CN1030285C - Non-noble metal oxide CO combustion adjuvant and its preparing process - Google Patents
Non-noble metal oxide CO combustion adjuvant and its preparing process Download PDFInfo
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- CN1030285C CN1030285C CN 92111005 CN92111005A CN1030285C CN 1030285 C CN1030285 C CN 1030285C CN 92111005 CN92111005 CN 92111005 CN 92111005 A CN92111005 A CN 92111005A CN 1030285 C CN1030285 C CN 1030285C
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Abstract
The present invention provides a non noble metal oxide CO combustion promotor which is characterized in that Cu-M1-M2-O, as an active constituent, is formed by matching CuO with the oxides of metal M1 and/or the oxides of metal M2 and loaded on preroasted microspheric alumina supporters of supported alkaline earth metal or rare earth metal. The active constituent of the catalyst has the following carrying capacity: 5 to 15 wt% of CuO and 0 to 10 wt% of M1 and/or M2O. Indicated by CO combustion tests, the CO combustion promotor has good activity and hydrothermal stability under the conditions that a fixed fluidized bed is regenerated and is at a high air speded, and has equivalent performance as combustion industrial promotors with noble metal Pt or Pd. When the concentration of oxygen is equal to that of CO, the combustion promotor also presents good activity.
Description
The non-noble metal oxide CO combustion catalyst that the present invention relates to, mainly be at being used for catalytic cracking unit required CO combustion adjuvant and preparation method, be non-noble metal oxide (non-perofskite type oxide) CO combustion adjuvant of carrier and preparation method thereof with alumina microsphere or through the alumina microsphere of surface preparation promptly, its international Patent classificating number is B01J20/34.
The CO combustion adjuvant that uses in the present catalytic cracking process, its active component is a VIII family noble metal, Pt and Pd, as US4,148,751; US4,290,878; YS4,093,535 and CN1049301 etc.Since mid-1980s, CO and hydrocarbon combustion reaction there are some non-noble metal oxide of fine catalytic activity, mainly contain two kinds of forms of general oxide of perofskite type oxide and non-Ca-Ti ore type at present, active component as CO and hydrocarbon combustion catalyst, replace or partly replace noble metal, be subjected to increasing attention, to solve the noble metal resource shortage and to reduce production costs.In the purifying vehicle exhaust field, the report of this respect application study is a lot.At the CO combustion adjuvant that uses in the catalytic cracking process, in publication (US4,179,409; 4,325,814,2,647,860 and 3,364,136 and CN 1058357 etc.) the reactive metal element mentioned except that noble metals such as Pt, also have Cr, Cu, Co, Mn, Ni, transition metal such as Fe, they can be oxide or other compounds such as sulfide.Carrier is generally used γ-Al
2O
3, also useful small-bore molecular sieve or other Si-Al compounds.Because activity and stability reasons, have only noble metal CO combustion adjuvant such as Pt to obtain using at present.
The objective of the invention is to replace precious metals pt or the Pd combustion adjuvant that uses in the present FCC technical process with a kind of microballoon non-noble metal oxide (non-perofskite type oxide) CO combustion adjuvant.
The technology of the present invention is by the preliminary treatment to the alumina microsphere carrier, and the effect of active component is more effectively brought into play, and collocation and the co-catalyst of having selected active component effectively.Provide a kind of microballoon non-noble metal oxide of suitable catalytic cracking FCC technical process needs (to annotate: non-calcium attitude ore deposit type oxide) CO combustion adjuvant and its preparation method thus.
This CO combustion adjuvant and preparation method thereof is as follows:
(1) a kind of microballoon non-noble metal oxide CO combustion adjuvant, its active component: Cu-M
1-M
2-O, promptly CuO is equipped with metal M
1Oxide and/or metal M
2Oxide is carried on the alumina microsphere carrier through preroast or preload alkaline-earth metal or rare earth metal, active component except that CuO, M
1Refer to transition metal, Co preferably, Mn, M
2Be rare earth metal, Ce preferably;
(2) described catalyst activity component load capacity: CuO is 5-15wt%, 7-10wt% preferably, M
1-O and/or M
2-O is 0-10wt%, preferably 1-5wt%.
