CN108097264A - A kind of preparation method of catalyst cracking combustion-supporting agent - Google Patents
A kind of preparation method of catalyst cracking combustion-supporting agent Download PDFInfo
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Abstract
The present invention relates to a kind of preparation method of catalyst cracking combustion-supporting agent, step is：Platiniferous is selected to give up agent residue as raw material, crushes, is mixed with inorganic acid solution, adds organic acid, dry when standing 68 is small, roasting obtains catalyst；Using the catalyst as carrier, impregnated with the solution of one or several kinds of water soluble salts in copper, magnesium, tin, titanium, cobalt, the chloride of nickel, nitrate, acetate, be then dried to obtain catalyst cracking combustion-supporting agent.Acid treated FCC dead catalyst provided by the invention prepares catalyst cracking combustion-supporting agent for carrier, cost is relatively low, process is simple, itself has higher catalytic cracking activity and selectivity, and the performance and product of major catalyst in catalytic cracking process will not be distributed and impacted.
Description
Technical field
The present invention relates to solid waste to handle application field, particularly discloses a kind of platinum content by discarding and is
The useless agent residue of 0.06-0.1% is as raw material, the method for preparing catalyst cracking combustion-supporting agent.
Background technology
Heat caused by catalytic cracking catalyst regeneration, a part can be supplied to reactor to be used as raw material by catalyst
Heat source necessary to cracking.Coke burning heat be for technique heat source it is essential, but green coke amount number, to urging
Large effect can be generated by changing cracking operation.When green coke amount is more, regenerator air blower load increase, since the burning of coke can make
Regeneration temperature raises, and catalyst activity reduces, the CO contents rise in exhaust.When green coke amount is few, combustion heat deficiency, regeneration temperature
Low, regeneration is incomplete, and reaction temperature reduces.The measure taken is to reduce stripping vapor, and the combustion oil in regenerator improves regeneration
Efficiency.In order to reduce the carbon residue on catalyst, improve regeneration temperature, using CO combustion adjuvants, the CO parts in exhaust or
CO2 is completely converted into, temperature is improved and promotes coke burning.CO completely burneds can reduce regeneration to greatest extent and urge
The carbon content of agent reduces exhaust combustion and the discharge capacity of CO and SOx.Because regenerator temperature limitation does not allow CO completely burneds
When, combustion adjuvant can be added to realize the part burning of CO, and control the Excess oxygen content of flue gas simultaneously.
At present, catalyst cracking combustion-supporting agent is mainly using precious metal elements such as platinum, palladium, osmium, iridium, ruthenium, rhodium, silver, rheniums as work
Property component, wherein with the most widely used of platinum and palladium, most common carrier is aluminium oxide (CN 1032025A) United States Patent (USP)
USP4181600 discloses a kind of preparation method of catalyst cracking combustion-supporting agent, and this method is by noble-metal-supported in a part without place
The fresh cracking catalyst of reason, then with being used in mixed way for the cracking agent of carried noble metal, and United States Patent (USP) USP4097410 is then
Disclose a kind of catalytic cracking catalyst synthetic method containing combustion adjuvant, this method is by the superstable gamma-type molecule containing noble metal
The mixture of sieve and rare earth X-type or Y type molecular sieve, which is supported in inorganic oxide or clay carrier, makes Cracking catalyst.
CN1049301 discloses a kind of synthetic method of noble metal support type CO combustion adjuvants, and this method is aoxidizing noble-metal-supported
Aluminium-rare earth oxide-zirconium oxide composition meets on oxide carrier.CN 1179463 discloses a kind of carbon monoxide and helps
Fire agent and preparation method thereof, active component is platinum and palladium, carrier can be screened processing catalytic cracking equilibrium catalyst,
Dead catalyst, aging catalyst and the gasifying-aid agent of aging, octane-enhancing additive.CN 102430402A disclose a kind of catalytic cracking and help
The preparation method of agent is fired, catalyst cracking combustion-supporting agent is prepared as carrier using acid treated FCC dead catalyst, to solid waste
Rational recycling is carried out.Gained catalyst cracking combustion-supporting agent itself has higher catalytic cracking activity and selectivity, no
Performance and the product distribution of major catalyst in catalytic cracking process can be impacted；It but more or less can there are certain poison
Property, endanger people's health.
