CN1162623A - CO combustion adjuvant and preparation thereof - Google Patents
CO combustion adjuvant and preparation thereof Download PDFInfo
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- CN1162623A CN1162623A CN 96104701 CN96104701A CN1162623A CN 1162623 A CN1162623 A CN 1162623A CN 96104701 CN96104701 CN 96104701 CN 96104701 A CN96104701 A CN 96104701A CN 1162623 A CN1162623 A CN 1162623A
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- active ingredient
- ignition dope
- earth
- described ignition
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- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E20/00—Combustion technologies with mitigation potential
- Y02E20/16—Combined cycle power plant [CCPP], or combined cycle gas turbine [CCGT]
- Y02E20/18—Integrated gasification combined cycle [IGCC], e.g. combined with carbon capture and storage [CCS]
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Abstract
A combustion improver of compound oxide of perovskite-type rare-earth, alkali-earth or transition metal is prepared through mixing the nitrates of La, Sr and Mn (or Mn and Co), preparing aqueous solution, mixing with citric acid evaporating, drying, calcining at 600-800 deg.C for 1-6 hrs to obtain active component, mixing with the filtered cake of a mineral, drying and granulating. The content of active component is 8-15 Wt.% of Al2O3 weight. The combustion improver with good physical and chemical properties can be used in catalytic cracking apparatus.
Description
The present invention relates to perovskite typed CO and help right agent and preparation method thereof, more particularly, the present invention relates to a kind of is active ingredient with perovskite type rare-earth, alkaline earth and compound transition metal oxide, is the combustion-supporting Catalysts and its preparation method of CO of carrier with the alchlor.
At present in the refining of petroleum catalytic cracking process, mainly be divided into two big classes as the combustion-supporting catalyzer of CO, one class is to be the catalyst activity component with precious metals pt, Pd, it is carrier (US 4148751) that the carrier that adopts is generally alumina microsphere, alumina microsphere/silicon oxide etc., as Engelhard Corp (EngelhardCorp.), Praxair Technology, Inc (UOP), Dutch Aksu chemical company (AKZO) of the U.S., domestic Chang Ling refinery, hold up along second branch factory of oil etc.But because of Pt, Pd are precious metal, cost an arm and a leg, people are seeking new catalyst activity component always.The composite oxides that the beginning of the seventies occurred perovskite structure are as combustion supporting catalyst active ingredient (D.B Meadowcroft nature 1970 (226) P
847).Uhligite (TiCaO
3) structure be isometric system, if use molecular formula ABO
3Represent its structure, the A ion is represented the bigger metal ion of radius (as rare earth element, alkaline earth element), and the B ion is represented the less metal ion of radius (as transition metals such as Mn, Cu, Co), and O represents Sauerstoffatom.The A ion is by 12 oxygen coordinations, and the B ion is in octahedra center, and 6 oxygen atom ligands are arranged.General Study thinks that catalytic activity depends primarily on the metallic element of B position, and the metal ion of A position can influence catalytic activity by the modes such as electricity price that influence B bit element.When the ion of A position, B position was partly replaced by other element ion, molecular formula can be represented with following form:
[A
1-xA′
x]·[B
1-yB′
y]·O
3
0≤x in the formula≤1,0≤y≤1, A is a thulium, A ' is an alkali earth metal, B and the different transition metal of B ' representative.
The trans-substitution of this ion phase still can keep stable perovskite crystal structure.Because These characteristics, the combination of A position, the different substitute element in B position, different preparation methods will have in various degree influence to catalytic activity.The reported in literature that perovskite typed CO combustion supporting catalyst is all arranged in recent years both at home and abroad.As external USP4208269, USP 4446011, domestic patent CN 1058357A, CN 1072109A etc.The CN 1058357A report of Peking University, active ingredient is the composite oxides of rare earth metal, alkaline-earth metal and transition metal, support of the catalyst adopts mullite (3Al
2O
32SiO
2-2Al
2O
3SiO
2); The preparation method is fully flooded the nitrate solution that the mullite carrier that makes is put into rare earth, alkaline earth, transition metal, oven dry then, and, make catalyzer at 500-600 ℃ of following roasting 3-5 hour.