(3) described catalyst carrier refers to microballoon (size distribution: less than 40 μ, 0-3%; 40-80 μ,＞85.0%; Greater than 80 μ, 0-12.0%; Bulk specific weight 0.97-1.1 grams per milliliter)
1. aluminium oxide (Al
2O
3Content 〉=98% is through 700-900 ℃ of preroast;
Or 2. aluminium oxide (AL
2O
3Content 〉=98%, in advance through alkaline-earth metal, preferably the nitrate solution of Mg or Ba floods, 120 ℃ of dryings, 800-900 ℃ of roasting, last metal oxide content is the 1-5wt% of carrier, preferably 1-3wt%;
Or 3. aluminium oxide (Al
2O content 〉=98%), in advance through rare earth metal, preferably the nitrate aqueous solution of Ce floods, 120 ℃ of dryings, and 500-700 ℃ of roasting, last metal oxide content is the 1-5wt% of carrier, preferably 1-3wt%;
Or 4. boehmite, 1. microballoon (size distribution is the same, bulk specific weight 0.97-1.0 grams per milliliter) through above-mentioned or 2., 3. handle;
(4) described Preparation of catalysts method is to adopt equal-volume double-steeping and different temperatures two-stage calcination technology, that is:
1. by the weight ratio of catalyst activity composition (1) requirement, take by weighing the nitrate of required metal, be mixed, be dissolved in the distilled water of requirement, the solution that is made into is divided into A, B two equal portions.
2. take by weighing a kind of in a certain amount of above-mentioned carrier, immerse in the A mixed liquor, immerse again after the drying in the B solution,
3. then be warming up to 650-700 ℃ of roasting 2-3 hour at 500 ℃ of roasting 1-2 hours through dried sample again;
The microballoon combustion adjuvant of making, size distribution: less than 40 μ, 0.0-10.0%; 40-80 μ, 〉=86.0%; Greater than 80 μ, 0.0-4.0%, bulk specific weight 1.1-1.2 grams per milliliter.
The CO combustion adjuvant of the present invention's preparation reaches the fixed bed high-speed under fixed fluidized bed spent catalytic cracking agent regeneration condition, (1.2-1.25) * 10
6The time
-1Under the condition, CO combustion test result shows that it has good active and hydrothermal stability, and is suitable with industrial precious metals pt or Pd combustion adjuvant.Catalyst and active and hydrothermal stability thereof see Table 1,3 and accompanying drawing 1.Oxygen content equates under the condition with CO in anti-gas, and this combustion adjuvant also shows good activity, and is as shown in table 2.(table 1, continuous table 1, table 2, table 3 are seen the literary composition back)
Embodiment 1
(1) with an amount of alumina microsphere (Shandong Aluminum Plant's industrial products) 750 ℃ of following constant temperature calcining 3 hours in Muffle furnace.Take by weighing this aluminium oxide 10 grams;
(2) take by weighing copper nitrate Cu(NO
3)
23H
2O(Beijing Chemical Plant product AR) 3.02 grams are dissolved in the distilled water, make the copper nitrate solution of 18ml, and are divided into isopyknic two parts of solution, and the volume of every part of solution equals the pore volume of above-mentioned (1) step alumina support;
(3) above-mentioned alumina support is immersed in the above-mentioned a solution, wait to stir 10 minutes after, placed drier 4 hours.After the taking-up, immerse once more in (2) another part copper nitrate solution in step, stir after 10 minutes, 120 ℃ following dry 4 hours;
(4) dried sample was placed 500 ℃ of following constant temperature calcinings of Muffle furnace 1.5 hours, then be warming up to 700 ℃ of following constant temperature calcinings again 2.5 hours.The alumina support Supported CuO that promptly gets 750 ℃ of roastings is the combustion adjuvant A of 9.0wt%.
Embodiment 2
(1) gets in right amount and placed 900 ℃ of following constant temperature calcinings of Muffle furnace 3 hours with the aluminium oxide in (embodiment 1) identical source.Take by weighing this alumina support 10 grams;
(2), (3), (4) go on foot identical with (embodiment 1).Make and contain the combustion adjuvant B that CuO is 9.0wt%.
