CN1411908A - Copper-aluminium-cerium-aluminium composite oxide three-effect FCC adjuvant and its preparation method - Google Patents
Copper-aluminium-cerium-aluminium composite oxide three-effect FCC adjuvant and its preparation method Download PDFInfo
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- CN1411908A CN1411908A CN02129298A CN02129298A CN1411908A CN 1411908 A CN1411908 A CN 1411908A CN 02129298 A CN02129298 A CN 02129298A CN 02129298 A CN02129298 A CN 02129298A CN 1411908 A CN1411908 A CN 1411908A
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- aluminium
- cerium
- composite oxide
- copper
- aqueous solution
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- -1 Copper-aluminium-cerium-aluminium Chemical compound 0.000 title claims abstract description 10
- 239000002131 composite material Substances 0.000 title claims description 22
- 239000002671 adjuvant Substances 0.000 title abstract description 9
- 238000002360 preparation method Methods 0.000 title abstract description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 31
- 238000002485 combustion reaction Methods 0.000 claims abstract description 14
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000003546 flue gas Substances 0.000 claims abstract description 10
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 48
- 239000007864 aqueous solution Substances 0.000 claims description 27
- 229910018516 Al—O Inorganic materials 0.000 claims description 20
- 230000000694 effects Effects 0.000 claims description 16
- 239000012752 auxiliary agent Substances 0.000 claims description 15
- 239000010949 copper Substances 0.000 claims description 15
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 13
- 229910052802 copper Inorganic materials 0.000 claims description 13
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 9
- 239000004411 aluminium Substances 0.000 claims description 8
- 229910052782 aluminium Inorganic materials 0.000 claims description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 8
- 230000001172 regenerating effect Effects 0.000 claims description 7
- WLLURKMCNUGIRG-UHFFFAOYSA-N alumane;cerium Chemical compound [AlH3].[Ce] WLLURKMCNUGIRG-UHFFFAOYSA-N 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 6
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 229910052684 Cerium Inorganic materials 0.000 claims description 5
- 238000005979 thermal decomposition reaction Methods 0.000 claims description 5
- 238000009826 distribution Methods 0.000 claims description 3
- 238000004231 fluid catalytic cracking Methods 0.000 claims description 3
- 150000002500 ions Chemical class 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 238000005504 petroleum refining Methods 0.000 claims description 2
- 229910000329 aluminium sulfate Inorganic materials 0.000 claims 3
- 238000001802 infusion Methods 0.000 claims 2
- 229910000906 Bronze Inorganic materials 0.000 claims 1
- 150000000703 Cerium Chemical class 0.000 claims 1
- 159000000013 aluminium salts Chemical class 0.000 claims 1
- 239000010974 bronze Substances 0.000 claims 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 claims 1
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 claims 1
- 238000000354 decomposition reaction Methods 0.000 claims 1
- 239000002245 particle Substances 0.000 claims 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 abstract description 7
- 229910052697 platinum Inorganic materials 0.000 abstract description 5
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- 239000003054 catalyst Substances 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 238000011069 regeneration method Methods 0.000 description 5
- BWNDQJSNYWWTNG-UHFFFAOYSA-N alumane;cerium Chemical compound [AlH3].[AlH3].[Ce] BWNDQJSNYWWTNG-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 230000008929 regeneration Effects 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 150000001399 aluminium compounds Chemical class 0.000 description 3
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 3
- 239000003610 charcoal Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000006424 Flood reaction Methods 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000010335 hydrothermal treatment Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 229910001593 boehmite Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000011020 pilot scale process Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
Landscapes
- Catalysts (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invented three-efficiency adjuvant is an alumina loaded copper-aluminium-cerium-aluminium compound oxide, when said invented adjuvant is used instead of universal platinum combustion adjuvant, it not only has identical combustion-supporting CO catalytic activity, but also can reduce NOx in the flue gas by above 70% and can increase light oil yield by above one percentage point. Said invention also relates to the preparation method of said adjuvant.