The purpose of this invention is to provide a kind of perovskite typed CO ignition dope and preparation method thereof, this ignition dope catalytic activity is good, and preparation technology is simple, can be used for refining catalytic cracking technology.
Catalyst activity component provided by the present invention is with shown in the following general formula:
[La
1-xSr
x][Mn
1-yCo
y]O
3+δ???????(I)
0≤x≤0.4????0≤y≤0.4????0≤δ≤0.4
Active ingredient provided by the invention prepares by the following method: earlier with La
2O
3Make La (NO with nitric acid dissolve
3)
3, and strontium nitrate, manganous nitrate, Xiao Suangu and citric acid be mixed with certain density mixed aqueous solution, wherein La
2O
3: Sr (NO
3)
2: Mn (NO
3)
2: Co (NO
3)
2: citric acid=(1.8～7.0): 1: (2.0～8.4): (0～0.9): (2.5～7) (weight ratio), strength of solution can be 1～1.5M.Then above-mentioned mixed solution is placed on the electric furnace its moisture content of evaporation to make paste, again paste is put into stoving oven, 750 ℃ of following roasting 1-3 hour final active ingredients that obtain black powders in 600 ℃ of left and right sides roastings 1-5 hour.This active ingredient is loose finely powdered, and specific surface is 17-25m
2/ g.Prove that through the x-diffraction its structure is the perovskite structure (see figure 1).Have through preferred perovskite composite oxide active ingredient prescription:
La
0.8Sr
0.2Mn
0.8Co
0.2O
3
La
0.6Sr
0.4MnO
3
LaMn
0.8Co
0.2O
3
LaMnO
3
La
0.8Sr
0.2Mn
0.9Co
0.1O
3
La
0.8Sr
0.2MnO
3
Support of the catalyst provided by the invention is an aluminium sesquioxide, and method for preparing catalyst is with boehmite (Al
2O
3) make colloidal sol, and add the lanthanum nitrate of 1-3%, then by carrier A l
2O
38～15% of weight adds the catalyst activity component and makes the slip that mixes, and again mixed slurry is carried out drying, and is broken into suitable particulate catalyzer.Also mixed slurry can be carried out granulation with spray granulation plant.
CO ignition dope size distribution is as follows:
Median size 60-70 μ
＜40μ??????????????????????8％
40-60μ????????????????????30％
60-80μ????????????????????28.7％
80-110μ???????????????????23.5％
Specific surface 128-175m
2/ g
Active ingredient 8-15%
Abrasion index＜3%
Bulk density 0.9-1.05g/cm
3
Good thermal stability
Catalyzer La
0.8Sr
0.2MnO
3/ Al
2O
3In different air speeds, the activity under the different CO concentration sees Table 1.(oxygen level in the different concns CO gas mixture be under this concentration after the CO perfect combustion superfluous 1-2%).
