. the assistant for calalytic cracking of a preventing from heavy metal, be to adopt the kaolin slurry spray shaping to become kaolin microsphere, kaolin microsphere through 900～1100 ℃ of roastings after, carry out in alkaline system that the alkali extracting makes, it is characterized in that in the auxiliary agent containing Na by weight percentage
2O 0.3～0.8%, Al
2O
335～50%, MgO 1～10%, RE
2O
31～10%, specific surface is 120～200m
2/ g, pore volume are 0.12～0.30ml/g.
2. the preparation method of the described assistant for calalytic cracking of claim 1, after it is characterized in that kaolin added the making beating evenly of water, additive and magnesia or its predecessor, carry out spray drying forming, make kaolin microsphere, atomized microball is made the roasting microballoon at 900～1100 ℃ of roasting temperatures, the roasting kaolin microballoon is carried out the alkali extracting in alkali lye, extract product removes by filter mother liquor, wash again and fall sodium, obtain assistant for calalytic cracking after filtration after the precursor of mixed rare-earth oxide is handled, the drying.
3. preparation method according to claim 2 is characterized in that kaolin microsphere is meant and kaolin is added water to make solid content be 20～55% slurries that add additive, magnesia or its precursor in slurries, spray drying forming is a microballoon.
4. preparation method according to claim 2, it is characterized in that the aqueous slkali extracting be meant the kaolin roasting microballoon that will obtain under stirring in 70～95 ℃ of alkali extractings 1～10 hour, obtain extract product.
5. preparation method according to claim 2 is characterized in that washing extract product and handles in pH6.0～9.0 scopes with the precursor of rare earth oxide, 20～90 ℃ of temperature, and its addition is counted with its rare earth oxide weight: RE
2O
3/ microballoon=0.01～0.10.
6. according to claim 2 or 3 described methods, it is characterized in that kaolin comprises soft kaolin, hard Raolinite, gangue, its meso-position radius is not more than 4.0 μ m, kaolinite content greater than 80%, quartz is lower than 1.2%, iron oxide is lower than 1.0%, sodium oxide molybdena and potassium oxide sum are lower than 0.6%.
7. according to claim 2 or 3 described methods, it is characterized in that additive comprises one or more in sodium metasilicate, NaOH, sodium pyrophosphate, calgon, the sodium carbonate.
8. according to claim 2 or 3 described methods, it is characterized in that magnesia comprises the light magnesium oxide powder.
9. according to claim 2 or 3 described methods, it is characterized in that the magnesia precursor comprises magnesium hydroxide, magnesium chloride.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103789013A (en) * | 2012-10-29 | 2014-05-14 | 中国石油化工股份有限公司 | Metal chelating agent, preparation method and application thereof, and catalytic cracking method |
| CN103785370A (en) * | 2012-10-29 | 2014-05-14 | 中国石油化工股份有限公司 | Metal chelating agent, preparation method and application thereof, and catalytic cracking method |
| CN103789014B (en) * | 2012-10-29 | 2016-03-02 | 中国石油化工股份有限公司 | A kind of metal traps and its preparation method and application and a kind of catalyst cracking method |
| CN115430413A (en) * | 2022-08-30 | 2022-12-06 | 青岛惠城环保科技集团股份有限公司 | Preparation method of kaolin-based metal trapping agent |
| CN115555011A (en) * | 2022-08-24 | 2023-01-03 | 碳中能源科技(北京)有限公司 | Auxiliary agent for improving heavy metal pollution resistance of FCC (fluid catalytic cracking) catalyst |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0122572A3 (en) * | 1983-04-13 | 1985-01-23 | W.R. Grace & Co. | Catalysts and catalyst supports |
| US5300469A (en) * | 1992-12-08 | 1994-04-05 | Engelhard Corporation | Composition for passivating vanadium in catalytic cracking and preparation thereof |
| CN1334314A (en) * | 2000-07-19 | 2002-02-06 | 中国石油天然气股份有限公司兰州炼化分公司 | Vanadium-resistant catalytic cracking assistant containing Y-type molecular sieve and its preparing process |
| US6673235B2 (en) * | 2000-09-22 | 2004-01-06 | Engelhard Corporation | FCC catalysts for feeds containing nickel and vanadium |
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| CN103789013A (en) * | 2012-10-29 | 2014-05-14 | 中国石油化工股份有限公司 | Metal chelating agent, preparation method and application thereof, and catalytic cracking method |
| CN103785370A (en) * | 2012-10-29 | 2014-05-14 | 中国石油化工股份有限公司 | Metal chelating agent, preparation method and application thereof, and catalytic cracking method |
| CN103789013B (en) * | 2012-10-29 | 2015-11-25 | 中国石油化工股份有限公司 | A kind of metal traps and its preparation method and application and a kind of catalyst cracking method |
| CN103789014B (en) * | 2012-10-29 | 2016-03-02 | 中国石油化工股份有限公司 | A kind of metal traps and its preparation method and application and a kind of catalyst cracking method |
| CN103785370B (en) * | 2012-10-29 | 2016-05-25 | 中国石油化工股份有限公司 | A kind of metal traps and its preparation method and application and a kind of catalyst cracking method |
| CN115555011A (en) * | 2022-08-24 | 2023-01-03 | 碳中能源科技(北京)有限公司 | Auxiliary agent for improving heavy metal pollution resistance of FCC (fluid catalytic cracking) catalyst |
| CN115430413A (en) * | 2022-08-30 | 2022-12-06 | 青岛惠城环保科技集团股份有限公司 | Preparation method of kaolin-based metal trapping agent |
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