Description
The present invention relates to load copper aluminium and cerium aluminium compound oxide combustion catalyst and preparation method thereof on the aluminium oxide, the FCCU (fluidized catalytic cracker) that relates in particular at oxygen enrichment completing combustion formula regenerative system goes up efficient combustion-supporting and removes CO in the flue gas and reduce NOx discharge capacity in the flue gas and increase the application of yield of light oil.Technical field belongs to Int Cl BO 1J23/70 by International Classification of Patents
Fluid catalytic cracking is the important secondary operations technology of petroleum refining, cause that feedstock oil density is tending towards becoming big owing to mix heavy ends such as refining residual oil, hydrogen-to-carbon ratio diminishes, nitrogenous increasing in the coke, in operational process of craft, in order to recover making full use of of activity level that catalyst uses and reaction one regeneration reasonable thermal balance of two devices and energy, require regenerative system fully to make charcoal and CO rationally burns at dense bed and dilute-phase leanphase fluidized bed, bring some new features also for the distribution of technological operation and product.Wherein important has
1., for reaction-regeneration two device thermal balances, technological operation steadily and are fully recovered energy, and the activity level that recovers the application of FCC catalyst, strict regeneration is made charcoal and the burning of reasonable distribution CO at rare close two-phase bed, reply has produced multiple newly-designed fast bed two-stage regeneration and the front and rear system that makes charcoal, and it is still significant that a certain amount of CO combustion adjuvant of admixture satisfies above-mentioned requirements to oxygen enrichment completing combustion formula regenerative system;
2., NOx concentration improves in the oxygen enrichment completing combustion formula regenerative system flue gas, brings the severe corrosion equipment problem for environmental protection and FCCU, needs exploitation to decompose new technology and the catalyst that reduces NOx content in the flue gas;
3., light oil during product distributes, especially diesel yield is not high, need develop new catalyst promoter when improving technology.
The inventor uses the structural chemistry principle once to develop the burning catalyst for composite oxide CN1058357 and the CN1345629 of two kinds of non-structural intergrities, solved non-noble metal combustion catalyst under FCC process high-temperature water heat condition as the due stabilizing active of CO combustion adjuvant, and have concurrently and reduce the above performance of 50%NOx in the flue gas.The objective of the invention is on above-mentioned CN1345629 invention basis, further improve the composition and the method for making thereof of copper aluminium-cerium-aluminium composite oxide, acquisition is applicable to that the FCCU of oxygen enrichment completing combustion formula regenerative system has higher CO combustion activity, the performance of NOx activity and increase clean or white yield is fallen, more particularly, the present invention is by regulating the composition of imperfect structure I and II
〔Cu
1-3x/2Al
x□
x/2〕O??????????I，
〔Ce
1-yAl
y〕〔O
2-Y/2□
Y/2〕????II，
Room in the representative structure.
X=0.025-0.3 Y=0.025-0.35 expands to 2.5～20% and expand to 1～20% by 2～10% by 5～15% of CN1345629 respectively with the copper aluminium composite oxide of alumina load and cerium-aluminium composite oxide.The catalyst that is developed under identical FCC operating condition with the platinum combustion adjuvant 0.05%Pt/Al that adds identical reserve
2O
3Relatively, have identical CO combustion activity, reduce NOx content more than 70%, improve more than the yield of light oil one percentage point, thereby expanded the scope of application of copper aluminium-cerium-aluminium composite oxide.
The specific embodiments of Preparation of catalysts method of the present invention is: will contain oxide impregnation alumina supporter after cerium, the aluminium compound aqueous solution and citric acid or its aqueous solution according to the mol ratio of metal total ion concentration and citric acid, through thermal decomposition in 100～140 ℃ of oven dry 3～4 hours and 200～300 ℃ of air 2～3 hours, again 600～750 roastings 2～6 hours, preferred 3～4 hours, obtain Ce-Al-O/Al
2O
3According to the mol ratio of metal total ion concentration and citric acid with copper, the aluminium compound aqueous solution and citric acid or its aqueous solution, dipping Ce-Al-O/Al
2O
3, through 100～140 ℃ of oven dry 3～4 hours, thermal decomposition in 200～300 ℃ of air again 500～650 ℃ of roastings 2～6 hours, preferred 3～4 hours, obtained Catalysts Cu-Al-O/Ce-Al-O/Al of the present invention then
2O
3
According to method for preparing catalyst provided by the invention, described aluminium oxide is γ-Al
2O
3Or its precursor boehmite, be shaped as 40～80 μ m microspheroidals, specific area 100～200m
2/ g.Described copper, cerium, aluminium compound are respectively the nitrate of copper, cerium, aluminium.
According to method provided by the invention, the copper aluminium composite oxide mass fraction of load on the aluminium oxide is 2.5～20%, preferred 7～11%, the cerium-aluminium composite oxide mass fraction of load on the aluminium oxide is 1.0～20%, preferred 4～8%, the adjustable range of x is 0.025～0.3 in composite oxides I and the II formula, preferred 0.12～0.15, the adjustable range of Y is 0.025～0.35, preferred 0.12～0.20.