The content of the invention
It is an object of the present invention to overcome the above-mentioned technical problems, and to provide a kind of preparation method of catalyst cracking combustion-supporting agent,
Its activity recovery is made to FCC dead catalyst pickling processes, then combustion adjuvant is prepared using it as carrier again, is roasted in specific crucible
It burns, will so substantially increase the catalytic cracking activity and selectivity of combustion adjuvant, adding in catalytic cracking unit will substantially will not be right
Product yield and the product distribution of catalytic cracking impact, and safe and non-toxic, health discharge.
The technical solution for solving above-mentioned technical problem is as follows：
A kind of preparation method of catalyst cracking combustion-supporting agent, comprises the following steps：
1) it is raw material to select the useless agent residue that platinum content is 0.06-0.1%, and grain size is crushed to less than 30 μm with pulverizer,
The inorganic acid solution for being 3-4 with pH value is mixed, and when stirring 10-12 is small at normal temperatures, then adds in organic acid thereto, stirs
When 1-2 is small, stand 6-8 it is small when, when 110 DEG C of dry 2-5 are small, 350-750 DEG C roast 1-3 it is small when obtain catalyst, it is described
Inorganic acid solution：Organic acid soln：The weight ratio for the useless agent residue that platinum content is 0.06-0.1% is (5-8):(2-4):1；
2) using the catalyst after above-mentioned roasting as carrier, with copper, magnesium, tin, titanium, cobalt, the chloride of nickel, nitrate, vinegar
When the solution dipping 8-12 of one or several kinds of water soluble salts in hydrochlorate is small, catalyst cracking combustion-supporting agent is then dried to obtain.
It further says, the inorganic acid is one kind in aqueous hydrochloric acid solution, aqueous solution of nitric acid and aqueous sulfuric acid
Or several mixture.
It further says, the organic acid soln is any one in formic acid, tartaric acid, citric acid or oxalic acid.
Further say, it is a kind of or several in the copper, magnesium, tin, titanium, cobalt, the chloride of nickel, nitrate, acetate
The GOLD FROM PLATING SOLUTION category content of kind water soluble salt is the 0.1% of catalyst cracking combustion-supporting agent quality.
It further says, the roasting is that dried powder is put into graphite crucible to carry out, the rate of heat addition 20
℃/min。
Furthermore, for the graphite crucible inner wall covered with anti-sticking internal layer, dustproof cover is stamped at top, and graphite crucible is
Silicon ash is added in calcined petroleum coke particulate material, is crushed, the quality of silicon ash is the 1%-5% of material quality；The calcining stone
The formula of oil coke particulate material is：Grain graininess is 5~10mm: 30%~40%；Grain graininess for 11~15mm: 60%~
70%；Broken calcined petroleum coke particulate material and silicon ash are added in kneading pot and stirred, then liquid drip is added in kneading pot
Green grass or young crops continues to stir, and pitch is made to infiltrate petroleum coke particles；Using vacuum vibration formula pressure forming machine, molding vacuum degree for-
0.008MPa, crucible green compact are put into crucible roasting furnace carry out roasting 2-5 it is small when, it is ensured that crucible green compact in roasting process not
Deformation, obtains roasting product crucible；Roasting product crucible is fitted into impregnating autoclave, is vacuumized in tank, adds liquid asphalt, then into tank
Pressurization, pressure 1MPa go out after tank up to dipping crucible；Crucible graphite will be impregnated, obtains graphite crucible, and it is anti-in inner wall coating
It glues internal layer and adds dustproof cover in crucible top, obtain last graphite crucible.
The beneficial effects of the invention are as follows：
Acid treated FCC dead catalyst provided by the invention prepares catalyst cracking combustion-supporting agent for carrier, cost itself
Relatively low, the process of preparation is also fairly simple, and rational recycling has been carried out to solid waste.Gained catalytic cracking of the invention
Combustion adjuvant itself has higher catalytic cracking activity and selectivity, will not to the performance of major catalyst in catalytic cracking process and
Product distribution impacts.Also, since calcination steps carry out in specific crucible, will so it substantially increase combustion adjuvant
Catalytic cracking activity and selectivity, will substantially the product yield and product of catalytic cracking will not be distributed by adding in catalytic cracking unit
It impacts, and it is safe and non-toxic, and health discharge, hydrothermal stability is preferable, and the treatment industry of solid waste is made
Contribution, is worthy to be popularized.
The present invention will be further described in detail with reference to the specific embodiments.