Experimental data shows that CO concentration is not remarkable to the ignition dope activity influence, under the same air speed, and 50%, 100% invert point base of different CO concentration the same (longitudinal data in the table).Air speed improves, and reaches its temperature of same transformation efficiency and wants corresponding rising 20-50 ℃.No matter active charge capacity is 8% or 13%, and the firing point of CO all is lower than 400 ℃ (furnace temperature), and the temperature of perfect combustion is not higher than 520 ℃ (bed temperatures).(air speed is approximately 4200h according to the operational condition of catalytic cracking unit (FCC) revivifier
-1, 650-700 ℃ of regenerator bed temperature), this
Table 1 catalyzer La
0.8Sr
0.2MnO
3/ Al
2O
3Active
| Active component content % | ?????????????13％?? | ???????????????????8％ | ||||||
| Air speed l/h | ??????40000 | ??????80000 | ??????40000 | ???????80000 | ||||
| Transforming degree % | ?50 | ?100 | ?50 | ?100 | ?50 | ?100 | ?50 | ?100 |
| CO concentration | Invert point (℃) | |||||||
| ???3％ | ?340 (345) | ?380 (387) | ?355 (360) | ?432 (441) | ?350 (360) | ?420 (438) | ||
| ???5％ | ?340 (345) | ?390 (397) | ?355 (355) | ?432 (459) | ?355 (365) | ?410 (430) | ?385 (403) | ?465 (495) |
| ???8％ | ?340 (349) | ?390 (428) | ?360 (374) | ?432 (502) | ?350 (374) | ?410 (446) | ||
| ???11％ | ?335 (345) | ?390 (450) | ?360 (421) | ?400 (511) | ||||
Annotate: the Temperature numerical in the table refers to furnace temperature, and the CO ignition dope that the numerical value in the bracket provides for the bed temperature invention can satisfy the requirement of FCC apparatus fully, and this ignition dope and platinum agent comparison, load 13%La
0.8Sr
0.2MnO
3Ignition dope can realize perfect combustion at 380 ℃ at 340 ℃ of ignitions, its activity has met or exceeded the performance of platinum agent.
Embodiment:
Example 1. takes by weighing 86.58g gram La (NO
3)
36H
2O, 10.58 gram Sr (NO
3)
2, 14.55 gram Co (NO
3)
26H
2O, 71.58 gram 50%Mn (NO
3)
2The aqueous solution.Above-mentioned four kinds of reagent are dissolved in the 200ml water, add 30 gram citric acids after treating to dissolve fully again, on electric furnace, heat, citric acid is dissolved fully, heating is continued in the dissolving back, moisture content is steamed rapidly remove, and then the gained solids is inserted 800 ℃ of following roastings of retort furnace and takes out in 6 hours, obtain black powder and be active ingredient, its chemical constitution is La
0.8Sr
0.2Mn
0.8Co
0.2O
3, be perovskite structure through this black powder of X-diffraction.
Take by weighing the A1 of solid content 38%
2O
3Filter cake 1000 grams add suitable quantity of water and HNO
3, make colloidal sol routinely, add 50ml again and contain La (NO
3)
36H
2O
35.53 the aqueous solution of gram.Make it to mix with colloidal sol, with the above-mentioned black powder of producing 42 grams and colloidal sol thorough mixing evenly, dry back is broken, it is that the screening of 40-120 μ is as sample A that sieve is got particle diameter.This sample contains active ingredient 10%.
Example 2. takes by weighing 64.94 gram La (NO
3)
36H
2O, 21.16 gram Sr (NO
3)
2, and 89.48 gram 50%Mn (NO
3)
2The aqueous solution.These three kinds of reagent are dissolved in the 200ml water, press the method adding 35 gram citric acids that example 1 is introduced, burn till black powder then.Its chemical constitution is La
0.6Sr
0.4MnO
3
Press method and the amount and the Al of example 1
2O
3The mixed sample B that gets of filter cake.
Example 3. takes by weighing 108.23 gram La (NO
3)
36H
2O, 14.55 gram Co (NO
3)
26H
2O, 71.58 gram 50%Mn (NO
3)
2The aqueous solution is dissolved in these three kinds of reagent in the 200ml water, adds 38 gram citric acids and makes it dissolving, burns till pressed powder by the method that example 1 is introduced, and its chemical constitution is LaMn
0.8Co
0.2O
3
Press the method and the amount of example 1, make it and Al
2O
3The filter cake combination drying makes sample C.
Example 4. takes by weighing 108.23 gram La (NO
3)
36H
2O, 89.48 gram 50%Mn (NO
3)
2Be dissolved in the 200ml water, add 42 gram citric acids, burn till pressed powder by the method for example 1, its chemical constitution is LaMnO
3
Press the method and the amount of example 1, make it and Al
2O
3The mixed sample D that gets of filter cake.