The invention provides the catalyst of method preparation, on the small-sized reaction unit in laboratory, simulating industrial production pilot scale FCC apparatus and commercial scale FCC apparatus, carried out The effects, demonstrate to have concurrently simultaneously and take off CO, fall NO
xContent and three kinds of effects of increase yield of light oil.
Each following embodiment can be further specified the present invention, but does not limit the scope of the invention.
Embodiment 1
Microspheroidal γ-Al
2O
3Screening constitute granularity and account for 8% less than 20 μ m, account for 11% greater than 80 μ m, measure that water absorption rate is 53ml/100g under the room temperature.Get above-mentioned γ-Al
2O
3After 120 ℃ of oven dry, take by weighing 100g and make carrier.Add 2.0mol/L cerous nitrate aqueous solution 13.3ml in the beaker, 2mol/L aluminum nitrate aqueous solution 1.7ml and 3.2g citric acid add deionized water 38ml again, after mixing, with 100g microballoon γ-Al
2O
3Immersion stirs evenly, and places 2 hours.In 120 ℃ of oven dry 4 hours, 280 ℃ of thermal decompositions 2 hours moved into high temperature furnace in 700 ℃ of roastings 3 hours, obtain Ce-Al-O/Al after the cooling then
2O
3-(1)
Put into 3.0mol/L copper nitrate aqueous solution 37ml in another beaker, 2.0mol/L aluminum nitrate aqueous solution 9.0ml and 14g citric acid after mixing, add above-mentioned Ce-Al-O/Al
2O
3-(1) dipping was placed after 2 hours, dried 3 hours in 120 ℃, and 250 ℃ of thermal decompositions 3 hours, dislocation promptly gets alumina load copper-aluminium-cerium-aluminium composite oxide three-effect auxiliary agent 1 in 600 ℃ of roastings of high temperature furnace 2 hours again
#
Embodiment 2
Put into 2.0mol/L cerous nitrate aqueous solution 14.0ml in the beaker, 2.0mol/L aluminum nitrate aqueous solution 1.0ml and citric acid 3g, γ-Al of adding embodiment 1 behind the deionized water 37ml mixing
2O
3100g stirs evenly, and places 2 hours, proceeds to by embodiment 1 experimental procedure and obtains Ce-Al-O/Al
2O
3-(2).
Another beaker is put into 3.0mol/L copper nitrate aqueous solution 40ml, 2.0mol/L aluminum nitrate aqueous solution 4.1ml, and citric acid 13.6g, deionized water 9ml behind the mixing, floods above-mentioned Ce-Al-O/Al
2O
3-(2)., proceed to acquisition alumina load copper-aluminium-cerium-aluminium composite oxide three-effect auxiliary agent 2 by embodiment 1 experimental procedure
#
Embodiment 3
Get 2.0mol/L cerous nitrate aqueous solution 12ml, 2.0mol/L aluminum nitrate aqueous solution 4.2ml, citric acid 3.5g and deionized water 44ml after mixing, immerse γ-Al of water absorption rate 60ml/100g
2O
3Carrier stirs evenly, and places 4 hours, and following steps obtain Ce-Al-O/Al with embodiment 1
2O
3-(3).
Get 3.4mol/L copper nitrate aqueous solution 35.4ml again, 2.0mol/L aluminum nitrate aqueous solution 15.2ml, citric acid 15.0g mixes the back and immerses Ce-Al-O/Al
2O
3.120 ℃ of oven dry in-(3) 3 hours, following steps obtain alumina load copper-aluminium-cerium-aluminium composite oxide three-effect auxiliary agent 3 with embodiment 1
#
Embodiment 4
Get 2.0mol/L cerous nitrate aqueous solution 5.6ml, 2.0mol/L aluminum nitrate aqueous solution 0.4ml, citric acid 1.3g and deionized water 49ml after mixing, immerse γ-Al of water absorption rate 55ml/100g
2O
3Microballoon 100g, following steps obtain Ce-Al-O/Al with embodiment 1
2O
3-(4).
Get 3.4mol/L copper nitrate aqueous solution 17.5ml again, 2.0mol/L aluminum nitrate aqueous solution 7.0ml, citric acid 7.0g and deionized water 29ml mix the back and immerse Ce-Al-O/Al
2O
3-(4).Following steps obtain alumina load copper-aluminium-cerium-aluminium composite oxide three-effect auxiliary agent 4 with embodiment 1
#
Embodiment 5
Get 2.0mol/L cerous nitrate aqueous solution 24.0ml, 2.0mol/L aluminum nitrate aqueous solution 7.2ml, citric acid 6.0g and deionized water 24ml, after mixing, the aluminium oxide 100g that adds with embodiment 4 floods, and following steps obtain Ce-Al-O/Al with embodiment 1
2O
3-(5).