Specific embodiment
Embodiment 1：
A kind of preparation method of catalyst cracking combustion-supporting agent, comprises the following steps：
1) it is raw material to select the useless agent residue that platinum content (mass content) is 0.06-0.1%, and grain size is crushed to pulverizer
Less than 30 μm, the inorganic acid solution for being 3-4 with pH value is mixed, and when stirring 10 is small at normal temperatures, then adds in thereto organic
Acid, when stirring 1 is small, when standing 6 is small, when 110 DEG C of dryings 2 are small, 350 DEG C of roastings 1 obtain catalyst, inorganic acid solution when small：
Organic acid soln：The weight ratio for the useless agent residue that platinum content is 0.06-0.1% is 5:2:1；
2) using the catalyst after above-mentioned roasting as carrier, with the solution dipping 8 of the chloride water soluble salt of copper it is small when,
Then it is dried to obtain catalyst cracking combustion-supporting agent.
Inorganic acid is aqueous hydrochloric acid solution.Organic acid soln is formic acid.
The GOLD FROM PLATING SOLUTION category content of the chloride water soluble salt of copper is the 0.1% of catalyst cracking combustion-supporting agent quality.
Roasting is that dried powder is put into graphite crucible to carry out, and the rate of heat addition is 20 DEG C/min.
For graphite crucible inner wall covered with anti-sticking internal layer, dustproof cover is stamped at top, and graphite crucible is in calcined petroleum coke particle
Silicon ash is added in during raw material, is crushed, the quality of silicon ash is the 1% of material quality；The formula of calcined petroleum coke particulate material is：Particle
Granularity is 5~10mm: 30%；Grain graininess is 11~15mm: 70%；By broken calcined petroleum coke particulate material and silicon ash
It adds in kneading pot and stirs, then liquid asphalt is added in kneading pot, continue to stir, pitch is made to infiltrate petroleum coke particles；Using true
Empty oscillatory type pressure forming machine, molding vacuum degree are -0.008MPa, and crucible green compact are put into crucible roasting furnace and are roasted
2 it is small when, it is ensured that crucible green compact are indeformable in roasting process, obtain roasting product crucible；Roasting product crucible is fitted into impregnating autoclave, tank
It inside vacuumizes, adds liquid asphalt, then pressurize into tank, pressure 1MPa goes out after tank up to dipping crucible；Crucible will be impregnated
Graphitization obtains graphite crucible, and coats anti-sticking internal layer in inner wall and add dustproof cover in crucible top, obtains last graphite earthenware
Crucible.
Embodiment 2
A kind of preparation method of catalyst cracking combustion-supporting agent, comprises the following steps：
1) it is raw material to select the useless agent residue that platinum content (mass content) is 0.06-0.1%, and grain size is crushed to pulverizer
Less than 30 μm, the inorganic acid solution for being 3-4 with pH value is mixed, and when stirring 12 is small at normal temperatures, then adds in thereto organic
Acid, when stirring 2 is small, when standing 8 is small, when 110 DEG C of dryings 5 are small, 750 DEG C of roastings 3 obtain catalyst, the inorganic acid when small
Solution：Organic acid soln：The weight ratio for the useless agent residue that platinum content is 0.06-0.1% is 8:4:1；
2) using the catalyst after above-mentioned roasting as carrier, the solution dipping 12 with the nitrate water soluble salt of magnesium is small
When, then it is dried to obtain catalyst cracking combustion-supporting agent.
Inorganic acid is aqueous solution of nitric acid and the mixture of aqueous sulfuric acid.
Organic acid soln is tartaric acid.
The GOLD FROM PLATING SOLUTION category content of the nitrate water soluble salt of magnesium is the 0.1% of catalyst cracking combustion-supporting agent quality.
Roasting is that dried powder is put into graphite crucible to carry out, and the rate of heat addition is 20 DEG C/min.
For graphite crucible inner wall covered with anti-sticking internal layer, dustproof cover is stamped at top, and graphite crucible is in calcined petroleum coke particle
Silicon ash is added in during raw material, is crushed, the quality of silicon ash is the 5% of material quality；The formula of calcined petroleum coke particulate material is：Particle
Granularity is 5~10mm: 40%；Grain graininess is 11~15mm: 60%；By broken calcined petroleum coke particulate material and silicon ash
It adds in kneading pot and stirs, then liquid asphalt is added in kneading pot, continue to stir, pitch is made to infiltrate petroleum coke particles；Using true
Empty oscillatory type pressure forming machine, molding vacuum degree are -0.008MPa, and crucible green compact are put into crucible roasting furnace and are roasted
5 it is small when, it is ensured that crucible green compact are indeformable in roasting process, obtain roasting product crucible；Roasting product crucible is fitted into impregnating autoclave, tank
It inside vacuumizes, adds liquid asphalt, then pressurize into tank, pressure 1MPa goes out after tank up to dipping crucible；Crucible will be impregnated
Graphitization obtains graphite crucible, and coats anti-sticking internal layer in inner wall and add dustproof cover in crucible top, obtains last graphite earthenware
Crucible.