Embodiment 3
(1) identical with (embodiment 2) (1).Take by weighing this alumina support 15 grams;
(2) take by weighing copper nitrate Cu(NO
3)
23H
2O: 4.53 gram and cobalt nitrate Co(NO
3)
26H
2The O(Beijing Chemical Plant produces AR): 0.588 gram, be dissolved in after the mixing in the distilled water, make the 28ml nitrate mixed solution, and be divided into isopyknic two parts;
(3) carrier is immersed in the above-mentioned a nitrate mixed solution, wait to stir 10 minutes after, 120 ℃ dry 4 hours down.After the taking-up, immerse once more in (2) another part mixed solution in step, stir after 10 minutes, following dry 4 hours at 120 ℃ once more;
(4) dried sample was placed 500 ℃ of following constant temperature calcinings of Muffle furnace 1.5 hours, then be warming up to 700 ℃ of following constant temperature calcinings again 2.5 hours, get promptly that to contain CuO be that 8.9wt% and CoO are the combustion adjuvant C of 0.9wt%.
Embodiment 4
(1) identical with (embodiment 3) (1);
(2) take by weighing copper nitrate Cu(NO
3)
23H
2O: 4.53 gram and cobalt nitrate Co(NO
3)
26H
2O: be dissolved in the distilled water after 2.91 grams mix, make the 28ml nitrate mixed solution, and be divided into isopyknic two parts;
(3), (4) are identical with (embodiment 3).Obtain containing the combustion adjuvant D of CuO8.6wt% and CoO4.3wt%.
Embodiment 5
(1) identical with (embodiment 3) (1);
(2) take by weighing copper nitrate Cu(NO
3)
23H
2O: 4.53 gram and cerous nitrate Ce(NO
3)
36H
2(Beijing Chemical Plant's product AR): be dissolved in the distilled water after 1.894 grams mix, make the 28ml nitrate mixed solution, and be divided into isopyknic two parts;
(3), (4) step is identical with (embodiment 3).Obtain containing CuO8.6wt% and 4.4wt%CeO
2Combustion adjuvant E.
Embodiment 6
(1) takes by weighing alumina microsphere carrier 15 grams;
(2) weighing magnesium nitrate Mg(NO
3)
26H
2O(Beijing Chemical Plant product AR) 1.442 grams are dissolved in the distilled water, make the solution of 28ml;
(3) above-mentioned alumina support is immersed in the magnesium nitrate solution, stir after 30 minutes, 120 ℃ following dry 4 hours;
(4) dried sample was placed 500 ℃ of following constant temperature calcinings of Muffle furnace 1 hour, then be warming up to 900 ℃ of following constant temperature calcinings 4 hours.Promptly get the alumina microsphere carrier of 1.5wt%MgO coating.And the alumina support 15 of getting this MgO coating restrains;
(5), (6), (7) go on foot identical with (3), (4) of (embodiment 5).Obtain the alumina support load 10wt%CuO and the 5wt%CeO of MgO coating
2Combustion adjuvant F.
Embodiment 7
Identical with embodiment 6, employing be 1.5wt%BaO
2The alumina support of coating.Obtain combustion adjuvant G thus.
Embodiment 8
(1) gets alumina microsphere carrier 15 grams.
(2) take by weighing cerous nitrate Ce(NO
3)
36H
2The O1.893 gram is dissolved in the distilled water, is mixed with the cerium nitrate solution of 28ml;
(3) above-mentioned alumina support is immersed in the above-mentioned solution, stirs after 30 minutes, 120 ℃ dry 4 hours down, 500 ℃ of following constant temperature calcinings 2 hours in Muffle furnace were warming up to 650 ℃ of following constant temperature calcinings 8 hours more then.Promptly get 5wt%CeO
2The alumina support of coating;
(4) (5), (6) are consistent with (embodiment 3).Thereby obtain 5wt%CeO
2The alumina microsphere carrier of coating is loaded with the combustion adjuvant H of CuO10.0wt% and CoO1.4wt%.
Embodiment 9
(1) gets microballoon boehmite (Shandong Aluminum Plant's production) 15 grams.
(2) take by weighing copper nitrate Cu(NO
3)
23H
2O: 5.345 grams,
Cerous nitrate Ce(NO
3)
36H
2The O:2.233 gram,
50% manganese nitrate Mn(NO
3)
2Solution (analyze pure, Beijing chemical reagent three factories): 3.637 milliliters, above-mentioned three kinds of nitrate are mixed the back adding distil water, make the 28ml nitrate mixed solution, and be divided into isopyknic two parts.
(3), (4) step goes on foot consistent with (embodiment 1) (3), (4).What make the load of microballoon boehmite contains CuO10.0wt%, CeO
25.0wt% and MnO
2The combustion adjuvant I of 5.0wt%.