With containing CO 5%, O
24%, all the other are N
2Mixed gas estimate the activity of above-mentioned four samples to the CO oxidation, when air speed is 20000h
-1The time, catalytic activity sees Table 2.
Table 2.
| Sample | ??A | ??B | ??C | ??D |
| Firing point ℃ (50% transforms) | ??337 | ??387 | ??347 | ??345 |
| Perfect combustion temperature ℃ (100% transforms) | ??422 | ??485 | ??425 | ??455 |
Example 5. takes by weighing 5.47KgLa
2O
3(99%), be that 18.9 liters in rare nitric acid of 30% is with La with concentration
2O
3Dissolving takes by weighing 1.69KgSr (NO in addition
3)
2, 1.16KgCo (NO
3)
26H
2O and 12.88Kg50%Mn (NO
3)
2Solution is dissolved in these three kinds of industrial chemicals in 25 premium on currency, again with the La (NO of preceding preparation
3)
3Solution mixes mutually, adds the 5.6Kg citric acid then, treat citric acid dissolving after, steam rapidly and remove moisture, with the gained solids 600 ℃ of following roastings 3 hours, 750 ℃ of roastings 3 hours, the acquisition composition is La
0.8Sr
0.2Mn
0.9Co
0.1O
3Active ingredient.
Get 100KgAl
2O
3Filter cake is put into the still of band high speed agitator, and adding suitable quantity of water, to make solid contents be 18～22%, makes slip under high-speed stirring, adds 10 liters of concentration and be 30% La (NO
3)
3The active ingredient 6.18Kg of the aqueous solution and above-mentioned preparation stirs evenly the back and with pump slip is delivered to the nozzle of mist projection granulating top of tower, and the material of ejection is dried to particulate under hot blast, and its granularity is 40～120 μ, median size 74 μ, specific surface 127～75m
2/ g.
Example 6. takes by weighing 27.37g La
2O
3Be dissolved in 95ml concentration and be in rare nitric acid of 30%, take by weighing 8.46g Sr (NO again
3)
2And 71.58g50%Mn (NO
3)
2Solution uses 140ml water with these two kinds of agent dissolves, again with La (NO
3)
3Solution mixes mutually, puts into 300 ℃ of following roastings of retort furnace 3 hours after removing on the electric furnace moisture being steamed, 750 ℃ of roastings 4 hours, and the gained active ingredient is La
0.8Sr
0.2MnO
3
Get 250gAl
2O
3Dry powder adds suitable quantity of water and HNO
3Make colloidal sol, mix with the active ingredient 34.1g of above-mentioned preparation then, drying, fragmentation, after sieving product.
Description of drawings:
Fig. 1 .X-x ray diffration pattern x
Claims (7)
1. a perovskite type rare-earth, alkaline earth, compound transition metal oxide CO ignition dope, its active ingredient is expressed from the next:
[La
1-xSr
x]·[Mn
1-yCo
y]O
3+δ???????(I)
In the formula: 0≤x≤0.4 0≤y≤0.4 0≤δ≤0.4
This active constituent loading is on aluminum oxide micro-sphere or alumina/silica microballoon.