Embodiment 3
A kind of preparation method of catalyst cracking combustion-supporting agent, comprises the following steps：
1) it is raw material to select the useless agent residue that platinum content is 0.06-0.1%, and grain size is crushed to less than 30 μm with pulverizer,
The inorganic acid solution for being 3-4 with pH value is mixed, and when stirring 11 is small at normal temperatures, then adds in organic acid thereto, stirring 1.5
Hour, when standing 7 is small, when 110 DEG C of dryings 3 are small, 550 DEG C of roastings 2 obtain catalyst, inorganic acid solution when small：Organic acid is molten
Liquid：The weight ratio for the useless agent residue that platinum content is 0.06-0.1% is 6:3:1；
2) using the catalyst after above-mentioned roasting as carrier, with the chloride of tin, cobalt nitrate water soluble salt it is molten
When liquid dipping 10 is small, catalyst cracking combustion-supporting agent is then dried to obtain.
Inorganic acid is aqueous sulfuric acid.
Organic acid soln is citric acid.
The chloride of tin, the GOLD FROM PLATING SOLUTION category content of the nitrate water soluble salt of cobalt are catalyst cracking combustion-supporting agent quality
0.1%.
Roasting is that dried powder is put into graphite crucible to carry out, and the rate of heat addition is 20 DEG C/min.
For graphite crucible inner wall covered with anti-sticking internal layer, dustproof cover is stamped at top, and graphite crucible is in calcined petroleum coke particle
Silicon ash is added in during raw material, is crushed, the quality of silicon ash is the 3% of material quality；The formula of calcined petroleum coke particulate material is：Particle
Granularity is 5~10mm: 35%；Grain graininess is 11~15mm: 65%；By broken calcined petroleum coke particulate material and silicon ash
It adds in kneading pot and stirs, then liquid asphalt is added in kneading pot, continue to stir, pitch is made to infiltrate petroleum coke particles；Using true
Empty oscillatory type pressure forming machine, molding vacuum degree are -0.008MPa, and crucible green compact are put into crucible roasting furnace and are roasted
3 it is small when, it is ensured that crucible green compact are indeformable in roasting process, obtain roasting product crucible；Roasting product crucible is fitted into impregnating autoclave, tank
It inside vacuumizes, adds liquid asphalt, then pressurize into tank, pressure 1MPa goes out after tank up to dipping crucible；Crucible will be impregnated
Graphitization obtains graphite crucible, and coats anti-sticking internal layer in inner wall and add dustproof cover in crucible top, obtains last graphite earthenware
Crucible.
Embodiment 4：
A kind of preparation method of catalyst cracking combustion-supporting agent, comprises the following steps：
1) it is raw material to select the useless agent residue that platinum content is 0.06-0.1%, and grain size is crushed to less than 30 μm with pulverizer,
The inorganic acid solution for being 3-4 with pH value is mixed, and when stirring 10 is small at normal temperatures, then adds in organic acid thereto, and stirring 2 is small
When, when standing 7 is small, when 110 DEG C of dryings 4 are small, 600 DEG C of roastings 3 obtain catalyst, inorganic acid solution when small：Organic acid soln：
The weight ratio for the useless agent residue that platinum content is 0.06-0.1% is 7:3:1；
2) using the catalyst after above-mentioned roasting as carrier, soaked with the solution of titanium nitrate, nickel acetate water soluble salt
When stain 9 is small, catalyst cracking combustion-supporting agent is then dried to obtain.
Inorganic acid is aqueous solution of nitric acid.
Organic acid soln is oxalic acid.
Titanium nitrate, the GOLD FROM PLATING SOLUTION category content of nickel acetate water soluble salt are catalyst cracking combustion-supporting agent quality
0.1%.
Roasting is that dried powder is put into graphite crucible to carry out, and the rate of heat addition is 20 DEG C/min.