Embodiment 10
In the small stationary bed apparatus, estimate CO oxidation activity and the hydrothermal stability of combustion adjuvant A-I.CO oxidation assessing terms: CO combustion adjuvant and diluent Al
2O
3(22 times to the CO combustion adjuvant) fully mixing is placed in the fixed bed reactors, and reaction gas is formed: CO8.0vol%, O
27.6vol%, all the other are N
2, total air speed is (1.2-1.25) * 10
6The time
-1
Activity after the CO combustion adjuvant is aging refers to that combustion adjuvant is the N of 355.4mmHg at 800 ℃, steam partial pressure
2Handle the activity after 8 hours in the air-flow.
Activity and the hydrothermal stability of CO combustion adjuvant A-I under above-mentioned assessing terms is as shown in table 1, shows that prepared combustion adjuvant has good activity and hydrothermal stability, and be suitable with industrial Pt combustion adjuvant.
When oxygen concentration in the reaction gas was identical with CO concentration, the CO oxidation activity of combustion adjuvant F and the relation of reaction temperature saw Table 2, and data show that when oxygen content was not superfluous in the reaction system, combustion adjuvant still kept good activity.(table 2 is seen the literary composition back)
Accompanying drawing 1 is the activity of combustion-supporting F under different air speeds, and to represent air speed respectively be 1.91 * 10 for a, b, c and d among the figure
5, 2.87 * 10
5, 5.42 * 10
5With 1.25 * 10
6The time
-1, T is a reaction temperature, X is the CO conversion ratio.Curve reflects that combustion adjuvant has activity preferably under high-speed among the figure.
Embodiment 11
Estimate oxidation activity and the stability of combustion adjuvant A-I at small-sized fixed fluidized bed device. The activity assessment condition: catalytic cracking catalyst 30 grams (phosphorus content is 1.0-1.1wt%) to be regenerated add 300 milligrams of CO combustion adjuvants, 600 ℃ of reaction temperatures, 1000 vertical liter/mins of air mass flows, 3 minutes reaction time. The oxidation activity of CO combustion adjuvant represents:
R wherein0CO in the flue gas during for no combustion adjuvant2/ CO ratio, R are the CO when combustion adjuvant is arranged2/ CO ratio.
Evaluation result sees Table 3
Can see that base metal CO combustion adjuvant of the present invention has good CO combustion-supporting effect equally when spent catalytic cracking agent fluidisation is regenerated.
Active and the hydrothermal stability (fixed bed reactors) of table 1 CO combustion adjuvant
Active (CO conversion ratio %)
Combustion adjuvant
450℃ 500℃ 550℃ 600℃ 650℃
It is fresh aging fresh aging fresh aging fresh aging after the numbering fresh sample is aging
A 53.3 41.9 78.8 74.0 95.1 92.0 99.5 99.2 100.0 100.0
B 63.7 49.1 83.1 78.0 95.6 93.4 99.4 99.1 100.0 100.0
Continued 1
C 69.6 58.1 90.7 82.2 98.3 95.1 100 99.5 - 100.0
D 72.4 37.9 91.7 62.8 99.1 87.3 100 97.8 - 100.0
E 87.5 69.9 97.1 89.2 99.2 97.2 100 99.9 - 100.0
F 81.8 61.1 93.7 80.1 97.3 91.9 99.2 97.6 99.7 99.7
G 85.6 55.1 93.2 79.6 97.5 87.6 99.4 95.7 100.0 98.4
H 56.0 43.1 77.2 69.0 90.4 87.7 96.2 90.6 98.2 96.2
Industry
16.9 - 70.1 - 99.9 - 100.0 - - -
The Pt agent
Table 2: combustion adjuvant F is at different CO/O
CO conversion ratio under the mol ratio
Reaction temperature (℃) reaction condition CO/O mol ratio
0.55 1.00
300 - 49.7
350 - 75.9
400 92.4 92.0
450 98.1 98.1
500 100.0 99.9
Table 3 fluid catalystic cracking spent agent regeneration CO combustion adjuvant is active and stable
Combustion adjuvant numbering A B C D E F H I
Fresh combustion adjuvant 84.9 89.3 89.6 89.3 89.4 91.9 93.2 89.1
Live
The property
Combustion adjuvant 84.5 83.9 86.3 85.9 82.2 88.4 89.7 82.7 after aging
Claims (6)
1, a kind of non-noble metal oxide CO combustion adjuvant, it is characterized in that active constituent is the oxide that cupric oxide is equipped with cobalt, manganese and/or cerium, be carried on through preroast or on alkaline-earth metal or rare-earth metal modified alumina microsphere carrier, the combustion adjuvant activity component load quantity: cupric oxide is 5-15wt%, and the oxide of cobalt, manganese and/or cerium is 0-10wt%.