2. the described ignition dope of claim 1 is characterized in that active ingredient is:
La
0.8Sr
0.2Mn
0.8Co
0.2O
3
3. the described ignition dope of claim 1 is characterized in that active ingredient is:
La
0.6Sr
0.4MnO
3
4. the described ignition dope of claim 1 is characterized in that active ingredient is:
La
0.8Sr
0.2Mn
0.9Co
0.1O
3
5. the described ignition dope of claim 1 is characterized in that active ingredient is:
La
0.8Sr
0.2MnO
3
6. the described ignition dope of claim 1 is characterized in that active ingredient is:
LaMn
0.8Co
0.2O
3
7. the preparation method of a perovskite type rare-earth, alkaline earth, compound transition metal oxide CO ignition dope is characterized in that:
1). make the soluble salt mixed aqueous solution of 1.0～1.5M by the required metallic compound of active ingredient of general formula (I), and add (2.5～7) times Sr (NO
3)
2The citric acid of weight mixes;
2). with 1) solution that makes evaporates, drying treatment, and, obtain bulk powdered activated component 600～800 ℃ of following roastings 1～6 hour;
3). select the boehmite filter cake, add 1～3% La (NO
3)
2, and press Al in the softening aluminium stone filter cake
2O
38～15% of amount adds active ingredient, after mixing, carries out drying, granulation.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96104701A CN1065560C (en) | 1996-04-18 | 1996-04-18 | CO combustion adjuvant and preparation thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96104701A CN1065560C (en) | 1996-04-18 | 1996-04-18 | CO combustion adjuvant and preparation thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1162623A true CN1162623A (en) | 1997-10-22 |
| CN1065560C CN1065560C (en) | 2001-05-09 |
Family
ID=5118463
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN96104701A Expired - Fee Related CN1065560C (en) | 1996-04-18 | 1996-04-18 | CO combustion adjuvant and preparation thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1065560C (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1309811C (en) * | 2002-04-10 | 2007-04-11 | 北京三聚环保新材料有限公司 | Carbon mono oxide combustion improver and preparation method and use |
| CN100349654C (en) * | 2004-09-03 | 2007-11-21 | 石油大学(北京) | Nano superfine micro-particle catalyst for carbon particle combustion in diesel engine tail gas and preparing method therefor |
| US20120157301A1 (en) * | 2010-12-17 | 2012-06-21 | GM Global Technology Operations LLC | Method for preparing perovskite oxide-based catalyst particles |
| US8592491B2 (en) | 2003-10-09 | 2013-11-26 | Murata Manufacturing Co., Ltd. | Water-based rare earth metal compound sol, manufacturing method thereof, and method for manufacturing ceramic powder using the same |
| CN107812542A (en) * | 2016-09-14 | 2018-03-20 | 中国石油化工股份有限公司 | A kind of alpha-aluminium oxide carrier and preparation method and application |
| CN113003611A (en) * | 2021-04-07 | 2021-06-22 | 昆明理工大学 | Preparation method and application of lanthanum manganate |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1087111A (en) * | 1993-11-24 | 1994-05-25 | 林科 | Ca-Ti ore type rare-earth compound oxide as combustion assistant for carbon oxide and preparation method thereof |
-
1996
- 1996-04-18 CN CN96104701A patent/CN1065560C/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1309811C (en) * | 2002-04-10 | 2007-04-11 | 北京三聚环保新材料有限公司 | Carbon mono oxide combustion improver and preparation method and use |
| US8592491B2 (en) | 2003-10-09 | 2013-11-26 | Murata Manufacturing Co., Ltd. | Water-based rare earth metal compound sol, manufacturing method thereof, and method for manufacturing ceramic powder using the same |
| CN100349654C (en) * | 2004-09-03 | 2007-11-21 | 石油大学(北京) | Nano superfine micro-particle catalyst for carbon particle combustion in diesel engine tail gas and preparing method therefor |
| US20120157301A1 (en) * | 2010-12-17 | 2012-06-21 | GM Global Technology Operations LLC | Method for preparing perovskite oxide-based catalyst particles |
| CN102527374A (en) * | 2010-12-17 | 2012-07-04 | 通用汽车环球科技运作有限责任公司 | Method for preparing perovskite oxide-based catalyst particles |
| US8318119B2 (en) * | 2010-12-17 | 2012-11-27 | GM Global Technology Operations LLC | Method for preparing perovskite oxide-based catalyst particles |
| CN107812542A (en) * | 2016-09-14 | 2018-03-20 | 中国石油化工股份有限公司 | A kind of alpha-aluminium oxide carrier and preparation method and application |
| CN113003611A (en) * | 2021-04-07 | 2021-06-22 | 昆明理工大学 | Preparation method and application of lanthanum manganate |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1065560C (en) | 2001-05-09 |
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