Get 3.6mol/L copper nitrate aqueous solution 47.8ml again, 2.0mol/L aluminum nitrate aqueous solution 6.4ml, citric acid 19g mixes the back and immerses Ce-Al-O/Al
2O
3-(4).Following steps obtain alumina load copper-aluminium-cerium-aluminium composite oxide three-effect auxiliary agent 5 with embodiment 1
#
Embodiment 6
1
#～5
#The triple effect auxiliary agent respectively at 800 ℃, air speed 15000h
-1, 90% (v) steam～10% (v) hydrothermal treatment consists 12 hours under the air.
Take by weighing above-mentioned hydrothermal treatment consists triple effect auxiliary agent sample 1.0g and 60g Al
2O
3Mixing places fixed fluidized-bed reactor, feeds CO
23.2% (V), CO 5.3% (V), O
22.9% (V), all the other are N
2Reaction gas, at air speed 40000h
-1With react under 600 ℃ of conditions, all obtain CO and be converted into 100% result.
Embodiment 7～12
Press addition content 0.3% (m) with triple effect auxiliary agent 1
#, 2
#, 3
#, 4
#, 5
#With after industrial FCC catalyst (LV-23) mixes, carry out the evaluation test of embodiment 7～11 respectively on the small-sized riser FCC apparatus of XTL-5 type respectively, experimental condition sees Table 1, the results are shown in Table 2.For the reaction result with the foregoing description 7～11 contrasts, use 0.05%Pt/Al
2O
3Replace triple effect auxiliary agent of the present invention, under all identical situation of other condition, carry out the evaluation test of embodiment 12.Comparative example 7～11 and 12 experimental results show that alumina load copper aluminium-cerium-aluminium composite oxide of the present invention is under the 3000ppm situation of FCC catalyst, can increase production more than the light oil one percentage point at addition content, reduce NO in the flue gas
xMore than 70%.
Table 1 FCCU operating condition
| Feedstock oil | Grand celebration VGO admixture 25% decompression residuum |
| Reaction temperature, ℃ | ?500 |
| Catalystoil ratio, m/m | ?6.7 |
| The time of staying, sec | ?2.1 |
| Regeneration temperature, ℃ | ?680 |
| Promoter addition | 0.3% of FCC catalyst inventory |
Table 2 triple effect auxiliary agent is to the influence of FCC product
| The embodiment sequence number | The triple effect auxiliary agent | Content in the flue gas, ppm | Yield of light oil, % | |
| ????NO x | ????CO | |||
| 7 | ????1 # | ????67 | ????32 | ?????73.65 |
| 8 | ????2 # | ????80 | ????29 | ?????73.70 |
| 9 | ????3 # | ????72 | ????30 | ?????73.60 |
| 10 | ????4 # | ????60 | ????33 | ?????73.80 |
| 11 | ????5 # | ????86 | ????28 | ?????73.74 |
| 12 | Add 0.05%Pt/Al 2O 3With auxiliary agent contrast of the present invention | ????420 | ????30 | ?????72.10 |
Claims (11)
1, a kind of combustion-supporting CO that uses at FCCU with oxygen enrichment completing combustion regenerative system, remove the triple effect auxiliary agent of NOx and increase clean or white yield, it is characterized in that alumina load contains 0.3～20% bronze medal aluminium composite oxide Cu-Al-O and 0.1～15% cerium-aluminium composite oxide Ce-Al-O.
2, the described triple effect auxiliary agent of claim 1 is characterized in that being applied to having and has the combustion-supporting function that removes in the flue gas NOx among the CO and reduction decomposition flue gas and increase the clean or white yield in petroleum refining fluid catalytic cracking (FCC) process of oxygen enrichment completing combustion regenerative system.
3, the described aluminium oxide of claim 1 is characterized in that γ-Al
2O
3
4, the described copper aluminium composite oxide of claim 1 Cu-Al-O is characterized in that having general formula I:
〔Cu
1-3x/2Al
x□
X/2〕O????????????????I
Room in x=0.025 in the formula～0.30 representative structure
5, the described cerium-aluminium composite oxide Ce-Al-O of claim 1 is characterized in that having general formula I I:
〔Ce
1-yAl
y〕〔O
2-y/2□
y/2〕???????????II
Room in y=0.025 in the formula～0.35 representative structure
6, the described triple effect auxiliary agent of claim 1 is characterized in that adopting infusion process load copper aluminium composite oxide Cu-Al-O and cerium-aluminium composite oxide Ce-Al-O on aluminium oxide.