For graphite crucible inner wall covered with anti-sticking internal layer, dustproof cover is stamped at top, and graphite crucible is in calcined petroleum coke particle
Silicon ash is added in during raw material, is crushed, the quality of silicon ash is the 4% of material quality；The formula of calcined petroleum coke particulate material is：Particle
Granularity is 5~10mm: 32%；Grain graininess is 11~15mm: 68%；By broken calcined petroleum coke particulate material and silicon ash
It adds in kneading pot and stirs, then liquid asphalt is added in kneading pot, continue to stir, pitch is made to infiltrate petroleum coke particles；Using true
Empty oscillatory type pressure forming machine, molding vacuum degree are -0.008MPa, and crucible green compact are put into crucible roasting furnace and are roasted
4 it is small when, it is ensured that crucible green compact are indeformable in roasting process, obtain roasting product crucible；Roasting product crucible is fitted into impregnating autoclave, tank
It inside vacuumizes, adds liquid asphalt, then pressurize into tank, pressure 1MPa goes out after tank up to dipping crucible；Crucible will be impregnated
Graphitization obtains graphite crucible, and coats anti-sticking internal layer in inner wall and add dustproof cover in crucible top, obtains last graphite earthenware
Crucible.
Embodiment 5：
A kind of preparation method of catalyst cracking combustion-supporting agent, comprises the following steps：
1) it is raw material to select the useless agent residue that platinum content is 0.06-0.1%, and grain size is crushed to less than 30 μm with pulverizer,
The inorganic acid solution for being 3-4 with pH value is mixed, and when stirring 12 is small at normal temperatures, then adds in organic acid thereto, and stirring 2 is small
When, when standing 6 is small, when 110 DEG C of dryings 2 are small, 400 DEG C of roastings 2.5 obtain catalyst, inorganic acid solution when small：Organic acid is molten
Liquid：The weight ratio for the useless agent residue that platinum content is 0.06-0.1% is 8:2:1；
2) using the catalyst after above-mentioned roasting as carrier, with the solution dipping 8 of the acetate water soluble salt of nickel it is small when,
Then it is dried to obtain catalyst cracking combustion-supporting agent.
Inorganic acid is aqueous hydrochloric acid solution and the mixture of aqueous solution of nitric acid.
Organic acid soln is formic acid.
The GOLD FROM PLATING SOLUTION category content of the acetate water soluble salt of nickel is the 0.1% of catalyst cracking combustion-supporting agent quality.
Roasting is that dried powder is put into graphite crucible to carry out, and the rate of heat addition is 20 DEG C/min.
For graphite crucible inner wall covered with anti-sticking internal layer, dustproof cover is stamped at top, and graphite crucible is in calcined petroleum coke particle
Silicon ash is added in during raw material, is crushed, the quality of silicon ash is the 3.5% of material quality；The formula of calcined petroleum coke particulate material is：
Grain granularity is 5~10mm: 38%；Grain graininess is 11~15mm: 62%；By broken calcined petroleum coke particulate material and silicon
Ash is added in kneading pot and stirred, then adds in liquid asphalt to kneading pot, continues to stir, and pitch is made to infiltrate petroleum coke particles；Using
Vacuum vibration formula pressure forming machine, molding vacuum degree are -0.008MPa, and crucible green compact are put into crucible roasting furnace and are roasted
Burn 2.5 it is small when, it is ensured that crucible green compact are indeformable in roasting process, obtain roasting product crucible；Roasting product crucible is packed into impregnating autoclave
In, it is vacuumized in tank, adds liquid asphalt, then pressurize into tank, pressure 1MPa goes out after tank up to dipping crucible；It will leaching
Stain crucible graphite obtains graphite crucible, and coats anti-sticking internal layer in inner wall and add dustproof cover in crucible top, obtains last stone
Black crucible.
The above is only presently preferred embodiments of the present invention, not does limitation in any form to the present invention, it is every according to
According to above example is made in the technical spirit of the present invention any simple modification, equivalent variations, each fall within the guarantor of the present invention
Within the scope of shield.