2, combustion adjuvant according to claim 1 is characterized in that the combustion adjuvant activity component load quantity is that cupric oxide is 7-10wt%, and cobalt, manganese and/or cerium oxide are 1-5wt%.
3, combustion adjuvant according to claim 1, it is characterized in that carrier refers to alumina microsphere, its size distribution, less than 40 μ, 0-3%, 40-80 μ, 〉=85%, greater than 80 μ, 0-12%, bulk specific weight 0.97-1.1 grams per milliliter passes through 700-900 ℃ of preroast or in advance through the modification of alkaline earth oxide or rare earth metal oxidation, the amount of modified oxide is the 1-5wt% of aluminium oxide.
4, modified support according to claim 1 is characterized in that the used alkaline earth oxide of modification is magnesium, ba oxide.Rare-earth oxide is the oxide of cerium.
5, modified support according to claim 4, the amount that it is characterized in that alkaline earth or rare-earth oxide is the 1-3wt% of aluminium oxide.
6, a kind of method for preparing the described combustion adjuvant of claim 1, it is characterized in that adopting equal-volume double-steeping and different temperatures two-stage calcination technology, that is: press the weight ratio of the active composition requirement of combustion adjuvant, take by weighing the nitrate of required metal, be mixed, be dissolved in the distilled water, the solution that is made into is divided into A, B two equal portions, take by weighing a kind of in the carrier, immerse in the A mixed liquor, immerse after the drying in the B solution again, sample after drying was at 500 ℃ of roasting 1-2 hours, then heated up the microballoon combustion adjuvant of making 650-700 ℃ of roasting 2-3 hour; Less than 40 μ, 0.0-10.0%; 40-80 μ, 〉=86.0%, greater than 80 μ, 0.0-4.0%, bulk specific weight 1.1-1.2 grams per milliliter.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 92111005 CN1030285C (en) | 1992-09-26 | 1992-09-26 | Non-noble metal oxide CO combustion adjuvant and its preparing process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 92111005 CN1030285C (en) | 1992-09-26 | 1992-09-26 | Non-noble metal oxide CO combustion adjuvant and its preparing process |
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| Publication Number | Publication Date |
|---|---|
| CN1072109A CN1072109A (en) | 1993-05-19 |
| CN1030285C true CN1030285C (en) | 1995-11-22 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 92111005 Expired - Fee Related CN1030285C (en) | 1992-09-26 | 1992-09-26 | Non-noble metal oxide CO combustion adjuvant and its preparing process |
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Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1151878C (en) | 2000-09-29 | 2004-06-02 | 北京大学 | Copper aluminium-cerium aluminium compound oxide combustion catalyst, its preparation and use |
| 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 |
| CN1333044C (en) | 2003-09-28 | 2007-08-22 | 中国石油化工股份有限公司 | Method for cracking hydrocarbon oil |
| US7347930B2 (en) | 2003-10-16 | 2008-03-25 | China Petroleum & Chemical Corporation | Process for cracking hydrocarbon oils |
| CN101143321B (en) * | 2006-09-15 | 2011-05-25 | 中国人民解放军63971部队 | Low temperature co oxidation non-noble metal catalyst |
| US10792647B2 (en) * | 2009-04-21 | 2020-10-06 | Johnson Matthey Public Limited Company | Base metal catalysts for the oxidation of carbon monoxide and volatile organic compounds |
| CN102059127B (en) * | 2010-11-09 | 2012-11-21 | 华东理工大学 | Catalyst for CO normal temperature catalytic oxidation and preparation method thereof |
| CN117720954B (en) * | 2024-01-25 | 2024-05-28 | 青岛康洁聚能科技有限公司 | Non-noble metal carbon monoxide combustion improver and preparation method thereof |
-
1992
- 1992-09-26 CN CN 92111005 patent/CN1030285C/en not_active Expired - Fee Related
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| CN1072109A (en) | 1993-05-19 |
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