7, the described infusion process of claim 6, the aqueous solution and citric acid or its aqueous solution that it is characterized in that cupric, the aluminium salt compound aqueous solution or cerium, aluminium salt compound, by the citric acid and the mol ratio of copper aluminium or cerium aluminum metal total ion concentration is 0.3～1.0 to flood after mixing, then through 100～140 ℃ of oven dry, 200～300 ℃ of thermal decompositions, 500～750 ℃ of roastings.
8, the described mantoquita of claim 7 is characterized in that copper nitrate.
9, the described aluminium salt of claim 7 is characterized in that aluminum nitrate.
10, the described cerium salt of claim 7 is characterized in that cerous nitrate.
11, the described γ-Al of claim 3
2O
3, it is characterized in that particle size distribution is at 20～100 μ m.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021292981A CN1166453C (en) | 2002-10-08 | 2002-10-08 | Copper-aluminium-cerium-aluminium composite oxide three-effect FCC adjuvant and its preparation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021292981A CN1166453C (en) | 2002-10-08 | 2002-10-08 | Copper-aluminium-cerium-aluminium composite oxide three-effect FCC adjuvant and its preparation method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1411908A true CN1411908A (en) | 2003-04-23 |
| CN1166453C CN1166453C (en) | 2004-09-15 |
Family
ID=4746182
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB021292981A Expired - Lifetime CN1166453C (en) | 2002-10-08 | 2002-10-08 | Copper-aluminium-cerium-aluminium composite oxide three-effect FCC adjuvant and its preparation method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1166453C (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100443568C (en) * | 2006-02-16 | 2008-12-17 | 刘希尧 | Quadruple effect auxiliary agent in use for FCC technique |
| DE112010003357T5 (en) | 2009-08-21 | 2012-05-31 | Pangang Group Panzhihua Iron & Steel Research Institute Co., Ltd. | Passivation agent for Al-Zn hot dip coated sheet and method of manufacture and use thereof |
| CN105727983A (en) * | 2014-12-11 | 2016-07-06 | 中国石油天然气股份有限公司 | Catalyst promoter for fluid catalytic cracking and preparation method thereof |
| CN106111145A (en) * | 2015-05-04 | 2016-11-16 | 绿欣科技发展（天津）有限公司 | Imperfect structure copper oxide and cerium oxide symbiotic co-existence catalyst and preparation method thereof |
| CN109772347A (en) * | 2019-03-01 | 2019-05-21 | 黄河三角洲京博化工研究院有限公司 | A kind of resistant to sulfur denitration CO catalysis comburant and preparation method thereof |
-
2002
- 2002-10-08 CN CNB021292981A patent/CN1166453C/en not_active Expired - Lifetime
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100443568C (en) * | 2006-02-16 | 2008-12-17 | 刘希尧 | Quadruple effect auxiliary agent in use for FCC technique |
| DE112010003357T5 (en) | 2009-08-21 | 2012-05-31 | Pangang Group Panzhihua Iron & Steel Research Institute Co., Ltd. | Passivation agent for Al-Zn hot dip coated sheet and method of manufacture and use thereof |
| CN105727983A (en) * | 2014-12-11 | 2016-07-06 | 中国石油天然气股份有限公司 | Catalyst promoter for fluid catalytic cracking and preparation method thereof |
| CN105727983B (en) * | 2014-12-11 | 2018-05-04 | 中国石油天然气股份有限公司 | Co-catalyst of fluid catalystic cracking and preparation method thereof |
| CN106111145A (en) * | 2015-05-04 | 2016-11-16 | 绿欣科技发展（天津）有限公司 | Imperfect structure copper oxide and cerium oxide symbiotic co-existence catalyst and preparation method thereof |
| CN106111145B (en) * | 2015-05-04 | 2018-12-25 | 绿欣科技发展（北京）有限公司 | Imperfect structure copper oxide and cerium oxide symbiotic co-existence catalyst and preparation method thereof |
| CN109772347A (en) * | 2019-03-01 | 2019-05-21 | 黄河三角洲京博化工研究院有限公司 | A kind of resistant to sulfur denitration CO catalysis comburant and preparation method thereof |
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