Claims (6)
1. a kind of preparation method of catalyst cracking combustion-supporting agent, which is characterized in that comprise the following steps：
1) it is raw material to select the useless agent residue that platinum content is 0.06-0.1%, is crushed to grain size less than 30 μm with pulverizer, uses pH
It is worth the inorganic acid solution mixing for 3-4, when stirring 10-12 is small at normal temperatures, then adds in organic acid thereto, stir 1-2
Hour, stand 6-8 it is small when, when 110 DEG C of dry 2-5 are small, 350-750 DEG C roast 1-3 it is small when obtain catalyst, described is inorganic
Acid solution：Organic acid soln：The weight ratio for the useless agent residue that platinum content is 0.06-0.1% is (5-8):(2-4):1；
2) using the catalyst after above-mentioned roasting as carrier, with copper, magnesium, tin, titanium, cobalt, the chloride of nickel, nitrate, acetate
In one or several kinds of water soluble salts solution dipping 8-12 it is small when, be then dried to obtain catalyst cracking combustion-supporting agent.
2. the preparation method of catalyst cracking combustion-supporting agent according to claim 1, which is characterized in that the inorganic acid is salt
The mixture of one or more of aqueous acid, aqueous solution of nitric acid and aqueous sulfuric acid.
3. the preparation method of catalyst cracking combustion-supporting agent according to claim 1, which is characterized in that the organic acid soln is
Any one in formic acid, tartaric acid, citric acid or oxalic acid.
4. the preparation method of catalyst cracking combustion-supporting agent according to claim 1, which is characterized in that the copper, magnesium, tin, titanium,
The GOLD FROM PLATING SOLUTION category content of one or several kinds of water soluble salts in cobalt, the chloride of nickel, nitrate, acetate is split for catalysis
Change the 0.1% of combustion adjuvant quality.
5. the preparation method of catalyst cracking combustion-supporting agent according to claim 1, which is characterized in that the roasting is will be dry
Powder after dry is put into graphite crucible and carries out, and the rate of heat addition is 20 DEG C/min.
6. the preparation method of catalyst cracking combustion-supporting agent according to claim 5, which is characterized in that the graphite crucible inner wall
Covered with anti-sticking internal layer, dustproof cover is stamped at top, and graphite crucible is to add in silicon ash in calcined petroleum coke particulate material, is crushed,
The quality of silicon ash is the 1%-5% of material quality；The formula of the calcined petroleum coke particulate material is：Grain graininess for 5~
10mm: 30%~40%；Grain graininess is 11~15mm: 60%~70%；By broken calcined petroleum coke particulate material and
Silicon ash is added in kneading pot and stirred, then adds in liquid asphalt to kneading pot, continues to stir, and pitch is made to infiltrate petroleum coke particles；It adopts
With vacuum vibration formula pressure forming machine, molding vacuum degree is -0.008MPa, and crucible green compact are put into crucible roasting furnace and are carried out
When roasting 2-5 is small, it is ensured that crucible green compact are indeformable in roasting process, obtain roasting product crucible；Roasting product crucible is packed into and is impregnated
It in tank, is vacuumized in tank, adds liquid asphalt, then pressurizeed into tank, pressure 1MPa goes out after tank up to dipping crucible；It will
Crucible graphite is impregnated, obtains graphite crucible, and coats anti-sticking internal layer in inner wall and adds dustproof cover in crucible top, is obtained last
Graphite crucible.
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| CN111099572A (en) * | 2018-10-29 | 2020-05-05 | 中国石油化工股份有限公司 | Carbon oxide-based material, method for oxidizing carbon-based material, and method for catalytically oxidizing cyclic hydrocarbon |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1093734A (en) * | 1993-04-15 | 1994-10-19 | 中国石油化工总公司石油化工科学研究院 | Method for preparation of catalyst cracking combustion-supporting agent |
| CN102249237A (en) * | 2010-12-20 | 2011-11-23 | 龚炳生 | Graphite crucible |
| CN102430402A (en) * | 2011-08-24 | 2012-05-02 | 青岛惠城石化科技有限公司 | Preparation method of catalytic cracking combustion improver |
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2017
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1093734A (en) * | 1993-04-15 | 1994-10-19 | 中国石油化工总公司石油化工科学研究院 | Method for preparation of catalyst cracking combustion-supporting agent |
| CN102249237A (en) * | 2010-12-20 | 2011-11-23 | 龚炳生 | Graphite crucible |
| CN102430402A (en) * | 2011-08-24 | 2012-05-02 | 青岛惠城石化科技有限公司 | Preparation method of catalytic cracking combustion improver |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111099572A (en) * | 2018-10-29 | 2020-05-05 | 中国石油化工股份有限公司 | Carbon oxide-based material, method for oxidizing carbon-based material, and method for catalytically oxidizing cyclic hydrocarbon |
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Application publication date: 20180601 |